U.S. patent application number 11/645968 was filed with the patent office on 2007-06-21 for reduced byproduct polyamine-epihalohydrin resins.
Invention is credited to Anthony J. Allen, Ronald Busink, Francis J. JR. Carlin, Huai Nan Cheng, Mark T. Crisp, Alfred Jacques Haandrikman, Michaela Hofbauer, John James Hoglen, Harold Jabloner, John Arthur Lapre, Richard James Riehle.
Application Number | 20070137821 11/645968 |
Document ID | / |
Family ID | 26987160 |
Filed Date | 2007-06-21 |
United States Patent
Application |
20070137821 |
Kind Code |
A1 |
Riehle; Richard James ; et
al. |
June 21, 2007 |
Reduced byproduct polyamine-epihalohydrin resins
Abstract
Processes for rendering a polyamine-epihalohydrin resin storage
stable, including processes that prepare a storage stable resin
and/or processes that treat resins. A composition containing a
polyamine-epihalohydrin resin which includes CPD-forming species
can be treated with at least one agent under conditions to at least
one of inhibit, reduce and remove the CPD-forming species to obtain
a reduced CPD-forming resin so that a composition containing the
reduced CPD-forming polyamine-epihalohydrin resin when stored for 2
weeks at 50.degree. C., and a pH of about 2.5 to 3.5 contains less
than about 250 ppm dry basis of CPD. The invention is also directed
to a gelation storage stable reduced CPD-forming resin so that a
composition containing the reduced CPD-forming
polyamine-epihalohydrin resin, when stored at pH 1 for 24 hours at
50.degree. C. and measured at 24 hours, produces less than about
1000 ppm dry basis of CPD. A paper product containing the storage
stable polyaminopolyamide-epihalohydrin resin, when corrected for
adding at about a 1 wt % addition level of the
polyaminopolyamide-epihalohydrin resin, contains less than about
250 ppb of CPD. Moreover, a resin can be prepared starting from a
prepolymer having a low acid number or low concentration of acid
end groups. The invention is also directed to papers containing the
resins.
Inventors: |
Riehle; Richard James;
(Wilmington, DE) ; Allen; Anthony J.; (Wilmington,
DE) ; Hofbauer; Michaela; (Roosendaal, NL) ;
Haandrikman; Alfred Jacques; (Amersfoort, NL) ;
Busink; Ronald; (Bennekom, NL) ; Crisp; Mark T.;
(Amersfoort, NL) ; Hoglen; John James; (Newark,
DE) ; Cheng; Huai Nan; (Wilmington, DE) ;
Carlin; Francis J. JR.; (Newark, DE) ; Lapre; John
Arthur; (Ede, NL) ; Jabloner; Harold;
(Landenburg, PA) |
Correspondence
Address: |
HERCULES INCORPORATED;HERCULES PLAZA
1313 NORTH MARKET STREET
WILMINGTON
DE
19894-0001
US
|
Family ID: |
26987160 |
Appl. No.: |
11/645968 |
Filed: |
December 27, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10438117 |
May 14, 2003 |
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11645968 |
Dec 27, 2006 |
|
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10396155 |
Mar 25, 2003 |
7175740 |
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10438117 |
May 14, 2003 |
|
|
|
09592681 |
Jun 12, 2000 |
6554961 |
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10396155 |
Mar 25, 2003 |
|
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09363224 |
Jul 30, 1999 |
|
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09592681 |
Jun 12, 2000 |
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09330200 |
Jun 11, 1999 |
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09363224 |
Jul 30, 1999 |
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Current U.S.
Class: |
162/164.6 ;
528/297 |
Current CPC
Class: |
D21H 27/10 20130101;
C08G 73/0286 20130101; C08G 73/022 20130101; D21H 17/56 20130101;
D21H 17/55 20130101; D21H 27/08 20130101 |
Class at
Publication: |
162/164.6 ;
528/297 |
International
Class: |
D21H 19/30 20060101
D21H019/30; C08G 69/48 20060101 C08G069/48 |
Claims
1. A storage stable polyaminopolyamide-epihalohydrin resin, said
resin when stored as an aqueous composition containing the resin,
and when stored at pH 1 for 24 hours at 50.degree. C. and measured
at 24 hours, produces less than about 1000 ppm dry basis of CPD;
said resin being produced from a reaction of a) polyaminoamide
prepolymer having an acid functionality less than about 0.5
milliequivalents/dry gram of prepolymer and b) epihalohydrin, said
prepolymer being end-capped prior to reaction with epihalohydrin by
reaction with an endcapping agent.
2. The resin of claim 1 wherein the endcapping agent is selected
from (i) a monofunctional amine, (ii) a monofunctional carboxlic
acid, or (iii) a monofunctional carboxylic ester.
3. The resin of claim 1 wherein the endcapping agent is a
monofunctional amine selected from the class consisting of
monofunctional primary amines and monufunctional secondary
amines.
4. The resin of claim 1 wherein the endcapping agent is a
monofunctional amine selected from butylamine, monoethanolamine,
cyclohexylamine, 2-methylcyclohexylamine, 3 methylcyclohexylamine,
4-methylcyclohexylamine, benzylamine, isopropanolamine (i.e.,
monoisopropanolamine), mono-sec-butanolamine,
2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane,
tetrahydrofurfurylamine, furfurylamine, 3-amino-1,2-propanediol,
1-amino-1-deoxy-D-sorbitol, 2-amino 2-ethyl-1,3-propanediol, less
preferred, diethylamine, dibutylamine, diethanolamine,
di-n-propylamine, diisopropanolamine, di-sec-butanolamine, and
N-methylbenzylamine.
5. The resin of claim 1 wherein the endcapping agent is a
monofunctional carboxylic acid or ester thereof selected from
benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, acetic
acid, phenylacetic acid, propionic acid, butyric acid, valeric
acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, oleic
acid, ortho-toluic acid, meta-toluic acid, para-toluic acid,
ortho-methoxybenzoic acid, meta-methoxybenzoic acid,
para-methoxybenzoic acid, methyl acetate, ethyl acetate, methyl
benzoate, ethyl benzoate, methyl propionate, ethyl propionate,
methyl butyrate, ethyl butyrate, methyl phenyl acetate, and ethyl
phenyl acetate.
6. Paper or paper pulp treated with the resin of claim 1.
7. Paper or paper treated with the resin of claim 2.
8. Paper or paper treated with the resin of claim 3.
9. Paper or paper treated with the resin of claim 4.
10. Paper or paper treated with the resin of claim 5.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of application Ser. No.
10/438,117 filed May 14, 2003, which is a Continuation of
application Ser. No. 10/396,155, filed Mar. 25, 2003, which is a
Continuation of application Ser. No. 09/592,681, filed Jun. 12,
2000, (now U.S. Pat. No. 6,554,961B1), which is a
Continuation-In-Part of application Ser. No. 09/363,224, filed Jul.
30, 1999, (now abandoned), which is a Continuation-in-Part of
application Ser. No. 09/330,200, filed Jun. 11, 1999 (now
abandoned). The disclosures of each of these applications are
incorporated by reference herein in their entireties.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to polyamine-epihalohydrin
resin products, particularly polyamine-epihalohydrin resin products
which can be stored with at least reduced formation of halogen
containing residuals, such as 3-chloropropanediol (CPD). Moreover,
the present invention relates to formation of
polyamine-epihalohydrin resins having at least reduced formation of
halogen containing residuals, and to various uses of the resins,
such as wet strength agents. More specifically, the present
invention relates to polyamine-epihalohydrin resin products which
have reduced levels of formation of CPD upon storage, such as paper
products. Moreover, the present invention relates to the production
of polyamine-epihalohydrin resins prepared from polyaminoamide
prepolymers containing low levels of acid functionalities, and to
resins formed thereby.
[0004] 2. Discussion of Background Information
[0005] Polyamine-epihalohydrin resins, such as
polyaminopolyamide-epihalohydrin resins are cationic thermosetting
materials used to increase the wet strength of papers. Often these
materials contain large quantities of epihalohydrin hydrolysis
products. For example, commercial
polyaminopolyamide-epichlorohydrin resins typically contain 1-10 wt
% (dry basis) of the epichlorohydrin (epi) by-products,
1,3-dichloropropanol (1,3-DCP), 2,3-dichloropropanol (2,3-DCP) and
3-chloropropanediol (CPD). Production of wet-strength resins with
reduced levels of epi by-products has been the subject of much
investigation. Environmental pressures to produce wet-strength
resins with lower levels of absorbable organic halogen (AOX)
species have been increasing. "AOX" refers to the adsorbable
organic halogen content of the wet strength resin which can be
determined by means of adsorption onto carbon. AOX includes
epichlorohydrin (epi) and epi by-products (1,3-dichloropropanol,
2,3-dichloropropanol and 3-chloropropanediol) as well as organic
halogen bound to the polymer backbone.
[0006] Commercial papermaking operations typically utilize paper
wet strengthening formulations which comprise cationic
thermosetting polymers. In the papermaking process, waste material
is frequently disposed of in landfills, etc. It is desirable to
reduce the organohalogen content of such wastes to as low a level
as possible. This waste is a substantially solid mass of material
which is exposed to the environment. The exposure of the waste to
the environment results in the selection of microorganisms which
feed on the components in the waste. It is known that there are
microorganisms which feed on the organohalogen compounds in the
solid waste.
[0007] In the papermaking process the epichlorohydrin hydrolysis
products are released into the environment in the water used to
make paper, or into the air by evaporation during the paper drying
step, or into the paper itself or a combination of these events. It
is desirable to reduce and control these emissions into the
environment to as low a level as possible. Reduced levels of CPD
are especially desirable in applications where food is the end
use.
[0008] Several ways of reducing the quantities of epihalohydrin
hydrolysis products have been devised. Reduction in the quantity of
epihalohydrin used in the synthetic step is an alternative taught
in U.S. Pat. No. 5,171,795. A longer reaction time results. Control
over the manufacturing process is taught in U.S. Pat. No. 5,017,642
to yield compositions of reduced concentration of hydrolysis
products. These patents are incorporated by reference in their
entireties.
[0009] Post-synthesis treatments are also taught. U.S. Pat. No.
5,256,727, which is incorporated by reference in its entirety,
teaches that reacting the epihalohydrin and its hydrolysis products
with dibasic phosphate salts or alkanolamines in equimolar
proportions converts the chlorinated organic compounds into
non-chlorinated species. To do this it is necessary to conduct a
second reaction step for at least 3 hours, which adds significantly
to costs and generates quantities of unwanted organic materials in
the wet strength composition. In compositions containing large
amounts of epihalohydrin and epihalohydrin hydrolysis products
(e.g., about 1-6% by weight of the composition), the amount of
organic material formed is likewise present in undesirably large
amounts.
[0010] U.S. Pat. No. 5,516,885 and WO 92/22601, which are
incorporated by reference in their entireties, disclose that
halogenated by-products can be removed from products containing
high levels of halogenated by-products as well as low levels of
halogenated by-products by the use of ion exchange resins. However,
it is clear from the data presented that there are significant
yield losses in wet strength composition and a reduction in wet
strength effectiveness.
[0011] It is known that nitrogen-free organohalogen-containing
compounds can be converted to a relatively harmless substance. For
example, 1,3-dichloro-2-propanol, 3-chloro-1,2-propanediol (also
known as 3-chloropropanediol, 3-monochloropropanediol,
monochloropropanediol, chloropropanediol, CPD, 3-CPD, MCPD and
3-MCPD ) and epichlorohydrin have been treated with alkali to
produce glycerol.
[0012] The conversion of nitrogen-free organohalogen compounds with
microorganisms containing a dehalogenase is also known. For
example, C. E. Castro, et al. ("Biological Cleavage of
Carbon-Halogen Bonds Metabolism of 3-Bromopropanol by Pseudomonas
sp.", Biochimica et Biophysica Acta, 100, 384-392, 1965), which is
incorporated by reference in its entirety, describes the use of
Pseudomonas sp. isolated from soil that metabolizes 3-bromopropanol
in sequence to 3-bromopropionic acid, 3-hydroxypropionic acid and
CO.sub.2.
[0013] Various U.S. patents also describe the use of microorganisms
for dehalogenating halohydrins, e.g., U.S. Pat. Nos. 4,452,894;
4,477,570; and 4,493,895. Each of these patents is hereby
incorporated by reference as though set forth in full herein.
[0014] U.S. Pat. Nos. 5,470,742, 5,843,763 and 5,871,616, which are
incorporated by reference in their entireties, disclose the use of
microorganisms or enzymes derived from microorganisms to remove
epihalohydrin and epihalohydrin hydrolysis products from wet
strength compositions without reduction in wet strength
effectiveness. Processes of removal are described which remove up
to 2.6 weight per cent of halogenated by-product based on the
weight of the composition. The amount of microorganism or enzyme
used is in direct proportion to the quantity of halogenated
by-product present. Thus, when present in large quantities (e.g.,
more than about 1% by weight of the composition) a large proportion
of microorganism or enzyme is needed to adequately remove the
unwanted product. Large quantities of halogenated byproduct can be
toxic to the microbes employed in such dehalogenation processes.
Each of these documents is hereby incorporated by reference as
though set forth in full herein.
[0015] Still further, U.S. application Ser. No. 08/482,398, now
U.S. Pat. No. 5,972,691 and WO 96/40967, which are incorporated by
reference in their entireties, disclose the treatment of wet
strength compositions with an inorganic base after the synthesis
step (e.g., after the polymerization reaction to form the resin)
has been completed and the resin has been stabilized at low pH, to
reduce the organo halogen content of wet strength compositions
(e.g., chlorinated hydrolysis products) to moderate levels (e.g.,
about 0.5% based on the weight of the composition). The composition
so formed can then be treated with microorganisms or enzymes to
economically produce wet strength compositions with very low levels
of epihalohydrins and epihalohydrin hydrolysis products.
[0016] It is also known that epihalohydrin and epihalohydrin
hydrolyzates can be reacted with bases to form chloride ion and
polyhydric alcohols. U.S. Pat. No. 4,975,499 teaches the use of
bases during the synthetic step to reduce organo chlorine contents
of wet strength composition to moderate levels (e.g., to moderate
levels of from about 0.11 to about 0.16%) based on the weight of
the composition. U.S. Pat. No. 5,019,606 teaches reacting wet
strength compositions with an organic or inorganic base. These
patents are incorporated by reference in their entireties.
[0017] Moreover, U.S. application Ser. No. 09/001,787, filed Dec.
31, 1997, and Ser. No. 09/224,107, filed Dec. 22, 1998 to Riehle,
and WO 99/33901, and which are incorporated by reference in their
entireties, disclose amongst other features, a process for reducing
the AOX content of a starting water-soluble wet-strength resin
comprising azetidinium ions and tertiary aminohalohydrin, which
includes treating the resin in aqueous solution with base to form
treated resin, wherein at least about 20% of the tertiary
aminohalohydrin present in the starting resin is converted into
epoxide and the level of azetidinium ion is substantially
unchanged, and the effectiveness of the treated resin in imparting
wet strength is at least about as great as that of the starting
wet-strength resin.
[0018] The use of endcapping agents to prepare polyaminoamide
prepolymers of controlled molecular weight is described in U.S.
Pat. Nos. 5,786,429 and 5,902,862, which are incorporated by
reference in their entireties. The endcapping agents described were
either monofunctional carboxylic acids, monofunctional carboxylic
esters or monofunctional amines. These polyaminoamides were
subsequently reacted with a minimal amount of an intralinker to
give highly branched polyamidoamines having either no or very low
levels of reactive functionality.
[0019] WO 99/09252 describes thermosetting wet strength resins
prepared from end-capped polyaminoamide polymers. The endcappers
used are monocarboxylic acids or monofunctional carboxylic esters,
and are used to control the molecular weight of the polyaminamide
in order to obtain wet strength resins with a high solids
content.
[0020] Each of the foregoing approaches has provided various
results, and there has been a continuing need for improvement.
SUMMARY OF THE INVENTION
[0021] The present invention is directed to polyamine-epihalohydrin
resin products, particularly polyamine-epihalohydrin resin products
which can be stored with at least reduced formation of halogen
containing residuals, such as 3-chloropropanediol (CPD). The
present invention is also directed to various uses of
polyamine-epihalohydrin resins having at least reduced formation of
halogen containing residuals, such as wet strength agents.
[0022] The present invention is also directed to
polyamine-epihalohydrin resin products which have reduced levels of
formation of CPD upon storage, particularly paper products.
[0023] The present invention is also directed to the preparation of
polyamine-epihalohydrin resins, especially
polyaminopolyamide-epihalohydrin resins and/or the treatment of
polyamine-epihalohydrin resins, especially
polyaminopolyamide-epihalohydrin resins.
[0024] The present invention is also directed to the preparation of
storage stable polyamine-epihalohydrin resins, especially
polyaminopolyamide-epihalohydrin resins and/or the treatment of
polyamine-epihalohydrin resins, especially
polyaminopolyamide-epihalohydrin resins to render such resins
storage stable.
[0025] In one aspect of the present invention wherein the
polyamine-epihalohydrin resin is treated to obtain a storage stable
product, the present invention is directed to a process for
rendering a polyamine-epihalohydrin resin storage stable,
comprising treating a composition containing
polyamine-epihalohydrin resin which includes CPD-forming species
with at least one agent under conditions to at least one of
inhibit, reduce and remove the CPD-forming species to obtain a
gelation storage stable reduced CPD-forming resin so that
composition containing the reduced CPD-forming
polyamine-epihalohydrin resin when stored for 2 weeks at 50.degree.
C., and a pH of about 2.5 to 3.5 contains less than about 250 ppm
dry basis of CPD, preferably less than about 150 ppm dry basis of
CPD after two weeks, more preferably less than about 75 ppm dry
basis of CPD after two weeks, even more preferably less than about
40 ppm dry basis of CPD after two weeks, and even more preferably
less than about 10 ppm dry basis of CPD after two weeks.
[0026] Moreover, the present invention is also directed to a
process for rendering a polyamine-epihalohydrin resin storage
stable, comprising treating a composition containing a
polyamine-epihalohydrin resin which includes CPD-forming species
with at least one agent under conditions to at least one of
inhibit, reduce and remove the CPD-forming species to obtain a
gelation storage stable reduced CPD-forming resin so that a
composition containing the reduced CPD-forming
polyamine-epihalohydrin resin, when stored at pH 1 for 24 hours at
50.degree. C. and measured at 24 hours, produces less than about
1000 ppm dry basis of CPD, more preferably produces less than about
750 ppm dry basis of CPD, even more preferably produces less than
about 500 ppm dry basis of CPD, even more preferably produces less
than about 250 ppm dry basis of CPD, even more preferably produces
less than about 150 ppm dry basis of CPD, even more preferably
produces less than about 100 ppm dry basis of CPD, even more
preferably produces less than about 75 ppm dry basis of CPD, even
more preferably produces less than about 50 ppm dry basis of CPD,
even more preferably produces less than about 25 ppm dry basis of
CPD, even more preferably produces less than about 15 ppm dry basis
of CPD, even more preferably produces less than about 5 ppm dry
basis of CPD, and even more preferably produces less than about 3
ppm dry basis of CPD, and even more preferably produces less than
about 1 ppm dry basis of CPD.
[0027] The present invention is also directed to a storage stable
polyaminopolyamide-epihalohydrin resin, the
polyaminopolyamide-epihalohydrin resin when stored as an aqueous
composition containing the resin, when stored at pH 1 for 24 hours
at 50.degree. C. and measured at 24 hours, produces less than about
1000 ppm dry basis of CPD, more preferably produces less than about
750 ppm dry basis of CPD, even more preferably produces less than
about 500 ppm dry basis of CPD, even more preferably produces less
than about 250 ppm dry basis of CPD, even more preferably produces
less than about 150 ppm dry basis of CPD, even more preferably
produces less than about 100 ppm dry basis of CPD, even more
preferably produces less than about 75 ppm dry basis of CPD, even
more preferably produces less than about 50 ppm dry basis of CPD,
even more preferably produces less than about 25 ppm dry basis of
CPD, even more preferably produces less than about 15 ppm dry basis
of CPD, even more preferably produces less than about 5 ppm dry
basis of CPD, and even more preferably produces less than about 3
ppm dry basis of CPD, and even more preferably produces less than
about 1 ppm dry basis of CPD.
[0028] In another aspect, the present invention is also directed to
a storage stable polyaminopolyamide-epihalohydrin resin, the
polyaminopolyamide-epihalohydrin resin being capable of forming a
paper product, so that a paper product containing said
polyaminopolyamide-epihalohydrin resin, when corrected for adding
at about a 1 wt % addition level of the
polyaminopolyamide-epihalohydrin resin, contains less than about
250 ppb of CPD, more preferably less than about 100 ppb of CPD,
more preferably less than about 50 ppb of CPD, more preferably less
than about 10 ppb of CPD and even more preferably less than about 1
ppb of CPD.
[0029] A paper product containing the reduced CPD-forming resin,
when corrected for adding at about a 1 wt % addition level of the
reduced CPD-forming resin, preferably contains less than about 250
ppb of CPD, more preferably less than about 100 ppb of CPD, more
preferably less than about 50 ppb of CPD, more preferably less than
about 10 ppb of CPD and even more preferably less than about 1 ppb
of CPD.
[0030] In another aspect of the present invention involving
preparation of the polyamine-epihalohydrin so as to have a reduced
acid number, the present invention is directed to the production of
polyaminopolyamide-epihalohydrin resins having reduced acid number,
compositions and solutions containing such resins, as well as
products, such as paper products, containing such resins.
[0031] In another aspect of the present invention, a storage stable
polyaminopolyamide-epihalohydrin resin is provided, wherein the
polyaminopolyamide-epihalohydrin resin when stored as an aqueous
composition containing the resin for 2 weeks at 50.degree. C., and
a pH of about 2.5 to 3.5 contains less than about 250 ppm dry basis
of CPD, preferably less than about 150 ppm dry basis of CPD after
two weeks, more preferably less than about 75 ppm dry basis of CPD
after two weeks, even more preferably less than about 40 ppm dry
basis of CPD after two weeks, and even more preferably less than
about 10 ppm dry basis of CPD after two weeks.
[0032] In still another aspect, the present invention is directed
to a polyaminopolyamide-epihalohydrin resin formed by reacting
polyaminoamide prepolymer with epihalohydrin, the polyaminoamide
prepolymer having an acid functionality less than about 0.5
milliequivalents/dry gram of prepolymer, and said
polyaminopolyamide-epihalohydrin resin being subjected to a
treatment to reduce at least one of epihalohydrins, epihalohydrin
hydrolysis by-products and CPD forming species.
[0033] Still further, the polyaminopolyamide-epihalohydrin resin
can be a polyaminopolyamide-epihalohydrin resin produced from
polyaminoamide prepolymer having an acid functionality less than
about 0.5 milliequivalents/dry gram of prepolymer, more preferably
less than about 0.25 milliequivalents/dry gram of prepolymer, more
preferably less than about 0.1 milliequivalents/dry gram of
prepolymer, more preferably less than about 0.075
milliequivalents/dry gram of prepolymer, even more preferably less
than about 0.05 milliequivalents/dry gram of prepolymer.
[0034] Still further, the polyaminopolyamide-epihalohydrin resin
can be a polyaminopolyamide-epihalohydrin resin produced from
polyaminoamide prepolymer having an acid end group concentration of
less than about 5%, as measured by .sup.13C NMR analysis, more
preferably, an acid end group concentration of less than about
2.5%, as measured by .sup.13C NMR analysis, more preferably an acid
end group concentration of less than about 1%, as measured by
.sup.13C NMR analysis, more preferably an acid end group
concentration less than about 0.7%, as measured by .sup.13C NMR
analysis, and even more preferably an acid end group concentration
of less than about 0.5%, as measured by .sup.13C NMR analysis.
[0035] In another aspect of the present invention, the prepolymer
can have a RSV of about 0.075 to 0.2 dL/g, more preferably about
0.1 to 0.15 dL/g, and is preferably at least about 0.05 dL/g, more
preferably at least about 0.075 dL/g, and even more preferably at
least about 0.1 dL/g.
[0036] As noted above, the composition preferably contains less
than about 150 ppm dry basis, more preferably less than about 75
ppm dry basis, more preferably less than about 40 ppm dry basis,
more preferably less than about 10 ppm dry basis of CPD after two
weeks.
[0037] Moreover, the present invention is also directed to a
process for preparing a paper product, comprising treating a
compositon containing polyamine-epihalohydrin resin which includes
CPD-forming species with at least one agent under conditions to at
least one of inhibit, reduce and remove the CPD-forming species to
obtain a gelation storage stable reduced CPD-forming resin, and
forming a paper product with the reduced CPD-forming
polyamine-epihalohydrin resin, so that a paper product, when
corrected for adding at about a 1 wt % addition level of the
reduced CPD-forming resin, contains less than about 250 ppb of CPD,
preferably less than about 100 ppb of CPD, even more preferably
less than about 50 ppb of CPD, even more preferably less than about
10 ppb of CPD, and even more preferably less than about 1 ppb of
CPD.
[0038] In still another aspect, the present invention is directed
to a process of producing a polyaminoamide prepolymer by reacting
polyalkyleneamine with dicarboxylic acid and/or dibasic ester in a
prepolymer forming reaction, and post-adding at least one amine at
a later stage of the prepolymer forming reaction. The amine can be
added in an amount so that a total molar quantity of
polyalkylenepolyamine plus post-added amine is greater than a total
molar amount of dicarboxylic acid.
[0039] Preferably, the prepolymer forming reaction is at least
about 70% complete at time of addition of the post-added amine,
more preferably at least about 80% complete, and even more
preferably at least about 90% complete.
[0040] The post-added amine can be a monofunctional amine and/or a
polyamine, such as a polyalkyleneamine.
[0041] In the various reactions, the dicarboxylic acid can comprise
at least one of oxalic acid, malonic acid, succinic acid, glutaric
acid, adipic acid and azelaic acid; the dibasic ester can comprise
at least one of dimethyl adipate, diethyl adipate, dimethyl
glutarate, diethyl glutarate, dimethyl succinate and diethyl
succinate, and the polyalkyleneamine can comprise at least one of
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
dipropylenetriamine, methylbisaminopropylamine,
bis-hexamethylenetriamine and methylbisaminopropylamine.
[0042] The polyamine-epihalohydrin resin can comprise
polyaminopolyamide-epihalohydrin resin, preferably
polyaminopolyamide-epichlorohydrin resin, and
polyaminoureylene-epihalohydrin resin, preferably
polyaminoureylene-epichlorohydrin resin.
[0043] The prepolymer can comprise endcapped prepolymer, amine
excess prepolymer and post-added amine prepolymer.
[0044] The at least one agent can comprise at least one acidic
agent. The at least one acidic agent is preferably added to provide
an initial pH of less than about 2, preferably less than about 1,
or about 1, the temperature is at least about 30.degree. C.,
preferably about 30.degree. C. to 140.degree. C., more preferably
about 40.degree. C. to 90.degree. C., with preferred temperatures
being at least about 50.degree. C., and the time is at least about
2 hours. The at least one acidic agent can be added to provide an
initial pH of about 1, the temperature can be about 50.degree. C.,
and the time can be about 24 hours. The at least one acidic agent
can added to provide an initial pH of about 1, the temperature can
be about 60.degree. C., and the time can be about 12 hours. The at
least one acidic agent can be added to provide an initial pH of
about 1, the temperature can be about 70.degree. C., and the time
can be about 6 hours. The at least one acidic agent can be added to
provide an initial pH of about 1, the temperature can be about
80.degree. C., and the time can be about 3 hours.
[0045] The at least one acidic agent can comprise a non-halogen
inorganic acid, preferably sulfuric acid.
[0046] Following the treating with the at least one acidic agent,
at least one basic agent can be added to raise the pH of the resin
solution to at least about 7, preferably to at least about 8, with
a preferred range of about 8 to 12. The resin solution during base
treatment preferably has a temperature of about 40.degree. C. to
70.degree. C. Following the addition of the at least one basic
agent, an acidic agent can be added in an amount effective to gel
stabilize the resin solution.
[0047] The at least one agent can comprise at least one basic
agent. The resin can comprise a resin formed in a
polyamide-epihalohydrin reaction having a molar ratio of
epihalohydrin to secondary amine group of less than 1, more
preferably the molar ratio of epihalohydrin to secondary amine
group is less than about 0.975, with a preferred range of the molar
ratio of epihalohydrin to secondary amine group being about 0.5 to
0.975, more preferably the molar ratio of epihalohydrin to
secondary amine group being about 0.8 to 0.975. The at least one
basic agent can raise the pH of the composition containing the
polyamine-epihalohydrin resin to a pH of at least about 8, more
preferably at least about 9, more preferably a pH of at least about
10, and the pH is preferably less than about 12.5, with a preferred
pH range pH about 10 to 12. The composition preferably has a
temperature of at least about 20.degree. C., more preferably a
temperature of at least about 40.degree. C., with one temperature
range being about 20.degree. C. to 80.degree. C. The composition
can have a temperature of about 50.degree. C., a pH of about 11.5,
and a treatment time is about 5 minutes. The composition can have a
temperature of about 55.degree. C., a pH of about 10.5 to 11.5, and
a treatment time is about 5 minutes. The reduced CPD-forming resin
can be acid stabilized, such as to a pH from about 2.5 to 4.
[0048] The at least one agent can comprise at least one enzymatic
agent, such as at least one of esterases, lipases and proteases,
preferably ALCALASE.
[0049] The at least one agent can comprise at least one pH
modifying agent to obtain a pH of about 5.5 to 7. The composition
can have a temperature of about 30.degree. C., a pH of about 6 and
a treatment time of about 6 days. The composition can have a
temperature of about 50.degree. C., a pH of about 6 and a treatment
time of about 6 hours.
[0050] Prior and/or subsequent to treating a
polyamine-epihalohydrin resin to obtain a reduced CPD-forming resin
and/or after production of a low acid number resin, the resin can
be contacted with at least one microorganism, or at least one
enzyme isolated from the at least one microorganism, in an amount,
and at a pH and temperature effective to dehalogenate residual
quantities of organically bound halogen. The at least one
microorganism can comprise at least one of Arthrobacter
histidinolovorans HK1, Agrobacterium radiobacter biovar 1 and
Agrobacterium tumefaciens HK7. The at least one microorganism can
comprise a mixture comprising at least one of Agrobacterium
tumefaciens HK7 and Agrobacterium radiobacter biovar 1, and
Arthrobacter histidinolovorans HK1
[0051] Moreover, prior and/or subsequent to the treating a
polyamine-epihalohydrin resin to obtain a reduced CPD-forming resin
and/or after production of a low acid number resin, the resin can
be treated to reduce at least one of epihalohydrins, epihalohydrin
hydrolysis by-products and organic halogen bound to the polymer
backbone.
[0052] The present invention is also directed to paper products
treated with resins produced according to the present invention, to
reduced CPD-forming resin produced according to the present
invention, and aqueous compositions comprising the reduced
CPD-forming resin according to the present invention, and such
aqueous compositions including at least one polyalkylene
polyamine-epihalohydrin resin.
[0053] The paper product can comprise a paper product which comes
into contact with food products, such as a tea bag or coffee
filter, or packaging board, or tissue and towel.
DETAILED DESCRIPTION OF THE INVENTION
[0054] Unless otherwise stated, all percentages, parts, ratios,
etc., are by weight.
[0055] Unless otherwise stated, a reference to a compound or
component includes the compound or component by itself, as well as
in combination with other compounds or components, such as mixtures
of compounds.
[0056] Further, when an amount, concentration, or other value or
parameter, is given as a list of upper preferable values and lower
preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of an upper preferred
value and a lower preferred value, regardless whether ranges are
separately disclosed.
[0057] Polyamine-epihalohydrin resins according to the present
invention include polyaminopolyamide-epihalohydrin resins (which
are also known as polyaminoamide-epihalohydrin resins,
polyamidepolyamine-epihalohydrin resins,
polyaminepolyamide-epihalohydrin resins,
aminopolyamide-epihalohydrin resins, polyamide-epihalohydrin
resins); polyalkylene polyamine-epihalohydrin; and
polyaminourylene-epihalohydrin resins,
copolyamide-polyurylene-epichlorohydrin resins,
polyamide-polyurylene-epichlorohydrin resins with the epihalohydrin
preferably being epichlorohydrin in each instance.
[0058] This invention is also directed towards the preparation, use
and treatment of polyamine-epihalohydrin resins, such as
polyaminopolyamide-epichlorohydrin resins, made by reacting
epihalohydrin, such as epichlorohydrin, with a prepolymer (also
interchangeably referred to herein as polymer), such as
polyaminoamide prepolymer. In the case of polyaminopolyamide
resins, it is noted that the polyaminoamide prepolymer is also
referred to as polyamidoamine, polyaminopolyamide,
polyamidopolyamine, polyamidepolyamine, polyamide, basic polyamide,
cationic polyamide, aminopolyamide, amidopolyamine or
polyaminamide.
[0059] While not wishing to be bound by theory, the present
invention is based upon the discovery that CPD that is formed in
polyamine-epihalohydrin resins, particularly
polyaminopolyamide-epihalohydrin resins, after storage, is due to
CPD-forming species that are associated with the oligomeric and/or
polymeric component of the resin. Thus, it has been discovered that
polyamine-epihalohydrin resins can be treated during and/or
subsequent to production in such a manner so as to prevent the
formation of, inhibit and/or remove elements associated with the
polyamine-epihalohydrin resin which form CPD upon storage.
[0060] In other words, the resins according to the present
invention are capable of being stored without undue formation of
CPD. More specifically, as an example, the solution will contain
less than about 10 ppm (parts per million), more preferably less
than about 5 ppm, and most preferably less than 1 ppm of CPD, when
stored at about 13.5 wt % resin solids content. In the context of
the present invention the phrase "resin solids" means the active
polyamine-epihalohydrin of the composition.
[0061] To determine storage stability of resin solutions according
to the present invention, a resin solution stability test is
performed wherein the resin solution is stored for a period of 2
weeks at 50.degree. C., and a pH of about 2.5 to 3.5, preferably
2.8, and the CPD content is measured at the end of the 2 week
period. Thus, a solution containing polyamine-epihalohydrin resin
according to the present invention will be storage stable if it
contains less than about 250 ppm dry basis of CPD when measured at
the end of the two week period, more preferably less than about 150
ppm dry basis of CPD when measured at the end of the 2 week period,
more preferably less than about 75 ppm dry basis of CPD when
measured at the end of the 2 week period, even more preferably less
than about 40 ppm dry basis of CPD when measured at the end of the
two week period, and even more preferably less than about 10 ppm
dry basis of CPD when measured at the end of the 2 week period.
[0062] The resin solution stability test can be performed on
solutions containing varying percent resin solids content; however,
the CPD produced should be corrected for solids content. For
example, for a 15 wt % resin solids content solution having a
measured CPD content of 15 ppm, the corrected CPD, on a dry basis,
will be 100 ppm dry basis (15 ppm/0.15 weight resin solids
content).
[0063] The resin solution stability test is performed by charging a
portion of the polyamine-epihalohydrin resin into a container
containing a stirrer. The container is placed in a 50.degree. C.
water bath and maintained at 50.degree. C. with stirring. An
aliquot is removed from the container and submitted for GC (gas
chromatography) analysis according to the GC procedure as set forth
in Comparative Example 1. Typically, a flame ionization detector
(FID) is first used to analyze the sample. An electrolytic
conductivity detector (ELCD) or a halogen-specific detector (XSD)
is used when increased sensitivity is needed, especially at less
than about 20 ppm of the species to be analyzed. Other sensitive
detectors can be used, e.g., electron capture detectors. This test
is an accelerated aging test to model ageing at longer periods of
time at about 32.degree. C.
[0064] Moreover, paper products containing resins according to the
present invention are capable of being stored without undue
formation of CPD. Thus, paper products according to the present
invention can have initial low levels of CPD, and can maintain low
levels of CPD over an extended period storage time. More
specifically, paper products according to the present invention,
made with a 1 wt % addition level of resin, will contain less than
about 250 parts per billion (ppb) of CPD, more preferably less than
about 100 ppb of CPD, even more preferably less than about 50 ppb
of CPD and even more preferably less than about 10 ppb of CPD when
stored for periods as long as 2 weeks, more preferably as long as
at least 6 months, and even more preferably as long as at least one
year. Moreover, paper products according to the present invention,
made with about a 1 wt % addition level of resin, will have an
increase in CPD content of less than about 250 ppb, more preferably
less than about 100 ppb of CPD, even more preferably less than
about 50 ppb of CPD, even more preferably less than about 10 ppb of
CPD, and even more preferably less than about 1 ppb of CPD when
stored for periods as long as 2 weeks, more preferably as long as
at least 6 months, and even more preferably as long as at least one
year. In other words, the paper products according to the present
invention have storage stability and will not generate excessive
CPD content in paper products when the paper products are stored as
little as one day and for periods of time greater than one year.
Thus, the resins according to the present invention give minimal
formation of CPD in paper products, particularly those exposed to
aqueous environments, especially hot aqueous environments, e.g.,
tea bag, coffee filters, etc. Further examples of paper products
include packaging board grade, and tissue and towel grade.
[0065] Paper can be made by adding the resin at addition levels
other than about 1 wt %; however, the CPD content should be
corrected for the addition level. For example, for a paper product
made by adding the resin at a 0.5 wt % addition level having a
measured CPD content of 50 ppb, the corrected CPD on a 1 wt %
addition level basis will be 100 ppb (50 ppb/0.5 percent addition
level).
[0066] To measure CPD in paper products, the paper product is
extracted with water according to the method described in European
standard EN 647, dated October 1993. Then 5.80 grams of sodium
chloride is dissolved into 20 ml of the water extract. The salted
aqueous extract is transferred to a 20 gram capacity Extrelut
column and allowed to saturate the column for 15 minutes. After
three washes of 3 ml ethyl acetate and saturation of the column,
the Extrelut column is eluted until 300 ml of eluent has been
recovered in about 1 hour. The 300 ml of ethyl acetate extract is
concentrated to about 5 ml using a 500-ml Kudema-Danish
concentrating apparatus (if necessary, further concentrating is
done by using a micro Kudema-Danish apparatus). The concentrated
extract is analyzed by GC using the instrumentation described in
Comparative Example 1. Typically, a flame ionization detector (FID)
is first used to analyze the sample. An electrolytic conductivity
detector (ELCD) or a halogen-specific detector (XSD) is used when
increased sensitivity is needed, especially at less than about 20
ppm of the species to be analyzed. Other sensitive detectors can be
used, e.g., electron capture detectors.
[0067] Preferably, the resin according to the present invention
contains less than 1 part per million (ppm) each of epihalohydrin,
e.g., epichlorohydrin, 1,3-DCP, 2,3-DCP and less than 10 ppm of CPD
after storage, at 13.5 wt. % total solids content, which, when
applied to paper at a dosage of up to 1 wt. % dry basis on fiber,
gives a level of less than about 30 ppb of each of epihalohydrin
and epihalohydrin byproducts, e.g., epichlorohydrin and 1,3-DCP and
2,3-DCP, and CPD content in paper, and the paper is stable at that
level for up to 6 months storage at room temperature, so that after
about 6 months, preferably after about 1 year, the level each of
these species will be less than about 30 ppb.
[0068] Polyaminopolyamide-epichlorohydrin resins comprise the
water-soluble polymeric reaction product of epichlorohydrin and
polyamide derived from polyalkylene polyamine and saturated
aliphatic dibasic carboxylic acid containing from about 2 to about
10 carbon atoms. It has been found that resins of this type impart
wet-strength to paper whether made under acidic, alkaline or
neutral conditions. Moreover, such resins are substantive to
cellulosic fibers so that they may be economically applied thereto
while the fibers are in dilute aqueous suspensions of the
consistency used in paper mills.
[0069] In the preparation of the cationic resins contemplated for
use herein, the dibasic carboxylic acid is first reacted with the
polyalkylene polyamine, under conditions such as to produce a
water-soluble polyamide containing the recurring groups
--NH(C.sub.nH.sub.2nNH).sub.x--CORCO-- where n and x are each 2 or
more and R is the divalent hydrocarbon radical of the dibasic
carboxylic acid. This water soluble polyamide is then reacted with
an epihalohydrin to form the water-soluble cationic thermosetting
resins.
[0070] The dicarboxylic acids contemplated for use in preparing the
resins of the invention are the saturated aliphatic dibasic
carboxylic acids containing from 2 to 10 carbon atoms such as
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic
acid, azelaic acid and the like. The saturated dibasic acids having
from 4 to 8 carbon atoms in the molecule, such as adipic and
glutaric acids are preferred. Blends of two or more of the
saturated dibasic carboxylic acids may also be used. Derivatives of
dibasic carboxylic acids, such as esters, half-esters and
anhydrides can also be used in the present invention, such as
dimethyl adipate, diethyl adipate, dimethyl glutarate, diethyl
glutarate, dimethyl succinate and diethyl succinate. Blends of two
or more of derivatives of dibasic carboxylic acids may also be
used, as well as blends of one or more derivatives of dibasic
carboxylic acids with dibasic carboxylic acids.
[0071] A variety of polyalkylene polyamines including polyethylene
polyamines, polypropylene polyamines, polybutylene polyamines,
polypentylene polyamines, polyhexylene polyamines and so on and
their mixtures may be employed of which the polyethylene polyamines
represent an economically preferred class. More specifically, the
polyalkylene polyamines contemplated for use may be represented as
polyamines in which the nitrogen atoms are linked together by
groups of the formula --C.sub.nH.sub.2n-- where n is a small
integer greater than unity and the number of such groups in the
molecule ranges from two up to about eight. The nitrogen atoms may
be attached to adjacent carbon atoms in the group
--C.sub.nH.sub.2n-- or to carbon atoms further apart, but not to
the same carbon atom. This invention contemplates not only the use
of such polyamines as diethylenetriamine, triethylenetetramine,
tetraethylenepentamine and dipropylenetriamine, which can be
obtained in reasonably pure form, but also mixtures and various
crude polyamine materials. For example, the mixture of polyethylene
polyamines obtained by the reaction of ammonia and ethylene
dichloride, refined only to the extent of removal of chlorides,
water, excess ammonia, and ethylenediamine, is a satisfactory
starting material. The term "polyalkylene polyamine" employed in
the claims, therefore, refers to and includes any of the
polyalkylene polyamines referred to above or to a mixture of such
polyalkylene polyamines and derivatives thereof. Additional
polyamines that are suitable for the present invention include;
bis-hexamethylenetriamine (BHMT), methylbisaminopropylamine
(MBAPA), other polyalkylene polyamines (e.g., spermine,
spermidine). Preferably, the polyamines are diethylenetriamine,
triethylenetetramine, tetraethylenepentamine and
dipropylenetriamine.
[0072] It is desirable, in some cases, to increase the spacing of
secondary amino groups on the polyamide molecule in order to change
the reactivity of the polyamide-epichlorohydrin complex. This can
be accomplished by substituting a diamine such as ethylenediamine,
propylenediamine, hexamethylenediamine and the like for a portion
of the polyalkylene polyamine. For this purpose, up to about 80% of
the polyalkylene polyamine may be replaced by molecularly
equivalent amount of the diamine. Usually, a replacement of about
50% or less will serve the purpose.
[0073] Appropriate aminocarboxylic acids containing at least three
carbon atoms or lactams thereof are also suitable for use to
increase spacing in the present invention. For example,
6-aminohexanoic acid and caprolactam.
[0074] Polyaminoureylene-epihalohydrin resins, particularly
polyaminoureylene-epichlorohydrin resins, are also contemplated in
the present invention, such as discussed in U.S. Pat. Nos.
4,487,884 and 3,311,594, which are incorporated by reference in
their entireties, such as Kymene.RTM. 450 type of resins (Hercules
Incorporated, Wilmington, Del.). The polyaminoureylene resins
contemplated for preparation and use herein are prepared by
reacting epichlorohydrin with polyaminoureylenes containing free
amine groups. These polyaminoureylenes are water-soluble materials
containing tertiary amine groups and/or mixtures of tertiary amine
groups with primary and/or secondary amino groups and/or quaternary
ammonium groups. However, tertiary amino groups should account for
at least 70% of the basic nitrogen groups present in the
polyaminoureylene. These polyaminoureylenes may be prepared by
reacting urea or thiourea with a polyamine containing at least
three amino groups, at least one of which is a tertiary amino
group. The reaction can, if desired, be carried out in a suitable
solvent such as xylene.
[0075] The polyamine reactant should preferably have at least three
amino groups, at least one of which is a tertiary amino group, the
polyamine reactant may also have secondary amino groups in limited
amounts. Typical polyamines of this type suitable for use as
hereinabove described are methyl bis(3-aminopropyl)amine (MBAPA),
methyl bis(2-aminoethyl)amine, N-(2-aminoethyl)piperazine,
4,7-dimethyltriethylenetetramine and so on, which can be obtained
in reasonably pure form, but also mixtures of various crude
polyamine materials.
[0076] To prepare the prepolymer from diacid and
polyalkylenepolyamine, a mixture of the reactants is preferably
heated at a temperature of about 125-200.degree. C. for preferably
about 0.5 to 4 hours, at atmospheric pressure. Where a reduced
pressure is employed, lower temperatures such as 75.degree. C. to
150.degree. C. may be utilized. This polycondensation reaction
produces water as a byproduct, which is removed by distillation. At
the end of this reaction, the resulting product is dissolved in
water at a concentration of about 50% by weight total polymer
solids.
[0077] Where diester is used instead of diacid, the
prepolymerization can be conducted at a lower temperature,
preferably about 100-175.degree. C. at atmospheric pressure. In
this case the byproduct will be an alcohol, the type of alcohol
depending upon the identity of the diester. For instance, where a
dimethyl ester is employed the alcohol byproduct will be methanol,
while ethanol will be the byproduct obtained from a diethyl ester.
Where a reduced pressure is employed, lower temperatures such as
75.degree. C. to 150.degree. C. may be utilized.
[0078] In converting the polyamide, formed as above described, to a
cationic thermosetting resin, it is reacted with epichlorohydrin at
a temperature from above about 0.degree. C., more preferably about
25.degree. C., to about 100.degree. C., and preferably between
about 35.degree. C. to about 70.degree. C. until the viscosity of a
20% solids solution at 25.degree. C. has reached about C or higher
on the Gardner Holdt scale. This reaction is preferably carried out
in aqueous solution to moderate the reaction. Although not
necessary, pH adjustment can be done to increase or decrease the
rate of crosslinking.
[0079] When the desired viscosity is reached, sufficient water can
be added to adjust the solids content of the resin solution to the
desired amount, i.e., about 15 wt % more or less, the product can
be cooled to about 25.degree. C. and then stabilized to permit
storage by improving the gelation stability by adding sufficient
acid to reduce the pH to less than about 6, preferably less than
about 5, and most preferably less than about 4. Any suitable
inorganic or organic acid such as hydrochloric acid, sulfuric acid,
methanesulfonic acid, nitric acid, formic acid, phosphoric acid and
acetic acid may be used to stabilize the product. Non-halogen
containing acids, such as sulfuric acid, are preferred.
[0080] In the polyamide-epichlorohydrin reaction, it is preferred
to use sufficient epichlorohydrin to convert most of the secondary
amine groups to tertiary amine groups. For prepolymers that contain
tertiary amine groups, it is preferred to use sufficient
epichlorohydrin to convert most of the tertiary amine groups to
quaternary amine groups. However, more or less may be added to
moderate or increase reaction rates. In general, satisfactory
results may be obtained utilizing from about 0.5 mole to about 1.8
moles of epichlorohydrin for each secondary amine group of the
polyamide. It is preferred to utilize from about 0.6 mole to about
1.5 moles for each secondary amine group of the polyamide.
[0081] Epichlorohydrin is the preferred epihalohydrin for use in
the present invention. The present application refers to
epichlorohydrin specifically in certain instances, however, the
person skilled in the art will recognize that these teachings apply
to epihalohydrin in general.
[0082] As to the CPD-forming species, not to be limited by theory,
it is believed that the acid groups in, for example,
polyaminopolyamides, react with epichlorohydrin during production
of, e.g., polyaminopolyamide-epichlorohydrin resins, to form a
small amount of chlorohydroxypropyl ester species (hereinafter also
referred to as CPD ester) on the resin backbone. Hydrolysis of CPD
ester upon aging would yield CPD and regenerate the acid group.
[0083] Without wishing to be limited by theory, it is noted that
epichlorohydrin is more reactive with secondary amine than with
acid groups. Therefore, by having a lower value of epihalohydrin,
the epihalohydrin will preferentially react with the secondary
amine than with acid groups. Also, as the epichlorohydrin to
secondary amine ratio increases there are more CPD forming species,
and would be more CPD forming species to remove. Still further, if
excess of epichlorohydrin is present, after the secondary amines
react with the epichlorohydrin, there would still be
epichlorohydrin present to react with the acid groups, which would
be capable of forming the CPD-forming species. Accordingly, it is
preferred that the epihalohydrin to secondary amine group molar
ratio be less than 1, more preferably less than about 0.975, with a
preferred range being about 0.5 to 0.975, a more preferred range
being about 0.8 to 0.975.
[0084] Any procedure can be utilized to remove or reduce the amount
of already produced CPD-forming species, including CPD-forming
species that may already be present in the resin. For example, the
resin can be formed under conditions that prevent and/or reduce the
formation of CPD-forming species on the polymer backbone and/or
inhibit the CPD-forming ability of already produced species.
Moreover, the resin can be treated, preferably as a last step in
its production, or immediately subsequent to its production, to
remove, reduce and/or inhibit the CPD-forming species. Thus, in one
aspect, the invention comprises processes for reducing the
CPD-forming species, especially in resins that have low amounts of
at least one of epihalohydrins, epihalohydrin hydrolysis
by-products and organic halogen bound to the polymer backbone. In
particular, the resin can comprise low residual resins such as
disclosed in U.S. Pat. Nos. 5,189,142, 5,239,047 and 5,364,927,
U.S. Pat. No. 5,516,885, WO 92/22601, WO 93/21384, U.S. application
Ser. No. 08/482,398, now U.S. Pat. No. 5,972,691, WO 96/40967, and
U.S. Pat. Nos. 5,470,742, 5,843,763 and 5,871,616. The disclosures
of each of these documents is incorporated by reference in their
entireties. For example, the concentration of hydrolyzates in the
wet strength composition can be preferably less than about 100 ppm
(parts per million by weight relative to the total weight of
aqueous solution containing wet strength resins), more preferably
less than about 50 ppm (parts per million by weight relative to the
total weight of aqueous solution containing wet strength resins),
more preferably less than about 10 ppm (parts per million by weight
relative to the total weight of aqueous solution containing wet
strength resins), more preferably less than about 5 ppm (parts per
million by weight relative to the total weight of aqueous solution
containing wet strength resins), and even more preferably less than
about 1 ppm (parts per million by weight relative to the total
weight of aqueous solution containing wet strength resins).
[0085] For example, with respect to the removal, reduction and/or
inhibition of CPD-forming species in the resin, the following
preferred non-limiting procedures are noted. It is noted that
procedures for removing, reducing and/or inhibiting the CPD-forming
species in the resin can be used alone or in combination.
[0086] The CPD-forming species in the resin can be reduced and/or
removed by treating the resin with an acid to lower the pH of the
solution to a pH less than about 2, more preferably less than about
1, and the pH can be as low as 0.5, or even as low as 0.1, for a
sufficient period of time and at a sufficient temperature to remove
and/or reduce CPD-forming species in the resin to obtain a storage
stable product. In particular, the temperature is preferably at
least about 30.degree. C., more preferably at least about
40.degree. C., and even more preferably at least 50.degree. C.,
with the upper temperature being preferably less than about
140.degree. C. Preferably, the temperature ranges from about
30.degree. C. to 140.degree. C., more preferably about 40.degree.
C. to 90.degree. C., and most preferably from about 50.degree. C.
to 80.degree. C. The time of treatment can be made shorter with
increasing temperature and decreasing pH, and is preferably at
least about 2 hours, with the time of treatment being preferably
about 24 hours at 50.degree. C., and preferably about 2 hours at
90.degree. C. Preferred combinations of temperature, time and pH,
include at 50.degree. C., a pH of about 1 and a treatment time of
about 24 hours; at 60.degree. C., a pH of about 1, and a treatment
time of about 12 hours; at 70.degree. C., a pH of about 1, and a
treatment time of about 6 hours; and at 80.degree. C., a pH of
about 1, and a treatment time of about 3 hours.
[0087] When referring to the pH, reference is being made to the pH
of the solution immediately after addition of the acidic agent. The
pH can vary after addition of the acidic agent, or can be
maintained at the initial pH. Preferably, the initial pH is
maintained.
[0088] The resin solids for acid treatment can be at least about 1
wt %, preferably at least about 2 wt %, more preferably at least
about 6 wt %, more preferably at least about 8 wt %, and most
preferably at least about 10 wt %. The resins solids can be up to
about 40 wt %, preferably up to about 25 wt %.
[0089] Both organic and inorganic acids can be used herein in the
present invention. An acid is defined as any proton donor (see
Advanced Organic Chemistry, Third Ed.; Jerry March; John Wiley
& Sons: New York, 1985, p 218-236, incorporated herein by
reference.) Suitable acids include hydrochloric acid, sulfuric
acid, methanesulfonic acid, nitric acid, formic acid, phosphoric
and acetic acid. Non-halogen containing acids, such as sulfuric
acid, are preferred.
[0090] It is noted that the acid treatment reduces the wet strength
effectiveness of the resin. However, the effectiveness can
preferably be recovered by a base treatment of the acid-treated
resin. Not to be limited by theory, it is believed that the
effectiveness increase is due to an increase in the molecular
weight of the polymer during the crosslinking base treatment.
Moreover, it would appear that if the base-treated resin were not
long-term stabilized against gelation with an acid treatment, an
additional effectiveness boost would also be likely due to the
conversion of aminochlorohydrin to the more reactive epoxide. The
base treatment is performed at a pH of at least about 7, more
preferably at least about 8, with a preferred range of about 8 to
12. The base temperature is preferably about 40.degree. C., more
preferably about 50.degree. C., even more preferably about
60.degree. C., and can be as high as at least about 70.degree. C.,
and even as high as about 100.degree. C.
[0091] The base treatment time is determined by the desired level
of crosslinking. The preferred Gardner-Holdt viscosity is dependent
upon solids. At about 12 wt % resin solids, a Gardner-Holt
viscosity of about A-M is preferred, with B-H being more preferred.
Within limits, the higher the crosslinking temperature and pH, the
faster the rate of crosslinking. It is preferred to perform the
base treatment for about 0.5 to 6 hours, more preferably about 1 to
4 hours.
[0092] Both organic and inorganic bases can be used as the basic
agent in the base treatment. A base is defined as any proton
acceptor (see Advanced Organic Chemistry, Third Ed.; Jerry March;
John Wiley & Sons: New York, 1985, p 218-236, incorporated
herein by reference.) Typical bases include alkali metal
hydroxides, carbonates and bicarbonates, alkaline earth metal
hydroxides, trialkylamines, tetraalkylammonium hydroxides, ammonia,
organic amines, alkali metal sulfides, alkaline earth sulfides,
alkali metal alkoxides, alkaline earth alkoxides, and alkali metal
phosphates, such as sodium phosphate and potassium phosphate.
Preferably, the base will be alkali metal hydroxides (lithium
hydroxide, sodium hydroxide and potassium hydroxide) or alkali
metal carbonates (sodium carbonate and potassium carbonate). Most
preferably, the base comprises inorganic bases including sodium
hydroxide and potassium hydroxide, which are especially preferred
for their low cost and convenience.
[0093] The base treated resin can be used without further
treatment, especially when the resin is to be used without storage.
Thus, the resin can be treated directly prior to application, e.g.,
in papermaking. However, if the resin is to be stored, it is
preferred to add an acid to the base treated resin to lower the pH
to less than about 6.0, with a preferred range being about 2.5 to
4.0. The stabilizing acid can be any suitable inorganic or organic
acid such as hydrochloric acid, sulfuric acid, methanesulfonic
acid, nitric acid, formic acid, phosphoric and acetic acid.
Non-halogen containing acids, such as sulfuric acid, are
preferred.
[0094] The amount of CPD-forming species can be determined using
the following test. A portion of resin to be tested is charged into
a container containing a stirrer. The pH is adjusted to 1.0 with 96
wt % sulfuric acid. The container is closed and placed in a
50.degree. C. water bath and maintained at 50.degree. C. with
stirring. An aliquot is removed from the container at 24 hours, and
submitted for GC analysis in the manner described in Comparative
Example 1 to provide an indication of the CPD-forming species. The
CPD-forming species at 24 hours preferably produces less than about
1000 ppm dry basis of CPD, more preferably less than about 750 ppm
dry basis of CPD, even more preferably less than about 500 ppm dry
basis of CPD, even more preferably less than about 250 ppm dry
basis of CPD, even more preferably less than about 150 ppm dry
basis of CPD, even more preferably less than about 100 ppm dry
basis of CPD, even more preferably less than about 75 ppm dry basis
of CPD, even more preferably less than about 50 ppm dry basis of
CPD, even more preferably less than about 25 ppm dry basis of CPD,
even more preferably less than about 15 ppm dry basis of CPD, even
more preferably less than about 5 ppm dry basis of CPD, even more
preferably less than about 3 ppm dry basis of CPD, and even more
preferably less than about 1 ppm dry basis of CPD.
[0095] The resin having at least reduced levels of formation of CPD
can be a resin as produced in a resin synthesis process without
further treatment. Moreover, the resin can be treated by various
processes prior to reduction and/or removal of the CPD-forming
species. Still further, after treatment to reduce and/or remove
CPD-forming species, the resin can be treated by various processes.
Yet still further, the resin can be treated by various processes
prior to reduction and/or removal of the CPD-forming species, and
the resin can also be treated by various processes after treatment
to reduce and/or remove CPD-forming species. For example, the resin
can be treated by various processes, such as processes to remove
low molecular weight epihalohydrin and epihalohydrin by-products,
e.g., epichliorohydrin and epichlorohydrin by-products, for
example, CPD in the resin solution. Without limiting the treatments
or resins that can be utilized, it is noted that resins, such as
Kymene.RTM. SLX2, Kymene.RTM. 617 and Kymene.RTM. 557LX (available
from Hercules Incorporated, Wilmington, Del.), could be treated
prior to and/or subsequent to reduction or removal of CPD-forming
species with a base ion exchange column, such as disclosed in U.S.
Pat. No. 5,516,885 and WO 92/22601; with carbon adsorption, such as
disclosed in WO 93/21384; membrane separation, e.g.,
ultrafiltration; extraction, e.g, ethyl acetate, such as disclosed
in U.S. Statutory Invention Registration H1613; or
biodehalogenation, such as disclosed in U.S. application Ser. No.
08/482,398, now U.S. Pat. No. 5,972,691, WO 96/40967 and U.S. Pat.
Nos. 5,470,742, 5,843,763 and 5,871,616. The disclosures of each of
these documents is incorporated by reference in their
entireties.
[0096] For example, with respect to biodehalogenation, such as
disclosed in any one of U.S. Pat. Nos. 5,470,742; 5,843,763 and
5,871,616, or previous base treatment and biodehalogenation as
disclosed in U.S. application Ser. No. 08/482,398, now U.S. Pat.
No. 5,972,691, and WO 96/40967, with or without a previous
inorganic base treatment, the wet strength composition may be
reacted with a microorganism or enzyme in adequate quantities to
process epihalohydrin hydrolyzates to very low levels.
Microorganisms use dehalogenase enzymes to liberate halide ion from
the epihalohydrin and haloalcohol and then use further enzymes to
break down the reaction products ultimately to carbon dioxide and
water.
[0097] While not wishing to be bound by theory, it is noted that
when the CPD-forming species is removed or reduced, CPD is released
from the oligomeric and/or polymeric component of the resin, and
therefore CPD is a component of the resin solution. With this in
mind, the resin is preferably subjected to treatment to remove or
reduce the CPD-forming species, and then the resin is
biodehalogenated. In this manner, epihalohydrin and epihalohydrin
hydrolyzate (also referred to as hydrolysis by-products), including
released CPD, can be removed, such as by the biodehalogenation.
However, the resin can be initially treated, such as by
biodehalogenation, and then subjected to treatment to remove,
inhibit and/or reduce the CPD-forming species. In particular, any
CPD that will be released by the treatment should be readily
soluble, and can therefore be at least partially washed away from
the resin. For example, when the resin with released CPD is
included in a paper product, the CPD can be at least partially
washed out of the paper product, and, due to the treatment, the
resin in the paper product will not produce CPD or will not produce
undesirable amounts of CPD.
[0098] Exemplary microorganisms which contain dehalogenating
enzymes capable of dehalogenating haloalcohols and epihalohydrins
have been found in the following species: TABLE-US-00001 NAME
NCIMB.sup.1 DEPOSIT IDENTITY Arthrobacter histidinolovorans 40274
Arthrobacter erithii 40271 Agrobacterium tumefaciens 40272
Rhodococcus dehalogenans 40383 Pseudomonas cepacia 40273 Mixtures
of the foregoing can also be employed. Several strains of
microorganisms from these species have been found to generate
enzymes suitable for the process. NCIMB .sup.1NCIMB stands for
"National Collection of Industrial and Marine Bacteria". NCIMB,
located at 23 St. Machar Drive, Aberdeen AB2 1RY, Scotland, UK is
an organization in the United Kingdom responsible for documenting
and retaining samples of bacteria submitted for patent application
purposes. In patent matters, NCIMB will supply to interested
parties who so request, authentic samples of bacteria claimed in
patent literature.
40271, 40272, 40273 and 40274 were deposited on Apr. 2, 1990. NCIMB
40383 was deposited on Mar. 11, 1991.
[0099] Such microorganisms are conventional. Such microorganisms
are obtainable by batch or continuous enrichment culture.
Inoculation of enrichment isolation media with soil samples taken
from organohalogen-contaminated soil results in mixed microbial
communities, which can be sub-cultured, in a plurality of
subculturing steps (preferably 2 to 5 subculturing steps), using
increasing concentrations of the particular
organohalogen-containing compound for which selection is
sought.
[0100] The microorganisms containing suitable enzymes are suitably
used to dehalogenate the epihalohydrin hydrolyzates contained in
the wet strength composition with or without an initial inorganic
base treatment. The enzymes and microorganisms are maintained in a
suitable concentration to substantially metabolize the hydrolyzates
to chloride ion and ultimately carbon dioxide and water. Thus the
concentration of hydrolyzates in the wet strength composition after
treatment is preferably less than about 100 ppm (parts per million
by weight relative to the total weight of aqueous solution
containing wet strength resins after the bioreaction step), more
preferably less than about 50 ppm (parts per million by weight
relative to the total weight of aqueous solution containing wet
strength resins after the bioreaction step), more preferably less
than about 10 ppm (parts per million by weight relative to the
total weight of aqueous solution containing wet strength resins
after the bioreaction step), more preferably less than about 5 ppm
(parts per million by weight relative to the total weight of
aqueous solution containing wet strength resins after the
bioreaction step), and even more preferably less than about 1 ppm
(parts per million by weight relative to the total weight of
aqueous solution containing wet strength resins after the
bioreaction step).
[0101] To achieve this, the concentration of microorganisms should
be at least about 5.times.10.sup.7 cells/ml, preferably at least
about 10.sup.8 cells/ml and most preferably at least about 10.sup.9
cells/ml. To maintain optimum active content of cells in the
reactor, the reaction is best carried out at about 30.degree.
C.+/-5.degree. C. in the presence of oxygen (e.g., from about 5 to
about 100% DOT) and nutrients in a stirred tank reactor. As used
herein, the term "DOT" refers to "dissolved oxygen tension" and is
the amount of oxygen, expressed as a percentage, dissolved in a
given volume of water relative to oxygen-saturated water at the
same temperature and pressure. The residence time is controlled by
flow rate and monitored to ensure complete reaction. Thus, at
steady state the concentration of epihalohydrin hydrolyzates in the
reactor will be from about 1 to about 1000 ppm.
[0102] The present invention also includes the reaction of an
enzyme with the organohalogen compound, whereby the organohalogen
is dehalogenated. As used herein, the term "enzyme" refers to any
dehalogenase, i.e., any enzyme capable of dehalogenating a
nitrogen-free organohalogen compound. Preferably, the enzyme is
obtained from a living cell, which is thereafter used for the
dehalogenation of nitrogen-free organohalogen compounds. Suitable
enzymes include those produced by the microorganisms identified
above.
[0103] Although the precise identity of the enzymes of the method
has not been determined, the enzymes which effectuate the method
belong to the class of enzymes variously termed "haloalcohol
dehalogenases" or "hydrogen halide lyase type dehalogenases" or
"halohydrin hydrogen-halide lyases".
[0104] Thus, for dehalogenation, the invention contemplates the use
of either living cells or an immobilized, unrefined cell-free
extract or refined dehalogenase. The term "biodehalogenation"
refers to the dehalogenation of an organohalogen compound using
such materials.
[0105] In general, if an enzyme is employed, the enzyme may be
added to the composition in an amount of from about
2.5.times.10.sup.-6 to 1.times.10.sup.-4 weight percent, based on
the weight of the composition. However, the enzyme is preferably
added to the composition in an amount of from about
2.5.times.10.sup.-5 to 0.75.times.10.sup.-4 weight percent, most
preferably in an amount of from about 4.times.10.sup.-5 to
6.times.10.sup.-5 weight percent, based on the weight of the
composition.
[0106] Suitable biocatalysts can also be employed. Such
biocatalysts can be readily selected by those of ordinary skill in
the art. Agrobacterium tumefaciens HK7 (NCIMB 40313) represents
another biocatalyst for use in the method of the present invention.
NCIMB 40313 was deposited on Aug. 30, 1990. Agrobacterium
tumefaciens HK7, as deposited under NCIMB 40313, based upon recent
tests may be Agrobacterium radiobacter biovar 1, which one having
ordinary skill in the art would expect to having similar activities
as Agrobacterium tumefaciens HK7. The most preferred biocatalyst
for use in the method of the present invention is a two-component
mixture of one or both of Agrobacterium tumefaciens HK7 and
Agrobacterium radiobacter biovar 1 with Arthrobacter
histidinolovorans. To ensure that both bacteria are present in the
biodehalogenation process, it is preferred to start the process
with one or both of Agrobacterium tumefaciens and Agrobacterium
radiobacter biovar 1, and to subsequently add the Arthrobacter
histidinolovorans. This would especially be the situation wherein
the biodehalogenation process is run in a continuous mode.
[0107] As noted above, although the precise identity of the enzymes
which make the method operable has not been made, it is believed
that the enzymes which effectuate the method belong to the class of
enzymes termed "hydrogen halide lyase type dehalogenase".
[0108] The method of biodehalogenation in accordance with the
present invention is carried out by contacting a microorganism or
cell-free enzyme-containing extract with the aqueous composition
containing the unwanted organohalogen contaminants. Such contact is
typically achieved by forming a slurry or suspension of the
microorganism or cell-free extract in the aqueous composition, with
sufficient stirring.
[0109] If desired, the microorganism or enzymes can be removed from
the product stream by filtration, sedimentation, centrifugation or
other means known to those skilled in the art. Alternatively the
microorganisms or enzymes can remain in the final product and
optionally deactivated by thermal sterilization (e.g., by treatment
at 140.degree. C. for 20 seconds) or by the addition of a suitable
concentration of a suitable biocidal agent. Suitable biocidal
agents can be readily selected by those of ordinary skill in the
art. Thus, deactivation of the microorganism can be performed by
reducing the pH of the aqueous mixture to 2.8, then adding a
proprietary biocidal agent (e.g. Proxell.RTM. BD biocidal agent,
which comprises 1,2-benzisothiazolin-3-one) in sufficient quantity,
normally 0.02% to 0.1%, based on the weight of the aqueous
composition. The biocidal agent may be added along with potassium
sorbate.
[0110] The removal of the microorganism may be performed by one or
more of the steps of filtration, centrifugation, sedimentation, or
any other known techniques for removing microbes from a mixture.
The microorganisms mineralize the nitrogen-free organohalogen
compounds, producing CO.sub.2, water, and biomass, with no glycerol
left in the resin. Where the biocatalyst is an immobilized
dehalogenase, the product of the reaction is glycidol.
[0111] A problem associated with the removal of the microbes from
the mixture is that intensive methods of separation, such as
microfiltration, remove not only microbes but also particles of
cationic polymer, with the result that the wet strength properties
are reduced, which is undesirable. Therefore, it is preferable to
leave the deactivated microorganism in the mixture to avoid the
problem of reducing wet strength properties.
[0112] The CPD-forming species in the resin can also be reduced,
and/or inhibited and/or removed by base treatment. In particular,
the resin can be treated with at least one basic agent to raise the
pH of the solution containing the polyamine-epihalohydrin resin to
a pH of at least about 8, more preferably at least about 9, more
preferably at least about 10, with a preferred upper limit being
about 12.5, and a preferred pH range of about 10 to 12 for a
sufficient period of time and at a sufficient temperature to remove
and/or inhibit CPD-forming species in the resin to obtain a storage
stable product. The temperature is preferably at least about
20.degree. C., more preferably at least about 40.degree. C., even
more preferably at least about 50.degree. C., even more preferably
at least about 55.degree. C., and even more preferably at least
about 60.degree. C., with the upper temperature being preferably
less than about 80.degree. C., and can be as high as 100.degree.
C.
[0113] It is understood that the temperature, time and pH are
related so that as the temperature and pH are increased, the time
of base treatment can be shortened to remove the CPD-forming
species. Thus, the time of treatment can be made shorter with
increasing temperature and pH, and is preferably at least about 1
minute, even more preferably at least about 3 min, and most
preferably at least about 5 min. The treatment time can be as long
as about 24 hours, but is preferably up to about 4 hours and most
preferably up to about 1 hour. Preferred combinations of
temperature, time and pH include the time of treatment preferably
being about 5 minutes at 50.degree. C. and pH of 11.5, and 5
minutes at 55.degree. C. and a pH of 10.5 to 11.5. Without being
wished to be bound by theory it is noted that for higher pH's,
shorter periods of time should be used, because the molecular
weight of the resin may get too high and the solution can gel.
[0114] For base treatment according to the present invention, the
polyamide-epihalohydrin reaction, preferably
polyamide-epichlorohydrin reaction, has an epihalohydrin,
preferably epichlorohydrin, to secondary amine group molar ratio of
less than 1, more preferably less than about 0.8, with a preferred
range being about 0.5 to 0.8, and a preferred value being about
0.8. Thus, in other words and being exemplary with respect to
epichlorohydrin, less than 1 mole of epichlorohydrin is utilized
for each secondary amine group of the polyamide, and more
preferably less than about 0.8 mole of epichlorohydrin is utilized
for each secondary amine group.
[0115] As noted above and without wishing to be limited by theory,
it is noted that epichlorohydrin is more reactive with secondary
amine than with acid end groups. Therefore, by having a lower value
of epichlorohydrin, the epichlorohydrin will preferentially react
with the secondary amine than with acid end groups. Also, as the
epichlorohydrin to secondary amine ratio increases there are more
CPD forming species, and would be more CPD forming species to
remove when base treating. Still further, if excess of
epichlorohydrin is present, after the secondary amines react with
the epichlorohydrin, there would still be epichlorohydrin present
to react with the acid end groups, which would be capable of
forming the CPD-forming species.
[0116] It is further noted that there may actually be an increase
of CPD during base treatment, such as when Kymene.RTM. ULX is base
treated. However, as discussed above, any CPD that will be released
by the treatment should be readily soluble, and can therefore be at
least partially washed away from the resin. For example, when the
resin with released CPD is included in a paper product, the CPD can
be at least partially washed out of the paper product, and, due to
the treatment, the resin in the paper product will not produce CPD
or will not produce undesirable amounts of CPD. Still further,
during base treatment, the CPD is reacted to glycidol, which is
hydrolyzed to glycerol.
[0117] The resin solids for base treatment, based upon the weight
of the composition, can be at least about 1%, preferably at least
about 2%, preferably at least about 6%, more preferably at least
about 8% and most preferably at least about 10%. The resin solids
for base treatment can be up to about 40 wt %, preferably up to
about 25 wt %, and most preferably up to about 15 wt %. After base
treatment, the resin can be diluted, typically, with water.
[0118] When referring to the pH, reference is being made to the pH
of the solution immediately after addition of the basic agent. The
pH can vary after addition of the basic agent, or can be maintained
at the initial pH.
[0119] Both organic and inorganic bases can be used as the basic
agent in the present invention. A base is defined as any proton
acceptor (see Advanced Organic Chemistry, Third Ed.; Jerry March;
John Wiley & Sons: New York, 1985, p 218-236, incorporated
herein by reference.) Typical bases include alkali metal
hydroxides, carbonates and bicarbonates, alkaline earth metal
hydroxides, trialkylamines, tetraalkylammonium hydroxides, ammonia,
organic amines, alkali metal sulfides, alkaline earth sulfides,
alkali metal alkoxides, alkaline earth alkoxides, and alkali metal
phosphates, such as sodium phosphate and potassium phosphate.
Preferably, the base will be alkali metal hydroxides (lithium
hydroxide, sodium hydroxide and potassium hydroxide) or alkali
metal carbonates (sodium carbonate and potassium carbonate). Most
preferably, the base comprises inorganic bases including sodium
hydroxide and potassium hydroxide, which are especially preferred
for their low cost and convenience.
[0120] After the base treatment, the resin is preferably stabilized
and stored prior to use. The resin can be stabilized by the
addition of an acid in a manner as discussed above. Thus, the
product can be stabilized to permit storage by improving the
gelation stability by adding sufficient acid to reduce the pH to
less than about 6, preferably less than about 5, and most
preferably less than about 4, with a preferred range being a pH
from about 2.5 to 4. As noted above, any suitable inorganic or
organic acid such as hydrochloric acid, sulfuric acid,
methanesulfonic acid, nitric acid, formic acid, phosphoric and
acetic acid may be used to stabilize the product. Non-halogen
containing acids, such as sulfuric acid, are preferred.
[0121] According to the present invention, the resin is storage
stable with respect to CPD and gelation. With respect to gelation,
the resin is storage stable, when stored at 25.degree. C., for at
least two days, and is more preferably stable for at least one
week, more preferably for at least one month, more preferably for
at least three months, and is even more preferably for at least six
months.
[0122] The acid stabilization is preferably performed about 1
minute to about 24 hours after base treatment, preferably about 1
minute to about 6 hours, most preferably about 1 minute to about 1
hour after the base treatment. The acid stabilized resin can be
stored for extended period of time, such as greater than about 6
months. Of course, the stabilized resin can be used at any time
after stabilization including about 1 minute to 24 weeks after
acidification, about 1 minute to 2 weeks after acidification, and
about 1 minute to 24 hours after acidification.
[0123] As with the acid treatment to remove, inhibit and/or reduce
CPD-forming species, for the base treatment, the resin having at
least reduced levels of formation of CPD can be a resin as produced
in a resin synthesis process without further treatment. Moreover,
the resin can be treated by various processes prior to reduction
and/or removal of the CPD-forming species. Still further, after
treatment to reduce and/or remove CPD-forming species, the resin
can be treated by various processes. Yet still further, the resin
can be treated by various processes prior to reduction and/or
removal of the CPD-forming species, and the resin can also be
treated by various processes after treatment to reduce and/or
remove CPD-forming species. For example, the resin can be treated
by various processes, such as processes to remove low molecular
weight epihalohydrin and epihalohydrin by-products, e.g.,
epichlorohydrin and epichlorohydrin by-products, for example, CPD
in the resin solution. Without limiting the treatments or resins
that can be utilized, it is noted that resins, such as Kymene.RTM.
SLX2, Kymene.RTM. 617 and Kymene.RTM. 557LX (available from
Hercules Incorporated, Wilmington, Del.), could be treated prior to
and/or subsequent to reduction or removal of CPD-forming species
with a base ion exchange column, such as disclosed in U.S. Pat. No.
5,516,885 and WO 92/22601; with carbon adsorption, such as
disclosed in WO 93/21384; membrane separation, e.g.,
ultrafiltration; extraction, e.g, ethyl acetate, such as disclosed
in U.S. Statutory Invention Registration H1613; or
biodehalogenation, such as disclosed in U.S. application Ser. No.
08/482,398, now U.S. Pat. No. 5,972,691, WO 96/40967 and U.S. Pat.
Nos. 5,470,742, 5,843,763 and 5,871,616. The disclosures of each of
these documents is incorporated by reference in their entireties.
In particular, one preferred manner of applying base treatment to
remove or reduce CPD-forming species includes base treatment after
biodehalogenation of the resin.
[0124] As another method to produce polyamine-epihalohydrin resin
products which have reduced levels of formation of CPD upon storage
and minimized levels of CPD in paper products is by treating the
resin utilizing either organic or inorganic bases, or organic or
inorganic acids, such as described above, to raise or lower the pH
of the resin solution to a pH less than 7, with a preferred pH
range being about 5.5 to less than 7, with one preferred pH being
about 6 for a sufficient period of time and at a sufficient
temperature to remove and/or inhibit CPD-forming species in the
resin. This method of treatment is referred to herein as the pH
modified treatment. Preferably, the base comprises alkali metal
hydroxides (lithium hydroxide, sodium hydroxide and potassium
hydroxide) or alkali metal carbonates (sodium carbonate and
potassium carbonate) or alkali metal bicarbonates (sodium
bicarbonate and potassium bicarbonate). Preferred acids include
hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric
acid, formic acid, phosphoric acid and acetic acid. Non-halogen
containing acids, such as sulfuric acid, are preferred.
[0125] The time of treatment can be made shorter with increasing
temperature and increasing pH. The temperature is preferably within
the range of about 30.degree. C. to 80.degree. C., the pH is
preferably about 6, and the time of treatment is preferably about 3
hours to 14 days, with a preferred time of treatment being up to
about 24 hours, more preferably up to about 6 hours. Preferred
combinations of temperature, time and pH, include at 30.degree. C.,
a pH of about 6 and a treatment time of about 6 days; and at
50.degree. C., a pH of about 6, and a treatment time of about 6
hours.
[0126] As with the other treatments to remove, inhibit and/or
reduce CPD-forming species, for the pH modified treatment, the
resin having at least reduced levels of formation of CPD can be a
resin as produced in a resin synthesis process without further
treatment. Moreover, the resin can be treated by various processes
prior to reduction and/or removal of the CPD-forming species. Still
further, after treatment to reduce and/or remove CPD-forming
species, the resin can be treated by various processes. Yet still
further, the resin can be treated by various processes prior to
reduction and/or removal of the CPD-forming species, and the resin
can also be treated by various processes after treatment to reduce
and/or remove CPD-forming species. For the sake of brevity, a
complete description of these processes is not being repeated.
[0127] As still another method of producing polyamine-epihalohydrin
resin products which have reduced levels of formation of CPD upon
storage and minimized levels of CPD in paper products, the resin
can be treated with other catalysts that will remove and/or reduce
the CPD forming species. For example, the resin can be treated with
enzymes. Thus, for example, the CPD-forming species in the resin
can also be reduced and/or removed by treating the resin with an
enzymatic agent that is capable of releasing CPD-forming species
from the resin. The enzymatic agent can comprise one or more
enzymes that are capable of releasing the CPD-forming species from
the resin, such as at least one of esterases, lipases and
proteases. A particularly preferred enzymatic agent according to
the present invention is ALCALASE, which is obtainable from Novo
Nordisk Biochem, North America, Inc. Franklinton, N.C.
[0128] It is noted that following the guidelines set forth in the
instant application one having ordinary skill in the art would be
capable of determining enzymatic agents that are useful to remove
CPD-forming species.
[0129] The use of enzymatic agents to release the CPD-forming
species is beneficial in that base treatment to rebuild molecular
weight, such as that which is utilized with an acid treatment is
utilized to remove CPD-forming species, as described in the acid
treatment embodiment of the present invention, is not needed.
However, base treatment to ensure a desired molecular weight can be
utilized with the enzymatic aspect of the present invention in a
similar manner to the base treatment utilized with the acid
treatment. Also, enzyme-treated resin provides greater wet strength
effectiveness relative to the acid treatment that utilizes base
treatment to rebuild molecular weight.
[0130] The at least one enzymatic agent is preferably added to the
resin under conditions to provide a concentration of enzyme and
suitable conditions to achieve sufficient hydrolysis of CPD forming
species in the resin. For example, depending upon the enzymatic
agent, the temperature can be at least about 0.degree. C.,
preferably about 10.degree. C. to 80.degree. C., and more
preferably about 20.degree. C. to 60.degree. C. The reaction time
can be about 3 minutes to 350 hours, more preferably about 30
minutes to 48 hours, more preferably about 1 hour to 24 hours, and
even more preferably about 2 hours to 6 hours. The pH of the
enzymatic reactions will depend on the pH dependence of the
specific enzyme. The pH can be from about 1 to 11, more preferably
about 2 to 10, even more preferably about 2.5 to 9, and even more
preferably about 7 to 9. The concentration of the enzyme will
depend upon its activity. For example, in the case of ALCALASE, the
enzyme can be present in an amount of about 0.0025 g of ALCALASE
(as received) to 30 g (as received)
polyaminopolyamide-epichlorohydrin resin to 2.5 g of ALCALASE (as
received) to 30 g (as received) polyaminopolyamide-epichlorohydrin
resin, also the enzyme can be present in an amount of about 0.025 g
of ALCALASE (as received) to 30 g (as received)
polyaminopolyamide-epichlorohydrin resin to 0.25 g of ALCALASE (as
received) to 30 g (as received) polyaminopolyamide-epichlorohydrin
resin.
[0131] The preferred reaction conditions can be varied by using the
appropriate types and amounts of enzymes. For example, if the
enzymatic agent has protease activity with a
polyaminopolyamide-epichlorohydrin resin, reaction conditions above
about pH 8 and 40.degree. C. are practical. Practical being defined
as obtaining a reduced CPD-forming resin while having a resin with
the desired viscosity.
[0132] As with the above-discussed procedures for removing and/or
reducing CPD-forming species, the enzyme treatment can be applied
on resins as produced in a resin synthesis process without further
treatment. Moreover, the resins can be treated by various processes
prior to reduction and/or removal of the CPD-forming species. Still
further, after treatment to reduce and/or remove CPD-forming
species, the resin can be treated by various processes. Yet still
further, the resin can be treated by various processes prior to
reduction and/or removal of the CPD-forming species, and the resin
can also be treated by various processes after treatment to reduce
and/or remove CPD-forming species. For the sake of brevity, a
complete description of these processes is not being repeated.
[0133] While the above-mentioned processes are directed to removal
of the CPD forming species from the polymer backbone in a late
stage of the resin synthesis, as noted above, there are other
approaches directed to the inhibition, reduction and/or elimination
of the amount of CPD forming species, such as CPD ester, that can
be formed during the epichlorohydrin reaction. Without wishing to
be bound by theory, CPD ester is formed by the reaction of
epichlorohydrin with residual carboxylic acid groups present in the
prepolymer, such as polyaminoamide prepolymer. Usually the
carboxylic acid groups are end groups. Reducing the amount of
residual carboxylic acid groups present in the prepolymer will
result in a reduction of the amount of CPD ester formed in the
resin. This may be achieved by reducing, minimizing or completely
eliminating carboxylic acid groups (also referred to as acid groups
or carboxylic acids) or residual carboxylic acid functionality
(also referred to as acid functionality and carboxylic
functionality) in the polyaminoamide prepolymer, to thereby obtain,
as discussed below, a low acid number prepolymer.
[0134] Preferably, the polyaminopolyamide-epihalohydrin resin is
produced from a polyaminoamide prepolymer having an acid
functionality less than about 0.5 milliequivalents/dry gram of
prepolymer, more preferably less than about 0.25
milliequivalents/dry gram of prepolymer, even more preferably less
than about 0.1 milliequivalents/dry gram of prepolymer, even more
preferably less than about 0.07 milliequivalents/dry gram of
prepolymer, and even more preferably less than about 0.05
milliequivalents/dry gram of prepolymer, and most preferably would
be undetectable, i.e., it is preferred that the acid functionality
be zero or as close to zero as possible.
[0135] Expressed in another manner, the
polyaminopolyamide-epihalohydrin resin is produced from a
polyaminoamide prepolymer having an acid end group concentration of
less than about 5% as measured by .sup.13C NMR analysis, more
preferably less than about 2.5%, even more preferably less than
about 1%, even more preferably less than about 0.7%, and even more
preferably less than about 0.5%, and most preferably would be
undetectable, i.e., it is preferred that the acid end group
concentration be zero or as close to zero as possible.
[0136] The amount of carboxylic acid groups present in a
polyaminoamide prepolymer can be determined by spectroscopy (NMR,
IR) or by titration. Preferably, the carboxylic acid groups are
determined utilizing NMR, because this technique is more sensitive,
especially when measuring low amounts of acid groups in the resin,
such as when the acid groups are equal to 0.25 milliequivalents/dry
gram of prepolymer or less. A typical procedure for determining the
acid number of prepolymer by .sup.13C NMR analysis is described in
Example 60 with respect to adipic acid and diethylenetriamine
(DETA).
[0137] Moreover, as noted above, titration can be utilized to
determine the number of acid groups, especially when the number of
acid groups is greater than 0.25 milliequivalents/per dry gram. The
procedure for determining the amount of acid groups utilizing
titration is set forth in Example 12.
[0138] The procedure for determining RSV is also set forth in
Example 12.
[0139] Preferably, the prepolymer has an RSV of at least about 0.05
dL/g (deciliter per gram), more preferably at least about 0.075
dL/g, even more preferably at least about 0.1 dL/g. The RSV is
preferably less than about 0.5 dL/g, more preferably less than
about 0.25 dL/g, even more preferably less than about 0.2 dL/g, and
even more preferably less than about 0.15 dL/g. The RSV is
preferably about 0.075 to 0.2 dL/g, more preferably about 0.1 to
0.15 dL/g.
[0140] Preferred combinations of acid functionality of the
prepolymer from which the polyamidopolyamine resin is produced and
the RSV of the prepolymer are wherein the prepolymer has an acid
functionality less than about 0.5 milliequivalents/dry gram of
prepolymer and a RSV of about 0.05 to about 0.25 dL/g, more
preferably about 0.075 to 0.2 dL/g, and even more preferably about
0.1 to 0.15 dL/g; the prepolymer has an acid functionality of less
than about 0.25 milliequivalents/dry gram of prepolymer and a RSV
of about 0.05 to about 0.25 dL/g, more preferably about 0.075 to
0.2 dL/g, and even more preferably 0.1 to 0.15 dL/g; the prepolymer
has an acid functionality of less than about 0.1
milliequivalents/dry gram of prepolymer and a RSV of about 0.05 to
about 0.25 dL/g, more preferably about 0.075 to 0.2 dL/g, and even
more preferably about 0.1 to 0.15 dL/g; the prepolymer has an acid
functionality of less than about 0.07 milliequivalents/dry gram of
prepolymer and a RSV of about 0.05 to about 0.25 dL/g, more
preferably about 0.075 to 0.2 dL/g, and even more preferably about
0.1 to 0.15 dL/g; and the prepolymer has an acid functionality of
less than about 0.05 milliequivalents/dry gram of prepolymer and a
RSV of about 0.05 to about 0.25 dL/g, more preferably about 0.075
to 0.2 dL/g, and even more preferably about 0.1 to 0.15 dL/g.
[0141] Preferred combinations of acid end group concentration, as
measured by .sup.13C NMR analysis, of the prepolymer from which the
polyamidopolyamine resin is produced and the RSV of the prepolymer
are wherein the prepolymer has an acid end group concentration of
less than about 5% and a RSV of about 0.05 to about 0.25 dL/g, more
preferably about 0.075 to 0.2 dL/g, and even more preferably about
0.1 to 0.15 dL/g; the prepolymer has an acid end group
concentration of less than about 2.5% and a RSV of about 0.05 to
about 0.25 dL/g, more preferably about 0.075 to 0.2 dL/g, and even
more preferably 0.1 to 0.15 dL/g; the prepolymer has an acid end
group concentration of less than about 1% and a RSV of about 0.05
to about 0.25 dL/g, more preferably about 0.075 to 0.2 dL/g, and
even more preferably about 0.1 to 0.15 dL/g; the prepolymer has an
acid end group concentration of less than about 0.7% and a RSV of
about 0.05 to about 0.25 dL/g, more preferably about 0.075 to 0.2
dL/g, and even more preferably about 0.1 to 0.15 dL/g; and the
prepolymer has an acid end group concentration of less than about
0.5% and a RSV of about 0.05 to about 0.25 dL/g, more preferably
about 0.075 to 0.2 dL/g, and even more preferably about 0.1 to 0.15
dL/g.
[0142] The choice of dicarboxylic acid or dicarboxylic acid
derivative used in the synthesis of the polyaminoamide can have a
significant effect on the acid end group concentration of the
polyaminoamide and the polyamidopolyamine resin prepared from it.
In particular and without wishing to be bound by theory, it is
hypothesized that 6 and 7 carbon aliphatic dicarboxylic acids and
their derivatives, such as adipic and pimelic acids, and to a
lesser extent an 8 carbon aliphatic dicarboxylic acid and its
derivatives, such as suberic acid, can undergo side reactions
during the course of the polyaminoamide synthesis that result in
increased levels of acid end groups. These side reactions are
believed to originate with a deprotonation of the carbon alpha to
the carbonyl group in the dicarboxylic acid, its derivatives or in
the polyaminoamide backbone. The conditions of the polyaminoamide
synthesis are conducive to such a deprotonation reaction because of
the basic conditions under which the reaction is carried out. The
deprotonation reaction is then followed by an intramolecular
reaction of the resulting anion with the other carbonyl group of
the diacid moiety to form a 5-membered ring in the case of adipic
acid, a 6-membered ring in the case of pimelic acid and a
7-membered ring in the case of suberic acid. These cyclic
byproducts can generate carboxylic acid end groups either under the
conditions of the polyaminoamide synthesis or when the
polyaminoamide is dissolved in water. Dicarboxylic acids that have
the potential to form 5, 6, and 7-membered rings as a result of
this type of intramolecular reaction are less favored than
dicarboxylic acids that will not form these structures. The use of
glutaric acid or its derivatives significantly reduce the formation
of such a cyclic byproduct since the intramolecular reaction would
result in the formation of a 4-membered ring which is much less
favored energetically than formation of 5, 6, and 7-membered rings.
Similarly, succinic acid, malonic acid, oxalic acid, azeleic acids
and their derivatives would be expected to have a much lower
tendency to undergo this type of side reaction. Moreover, esters
are preferred over acids. For example, with respect to the above,
it is noted that glutaric acid provides a lower concentration of
acid end groups than adipic acid, dimethyl glutarate provides a
lower concentration of acid end groups than glutaric acid, dimethyl
adipate is preferred over adipic acid, and preferred esters include
dimethyl glutarate and dimethyl succinate. Exemplary preferred
materials include DBE 4, DBE 5 and DBE 9, which are respectively,
dimethyl succinate, dimethyl glutarate, and a 2/1 mixture of
dimethyl glutarate/dimethyl succinate, obtainable from Dupont.
[0143] One method to minimize carboxylic acid groups is to use
endcapping agents in the preparation of the prepolymer (generally
referred to herein as "endcapping" or "endcapped prepolymer"). For
example, when preparing an endcapped polyaminoamide prepolymer one
may replace a portion of the diacid with a monofunctional acid
and/or may replace a portion of the polyalkylenepolyamine with a
monofunctional amine. Various procedures, conditions and materials
can be utilized when preparing the prepolymer, including
conventional procedures, conditions and materials, and include
those described herein. Starting with an equimolar mixture of
diacid and polyalkylenepolyamine, for every 1 mole of diacid or
polyalkylenepolyamine removed a quantity of preferably about 2
moles of monofunctional acid or monofunctional amine endcapper is
used. In this regard, as the replaced moles of monofunctional acid
is lowered below 2, the prepolymer ends up with increased amine end
groups, whereas the molecular weight of the prepolymer is lowered
as the replaced moles of monofunctional acid is raised above 2
moles. In contrast, as the replaced moles of monofunctional amine
is lowered below 2, the prepolymer ends up with acid groups,
whereas the molecular weight of the prepolymer is lowered as the
replaced moles of monofunctional amine is raised above 2 moles.
[0144] One can control the molecular weight of a condensation
polymer by adjusting the relative amounts of bifunctional and
monofunctional reactants (endcappers) in the system.
[0145] The theory of molecular weight control and the effect of
monofunctional additives for condensation polymer is well known, as
see, for example, P. J. Flory, "Principles of Polymer Chemistry",
pp. 91-95, Cornell University Press, Ithaca N.Y. (1953), which is
incorporated by reference in its entirety. DP.sub.n is defined as
the number-average degree of polymerization or the average number
of monomer units in a polymer chain. Equation 1 defines the
DP.sub.n in terms of the molar ratios of the components, assuming
complete reaction of all functional groups. DP.sub.n=(1+r)/(1-r)
[1.] where r is defined as the ratio of the monomer units and is
calculated as follows: r=A/(B+2C) [2.] A and B are the difunctional
monomer components and C is the monofunctional component
(end-capper). The quantity r will always be less than 1.
[0146] In this invention, a controlled molecular weight prepolymer
is prepared by using specific amounts of a monofunctional reactant.
The prepolymer composition may be defined in terms of a
polyaminoamide prepared from A parts dicarboxylic acid, B parts
polyalkylenepolyamine and C parts monofunctional endcapping moiety,
all parts given as molar quantities.
[0147] When A>B the endcapping moiety will be a monofunctional
amine and C will equal about 2(A-B). When B>A the endcapper will
be a monofunctional acid and C will be equal to about 2(B-A). For
this case Equation [2.] is rewritten as: r=B/(A+2C) [3.]
[0148] The prepolymers should have a molecular weight that is
sufficiently high so that the resulting resin is capable of
providing sufficient wet strength to a substrate, such as paper.
Moreover, the molecular weight of the prepolymers should not be so
high so that the resulting resin gels. Preferably, the prepolymers
have a range of DP.sub.n of from about 5 to 50, more preferably a
range of from about 10 to 50, and most preferably a range of
DP.sub.n is from about 15 to 50.
[0149] Various temperatures and reaction times can be utilized in
the reaction, including conventional temperatures and time forming
prepolymers. Temperatures of between about 125.degree. C. and
260.degree. C. are preferred, more preferably between about
165.degree. C. and 200.degree. C., and the reaction mixtures are
maintained at these temperatures for preferably between about 3 to
12 hours, more preferably between about 6 to 10 hours.
[0150] Suitable monofunctional amines include, but are not limited
to, monofunctional primary amines, including monoalkyl amines and
monoalkanol amines, and monofunctional secondary amines, including
dialkyl amines and dialkanol amines.
[0151] Monofunctional primary amines include, but are not limited
to butylamine, ethanolamine (i.e., monoethanolamine, or MEA),
cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine,
4-methylcyclohexylamine, benzylamine, isopropanolamine (i.e.,
monoisopropanolamine), mono-sec-butanolamine,
2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane,
tetrahydrofurfurylamine, furfurylamine, 3-amino-1,2-propanediol,
1-amino-1-deoxy-D-sorbitol, and 2-amino-2-ethyl-1,3-propanedi
Monofunctional secondary amines include, but are not limited to,
diethylamine, dibutylamine, diethanolamine (i.e., DEA),
di-n-propylamine, diisopropanolamine, di-sec-butanolamine, and
N-methylbenzylamine.
[0152] Monofunctional carboxylic acids suitable for the endcapped
polyaminoamide prepolymer include, but are not limited to, benzoic
acid, 2-hydroxybenzoic acid (i.e., salicylic acid),
3-hydroxybenzoic acid, acetic acid, phenylacetic acid, propionic
acid, butyric acid, valeric acid, caproic acid, caprylic acid,
2-ethylhexanoic acid, oleic acid, ortho-toluic acid, meta-toluic
acid, and para-toluic acid, ortho-methoxybenzoic acid,
meta-methoxybenzoic acid, and para-methoxybenzoic acid.
[0153] Monofunctional carboxylic acid esters suitable for the
endcapped polyaminoamide prepolymer include, but are not limited
to, methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate,
methyl propionate, ethyl propionate, methyl butyrate, ethyl
butyrate, methyl phenyl acetate, and ethyl phenyl acetate.
[0154] The volatility of the endcapping agent should be low enough
so that this agent remains in the prepolymerization reaction at the
temperature at which the reaction is being conducted. Particularly,
when the prepolymer is prepared by thermally driven
polycondensation, volatility is a significant feature of the
endcapping agent; in this instance, an endcapping agent of lesser
volatility is preferred. The boiling point of the endcapping agent
should be high enough so that, at the temperature being employed to
drive off the condensation product--i.e., water where a diacid
reactant is used, and alcohol in the case of diester--the agent is
not also removed.
[0155] These endcapped polyaminoamide prepolymers can then be
converted to polyaminoamide-epihalohydrin resins, preferably
polyaminoamide-epichlorohydrin resins, according to the practices
and procedures described earlier. The resins produced from these
polyaminoamide prepolymers can also be subjected to
biodehalogenation to remove epihalohydrin, e.g., epichlorohydrin,
based residual by-products, and these resins form CPD in the wet
strength resin solution or in the paper product at a much reduced
rate. In addition to biodehalogenation, the
polyaminoamide-epichlorohydrin resins may be treated to reduce or
remove CPD forming species by any desired treatment, such as by
utilizing the above-described acid treatment, and/or treated with
any procedure for removing halogen-containing residuals.
[0156] Expanding upon the above, it is once again noted that any
combination of treatments may be employed in order to bring about
desired low levels of CPD forming species and/or low levels of
halogen-containing residuals in the resin. Thus, the reduced acid
group resin can be treated to reduce or remove CPD forming species
and/or halogen-containing residuals, and therefore obtain even
lower levels of formation of CPD upon storage or reduce the level
of halogen-containing residuals therein. For example, the resin can
be treated by various processes, such as processes to remove low
molecular weight epihalohydrin and epihalohydrin by-products, e.g.,
epichlorohydrin and epichlorohydrin by-products, for example, CPD
in the resin solution, and/or to remove CPD forming species that
may still be present in the resin. Without limiting the treatments
that can be utilized, it is noted that produced low acid resins
could by various techniques, such as the acid treatments disclosed
herein, and as in U.S. application Ser. No. 09/330,200 to obtain an
even further reduction of CPD-forming species. Still further, the
resins could with treated with a base ion exchange column, such as
disclosed in U.S. Pat. No. 5,516,885 and WO 92/22601; with carbon
adsorption, such as disclosed in WO 93/21384; membrane separation,
e.g., ultrafiltration; extraction, e.g, ethyl acetate, such as
disclosed in U.S. Statutory Invention Registration H1613; or
biodehalogenation, such as disclosed in U.S. application Ser. No.
08/482,398, now U.S. Pat. No. 5,972,691, WO 96/40967 and U.S. Pat.
Nos. 5,470,742, 5,843,763 and 5,871,616. The disclosures of each of
these documents is incorporated by reference in their
entireties.
[0157] Moreover, the acid groups can be reduced by variation of the
dicarboxylic acid/polyalkylenepolyamine molar ratio and the cook
profile in the prepolymer synthesis. This route to obtaining
polyaminoamide prepolymers with low levels of acid groups employs
an excess of polyalkylenepolyamine in the synthesis. This variation
is generally referred to herein as "amine excess reaction" or
"amine excess prepolymer". This involves using a
polyalkylenepolyamine to diacid molar ratio of greater than 1 which
results in a polyaminoamide with a preponderance of amine end
groups. Moreover, various procedures, conditions and materials can
be utilized when preparing the prepolymer, including conventional
procedures, conditions and materials, and include those described
herein.
[0158] Expanding upon the above, it is noted that altering the
stoichiometry of polyalkylenepolyamine to dibasic acid, i.e.,
diethylenetriamine to adipic acid, to have an excess of the
polyalkylene polyamine results in more carboxyl groups being
converted to amide groups, thereby reducing the acid group
concentration in the prepolymer. The stoichiometry of
polyalkylenepolyamine to dibasic acid, e.g., diethylenetriamine to
adipic acid, can range from greater than about 1.0:1.0, on a molar
basis, to 1.7:1.0, more preferably, greater than about 1.01:1.0 to
1.4:1.0.
[0159] While changing of the stoichiometry of the reagents in favor
of excess polyalkylenepolyamine results in polyaminoamides with
lower acid group concentrations for a given time/temperature cook
profile, it also results in lower molecular weights for the
polymer. This lower molecular weight has a detrimental effect on
the ability of the resulting resin to impart significant wet
strength properties into paper. In order to maintain the desired
molecular weight characteristics of the polymer, extended cook
times and/or higher temperatures are employed to build prepolymers
with low acid group concentrations. Therefore, temperatures between
about 125.degree. C. and 260.degree. C. are used to cook the
prepolymer reaction mixture, preferably between about 165.degree.
C. and 200.degree. C., and the reaction mixtures are maintained at
these temperatures for between about 3 to 12 hours, preferably
between about 6 to 10 hours. These conditions result in
polyaminoamides with reduced acid groups. As with the
above-discussed end-capping, the prepolymers should have a
molecular weight that is sufficiently high so that the resulting
resin is capable of providing sufficient wet strength to a
substrate, such as paper. Moreover, the molecular weight of the
prepolymers should not be so high so that the resulting resin gels.
Thus, as discussed above with respect to end-capping, the
prepolymers preferably have a range of DP.sub.n of from about 5 to
50, more preferably a range of from about 10 to 50, and most
preferably a range of DP.sub.n is from about 15 to 50.
[0160] Preferably, the temperature of the reaction for forming the
prepolymer is varied from one or more lower temperatures during one
or more initial stages of the reaction and raised to one or more
higher temperatures during one or more later stages of the
reaction. In this manner, the molecular weight of the prepolymer
can be built up during the lower temperature stage, while avoiding
volatization of low molecular species, e.g., monomers. The
temperature can then be raised to reduce or remove the acid groups
while raising the molecular weight. For example, the prepolymer
reaction can be initially performed at temperatures of about 125 to
200.degree. C., preferably about 140 to 180.degree. C., for about
0.5 to 5 hours, more preferably about 1 to 4 hours. The reaction
temperature can then be raised to about 150 to 260.degree. C., more
preferably about 180 to 225.degree. C., in one or more stages, and
maintained at this one or more higher temperatures for about 0.25
to 10 hours, more preferably about 0.5 to 5 hours.
[0161] Alternatively, instead of raising the temperature, longer
cooking times can be utilized to build-up the molecular weight of
the prepolymer. Additionally, the temperature can be raised to a
lower extent, with an increase in cook time.
[0162] The amine excess prepolymer can then be converted to
polyaminoamide-epihalohydrin resins, such as
polyaminoamide-epichlorohydrin resins, according to the practices
and procedures described earlier. These resins can also be
subjected to any treatment and/or any combination of treatments,
such as discussed herein with respect to end capping. For example,
the resin can be subjected to any treatment and/or any combination
of treatments to reduce or remove CPD forming species and/or reduce
and/or remove halogen-containing residuals.
[0163] Another method of making polyaminoamide prepolymers with low
levels of residual acid functionality is to add a reactive amine at
later stages of the polycondensation reaction in forming the
prepolymer with continued heating in order to amidate any residual
acid groups. This method is referred to herein as "post-added amine
reaction" or "post-added amine prepolymer". Preferably, the
polycondensation reaction is at least about 70% complete, more
preferably at least about 80% complete, and even more preferably at
least about 90% complete when the reactive amine is added. The
degree of conversion, and hence the degree of completion of the
polycondensation reaction can be determined by monitoring the
amount of distillate, i.e., the amount of water or alcohol, that is
formed during the reaction and comparing this to the theoretical
value.
[0164] In order to facilitate the reaction with the reactive amine,
a vacuum, e.g., a slight vacuum to a high vacuum, may be applied to
the reactor to aid in removal of the byproducts formed in the
condensation reaction of the reactive amine with carboxylic acid
groups. Also, a gas sparge, e.g., an inert gas sparge, such as with
nitrogen, argon and/or helium, may be introduced to the reactor to
aid in the removal of condensation byproducts. This procedure can
be performed while applying vacuum or under conditions of normal
atmospheric pressure.
[0165] While not wishing to be bound by any particular theory,
monofunctional amines can be utilized in which instance it would
appear that amide, alkyl and/or hydrocarbon end groups would form.
Moreover, polyfunctional amines can be utilized in which instance
it would appear that amides would be formed.
[0166] The initial stages of the prepolymer reaction can be
initially performed at temperatures of about 125.degree. C. to
200.degree. C., preferably about 140.degree. C. to 180.degree. C.,
for about 0.5 to 5 hours, more preferably about 1 to 4 hours. After
the post-addition of the amine compound, the reaction temperature
can then be maintained or can be raised to about 150.degree. C. to
225.degree. C., more preferably about 170.degree. C. to 225.degree.
C., in one or more stages, and maintained at this one or more
higher temperatures for about 0.25 to 10 hours, more preferably
about 0.5 to 5 hours.
[0167] The post-added amine should be added in an amount such that
the total molar quantity of polyalkylenepolyamine plus post-added
amine is greater than the total molar amount of dicarboxylic acid.
The initial molar ratio of polyalkylenepolyamine to dicarboxylic
acid can range from about 0.6:1.0 to 1.4:1.0, preferably about
0.8:1.0 to 1.2:1.0, more preferably about 0.9:1.0 to 1.1:1.0 and
most preferably about 0.95:1.0 to 1.05:1.0. The post-added amine is
preferably added in a quantity such that the ratio of
polyalkylenepolyamine to dicarboxylic acid to post-added amine is
in the range of about 0.6:1.0:0.7 to 1.4:1.0:0.3, preferably about
0.8:1.0:0.4 to 1.2:1.0:0.2, more preferably about 0.9:1.0:0.2 to
1.1:1.0:0.1 and most preferably about 0.95:1.0:0.1 to
1.05:1.0:0.05.
[0168] A polyaminoamide prepared from an equimolar mixture of
polyalkylenepolyamine and diacid will theoretically have an equal
number of amine and carboxylic acid groups. By adding a reactive
amine in the later stages of the reaction, the acid groups present
in the polyaminoamide can be amidated. The reactive amine may be
any substance that contains at least one primary or secondary amine
functionality and may contain a mixture of primary and secondary
amine functionalities. This may be a monofunctional amine,
difunctional amine or polyfunctional amine. This reactive amine is
referred to as a "post-added amine". Preferred post-added amines
are aliphatic amines.
[0169] Suitable monofunctional primary amines include, but are not
limited to, butylamine, amylamine, hexylamine, heptylamine
octylamine, nonylamine, decylamine, ethanolamine (i.e.,
monoethanolamine, or MEA), cyclohexylamine, allylamine,
2-methylcyclohexylamine, 3-methylcyclohexylamine,
4-methylcyclohexylamine, benzylamine, isopropanolamine (i.e.,
monoisopropanolamine), mono-sec-butanolamine,
2-(2-aminoethoxy)ethanol, 2-amino-2-methyl-1-propanol,
tris(hydroxymethyl)aminomethane, tetrahydrofurfurylamine,
furfurylamine, 3-amino-1,2-propanediol, 1-amino-1-deoxy-D-sorbitol,
morpholine aminoethylmorpholine and
2-amino-2-ethyl-1,3-propanediol. Among the monofunctional secondary
amines which are suitable are diethylamine, dibutylamine,
diethanolamine (i.e., DEA), di-n-propylamine, diisopropanolamine,
di-sec-butanolamine, pyrrolidine, piperidine, diallylamine, and
N-methylbenzylamine.
[0170] Examples of appropriate diamines include, but are not
limited to, ethylenediamine, propylenediamine,
hexamethylenediamine, 1,10-diaminodecane,
1,3-diamino-3-hydroxypropane, 2-(2-aminoethylamino)ethanol,
1,2-diaminocyclohexane, 1,10-diaminodecane, and piperazine.
[0171] Polyfunctional amines that may be used as the post-added
amine include, but are not limited to, aminoethyl piperazine, the
polyalkylene polyamines, including polyethylene polyamines,
polypropylene polyamines, polybutylene polyamines, polypentylene
polyamines, polyhexylene polyamines and so on and their mixtures
may be employed of which the polyethylene polyamines represent an
economically preferred class. More specifically, the polyalkylene
polyamines contemplated for use may be represented as polyamines in
which the nitrogen atoms are linked together by groups of the
formula --C.sub.nH.sub.2n-- where n is a small integer greater than
unity and the number of such groups in the molecule ranges from two
up to about eight. The nitrogen atoms may be attached to adjacent
carbon atoms in the group --C.sub.nH.sub.2n-- or to carbon atoms
further apart, but not to the same carbon atom. This invention
contemplates not only the use of such polyamines as
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
and dipropylenetriamine, which can be obtained in reasonably pure
form, but also mixtures and various crude polyamine materials. For
example, the mixture of polyethylene polyamines obtained by the
reaction of ammonia and ethylene dichloride, refined only to the
extent of removal of chlorides, water, excess ammonia, and
ethylenediamine, is a satisfactory starting material. The term
"polyalkylene polyamine" employed in the claims, therefore, refers
to and includes any of the polyalkylene polyamines referred to
above or to a mixture of such polyalkylene polyamines and
derivatives thereof.
[0172] The post-capped polyaminoamides can then be converted to
polyaminoamide-epihalohydrin resins, such as
polyaminoamide-epichlorohydrin resins, according to the practices
and procedures described earlier. These resins can also be
subjected to any treatment and/or any combination of treatments,
such as discussed herein with respect to end capping and amine
excess treatment during the reaction. For example, the resin can be
subjected to any treatment and/or any combination of treatments to
reduce or remove CPD forming species and/or reduce and/or remove
halogen-containing residuals.
[0173] Moreover, any manner of providing polyamine-epihalohydrin
resin having reduced and/or removed CPD-forming species can be
utilized alone or in combination according to the instant
invention. When utilized in combination, the techniques can be
utilized simultaneously, sequentially or in an overlapping manner.
For example, and without limiting the combinations according to the
present invention, treatment with an enzymatic agent can be
followed by acid or base treatment.
[0174] Moreover, it noted that a mixture of wet strength agents can
be utilized according to the present invention. For example, it is
noted that cationic water-soluble resins, derived from the reaction
of epihalohydrins, such as epichlorohydrin, and polyalkylene
polyamines, such as ethylenediamine (EDA),
bis-hexamethylenetriamine (BHMT) and hexamethylenediamine (HMDA)
have long been known. These polyalkylene polyamine-epihalohydrin
resins are described in patents such as U.S. Pat. No. 3,655,506 to
J. M. Baggett, et al. and others such as U.S. Pat. No. 3,248,353
and U.S. Pat. No. 2,595,935 to Daniel et al. from which their
generic description as "Daniel's Resins" arises. The disclosures of
these patents are incorporated by reference herein in their
entireties.
[0175] While not wishing to be bound by theory, these
polyamine-epihalohydrin resins do not have acid end groups, and
therefore appear to not include CPD-forming species, e.g., CPD
esters. Thus, while their wet strength abilities are less than
those of polyaminopolyamide-epihalohydrin resins, it is beneficial
to include the polyalkylene amine-epihalohydrin resins in admixture
with the polyaminopolyamide-epihalohydrin resins in view of their
lower cost and their lack of formation of CPD upon storage.
[0176] The polyalkylene polyamine employed in the present invention
can preferably be selected from the group consisting of
polyalkylene polyamines of the formula:
H.sub.2N--[CHZ-(CH.sub.2).sub.n--NR--].sub.x--H
[0177] where:
[0178] n=1-7,
[0179] x=1-6
[0180] R=H or CH.sub.2Y,
[0181] Z=H or CH.sub.3,
[0182] and
[0183] Y=CH.sub.2Z, H, NH.sub.2, or CH.sub.3,
[0184] polyalkylene polyamines of the formula:
H.sub.2N--[CH.sub.2--(CHZ).sub.m--(CH.sub.2).sub.n--NR--].sub.x--H
[0185] where:
[0186] m=1-6, n=1-6, and m+n=2-7,
[0187] R=H or CH.sub.2Y,
[0188] Z=H or CH.sub.3,
[0189] and
[0190] Y=CH.sub.2Z, H, NH.sub.2, or CH.sub.3,
and mixtures thereof.
[0191] Polyalkylene polyamine-epihalohydrin resins comprise the
water-soluble polymeric reaction product of epihalohydrin and
polyalkylene polyamine. In making Daniel's Resins the polyalkylene
polyamine is added to an aqueous mixture of the epihalohydrin so
that during the addition the temperature of the mixture does not
exceed 60.degree. C. Lower temperatures lead to further
improvements, though too low a temperature may build dangerously
latent reactivity into the system. The preferred temperatures fall
within the range of about 25.degree. C. to about 60.degree. C. More
preferred is a range of from about 30.degree. C. to about
45.degree. C.
[0192] Alkylation of the polyamine occurs rapidly proceeding to
form secondary and tertiary amines depending on the relative
amounts of epihalohydrin and polyamine. The levels of epihalohydrin
and polyamine are such that between about 50% and 100% of the
available amine nitrogen sites are alkylated to tertiary amines.
Preferred levels are between about 50% and about 80% alkylation of
the amine nitrogen sites. Excess epihalohydrin beyond that required
to fully alkylate all the amine sites to the tertiary amine is less
preferred because this results in increased production of
epihalohydrin byproducts.
[0193] Following complete addition of the polyamine, the
temperature of the mixture is allowed to rise and /or the mixture
is heated to effect crosslinking and azetidinium formation. The
crosslinking rate is a function of concentration, temperature,
agitation, and the addition conditions of the polyamine, all of
which can be readily determined by those skilled in the art. The
crosslinking rate can be accelerated by the addition of small shots
of the polyamine or other polyamines of the present invention or
addition of various alkalies at or near the crosslinking
temperature.
[0194] The resin can be stabilized against further crosslinking to
gelation by addition of acid, dilution by water, or a combination
of both. Acidification to pH 5.0 or less is generally adequate.
[0195] The preferred polyamines are bishexamethylenetri amine,
hexamethylenediamine, and their mixtures.
[0196] In order to more clearly describe the present invention, the
following non-limiting examples are provides for the purpose of
representation, and are not to be construed as limiting the scope
of the invention. All parts and percentages in the examples are by
weight unless indicated otherwise. Moreover, ND in the Examples
indicates "Not Detected".
EXAMPLES
Comparative Example 1
Accelerated aging of a Polyaminopolyamide-epichlorohydrin (epi)
Resin (Control)
[0197] Kymene.RTM. ULX2 wet-strength resin, a
polyaminopolyamide-epi resin which contains less than about 5 ppm
of DCP and less than about 50 ppm of CPD and is available from
Hercules Incorporated (Wilmington, Del.), was obtained from the
Voreppe, France plant, and had a total solids of 13.6 wt % and a pH
of 2.7. This Kymene.RTM. is designated as Resin A. A portion of
Resin A was charged into a bottle containing a magnetic stirrer and
capped. The bottle was placed in a 50.degree. C. water bath and
maintained at 50.degree. C. Periodically, an aliquot was removed
from the bottle and submitted for GC analysis. The results are
reported in Table 1. Another portion of Resin A was charged into a
bottle and capped. The bottle was placed in a 32.degree. C. oven
and maintained at 32.degree. C. Periodically, an aliquot was
removed from the bottle and submitted for analysis by gas
chromatography (GC). The results are reported in Table 1.
[0198] GC was used to determine epi and epi by-products in the
treated and untreated resins using the following method. The resin
sample was absorbed onto an Extrelut column (available from EM
Science, Extrelut QE, Part #901003-1) and extracted by passing
ethyl acetate through the column. A portion of the ethyl acetate
solution was chromatographed on a wide-bore capillary column. If
flame ionization detector (FID) was used, the components are
quantitated using n-octanol as the internal standard. If an
electrolytic conductivity (ELCD) detector or if the
halogen-specific (XSD) detector was used, an external standard
method using peak matching quantitation was employed. The data
system was either a Millennium 2010 or HP ChemStation. The FID
detector was purchased from Hewlett-Packard (HP) as part of a Model
5890 GC. The ELCD detector, Model 5220, was purchased from OI
Analytical. The XSD detector was purchased from OI Analytical,
Model 5360 XSD. The GC instrument used was a HP Model 5890 series
II. The column was DB-WAX (Megabore, J&W Scientific, Inc.) 30
m.times.0.53 mm with 1.5 micron film thickness. For the FID and
ELCD, the carrier gas was helium with a flow rate of 10 mL/min. The
oven program was 35.degree. C. for 7 minutes, followed by ramping
at 8.degree. C./min to 200.degree. C. and holding at 200.degree. C.
for 5 minutes. The FID used hydrogen at 30 mL/min and air at 400
mL/min at 250.degree. C. The ELCD used n-propanol as the
electrolyte with an electrolyte flow rate setting of 50% with a
reactor temperature of 900.degree. C. The XSD reactor was operated
in an oxidative mode at 1100.degree. C. with a high purity air flow
rate of 25 mL/min. TABLE-US-00002 TABLE 1 Temp Time 1,3-DCP 2,3-DCP
3-CPD (Celsius) (hours) (ppm) (ppm) (ppm) 20 0 ND 0.6 3.6 50 25 ND
0.6 13.3 50 70 ND 0.6 20.6 50 146 ND 0.6 28.8 50 217 ND 0.7 36.3 50
369 ND 0.7 43.3 50 386 ND 0.8 47.0 50 482 ND 0.5 52.0 32 72 ND 0.6
11.0 32 96 ND 0.6 13.0 32 144 ND 0.7 16.1 32 240 ND 0.6 21.9 32 408
ND 0.5 28.7 32 576 ND 0.7 34.3 32 744 ND 0.8 36.8 32 1248 ND 0.8
46.3 32 1584 ND 0.8 48.3
Comparative Example 2
Lab Biodehalogenation of a Polyaminopolyamide-epi Resin and
Accelerated Aging
[0199] Kymene.RTM. SLX2 wet-strength resin, a
polyaminopolyamide-epi resin available from Hercules Incorporated
(Wilmington, Del.), was obtained from the Voreppe, France plant,
and had a total solids of 13.0 wt % and a pH of 2.9. This
Kymene.RTM. resin is designated as Resin B. A 200 gram sample of
Resin B was charged into a 3-necked, round-bottomed flask equipped
with a magnetic stirrer, a condenser and an air sparge. The pH was
adjusted to 5.8 with 10% aqueous sodium hydroxide. To the mixture
was added 100 grams of a blend of microorganisms comprising an
inoculum from a biodehalogenated polyaminopolyamide-epichlorohydrin
resin. This represents a starting value of cell concentration of
from about 10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 2.4
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 27480 ppm of urea, 4160
ppm of magnesium sulfate, and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
10% aqueous sodium hydroxide. After 28 hours, a sample was removed
and submitted for GC analysis. The mixture was cooled to room
temperature, and the pH was adjusted to 3.0 with 10% sulfuric acid.
The resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 2.
TABLE-US-00003 TABLE 2 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius)
(hours) (ppm) (ppm) (ppm) 20 0 ND 0.7 0.1 50 24 0.1 0.5 3.5 50 46
0.1 0.5 5.9 50 119 0.2 0.6 12.3 50 138 0.2 0.6 12.9 50 210 0.3 0.6
19.5 50 334 0.4 0.6 20.9 32 23 0.2 0.5 0.8 32 46 0.2 0.5 1.8 32 115
0.2 0.5 3.4 32 163 0.1 0.5 4.6 32 331 0.2 0.6 6.9 32 497 0.2 0.6
7.6 32 665 0.2 0.6 9.0 32 1001 0.2 0.5 13.1 32 1457 0.2 0.4
10.5
Comparative Example 3
Lab Biodehalogenation of a Polyaminopolyamide-epi Resin and
Accelerated Aging
[0200] A 180 gram sample of Resin B was charged into a 3-necked,
round-bottomed flask equipped with a magnetic stirrer, a condenser,
an air sparge and a pH meter. The pH was adjusted to 5.8 with 8.6
grams of 10% aqueous sodium hydroxide. To the mixture was added 18
g of a blend of microorganisms comprising an inoculum from a
biodehalogenated polyaminopolyamide-epichlorohydrin resin. This
represents a starting value of cell concentration of from about
10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 1.6
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 27480 ppm of urea, 4160
ppm of magnesium sulfate and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
10% aqueous sodium hydroxide. After 28 hours, the mixture was
cooled to room temperature, the pH was adjusted to 3.0 with 10%
sulfuric acid and 1.23 grams of biocide [Proxel.RTM. BD from Zeneca
Biocides, 1,2-benzisothiazolin-3-one, (CAS name,
1,2-benzisothiazol-3(2H)-one, RN=2634-33-5), 19.3% active solids]
was added. A sample was removed and submitted for GC analysis. The
resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 3.
TABLE-US-00004 TABLE 3 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius)
(hours) (ppm) (ppm) (ppm) 20 0 ND 0.6 0.1 50 18 ND 0.6 2.2 50 42 ND
0.6 4.0 50 137 ND 0.6 8.4 50 161 ND 0.6 9.0 50 233 ND 0.7 11.9 50
355 ND 0.7 14.2 50 526 ND 0.6 18.9 50 670 ND 0.6 18.7 32 41 ND 0.6
0.8 32 113 ND 0.6 3.2 32 335 ND 0.6 5.6 32 522 ND 0.3 3.3 32 671 ND
0.7 9.8 32 977 ND 0.7 11.3 32 1697 ND 0.7 7.8
Example 1
Lab Biodehalogenation of an Acid-treated Polyaminopolyamide-epi
Resin and Accelerated Aging
[0201] A 250 g portion of Resin B was charged into a bottle
containing a magnetic stirrer. The pH was adjusted to 1.0 with 96%
sulfuric acid. The bottle was capped and placed in a 50.degree. C.
water bath and maintained at 50.degree. C. Periodically, aliquots
were removed from the bottle and submitted for GC analysis. After
24 hours, the resin was cooled and had pH of 1.1 and a total solids
of 14.1 wt %. A 180 gram sample of this resin was charged into a
3-necked, round-bottomed flask equipped with a magnetic stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 23.2 grams of 10% aqueous sodium hydroxide. To the mixture was
added 18 g of a blend of microorganisms comprising an inoculum from
a biodehalogenated polyaminopolyamide-epichlorohydrin resin. This
represents a starting value of cell concentration of from about
10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 1.6
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 27480 ppm of urea, 4160
ppm of magnesium sulfate and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
10% aqueous sodium hydroxide. After 29 hours, the mixture was
cooled to room temperature, the pH was adjusted to 3.0 with 10%
sulfuric acid, and 0.57 grams of biocide [Proxel.RTM. BD from
Zeneca Biocides, 1,2-benzisothiazolin-3-one, (CAS name,
1,2-benzisothiazol-3(2H)-one, RN=2634-33-5), 19.3% active solids]
was added. A sample was removed and submitted for GC analysis. The
resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 4.
[0202] Using a pH lower than the typical storage pH reduced CPD
reformation. This treatment resulted in about a 77-80% reduction in
CPD reformation in the resin relative to an untreated control
(Comparative Example 3) and about a 93% reduction relative to
commercially obtained Kymene.RTM. ULX2 wet strength resin
(Comparative Example 1). TABLE-US-00005 TABLE 4 Temp Time 1,3-DCP
2,3-DCP 3-CPD (Celsius) (hours) (ppm) (ppm) (ppm) 20 0 0.0 0.8 0.1
50 17 0.0 0.8 0.3 50 88 ND 0.9 1.5 50 160 ND 0.8 2.7 50 255 ND 1.0
3.1 50 328 ND 0.9 3.2 50 496 ND 0.8 3.8 32 160 ND 0.9 0.8 32 256 ND
0.9 1.3 32 328 ND 1.0 2.8 32 496 ND 0.9 1.5 32 664 ND 0.9 1.9 32
1001 ND 1.0 2.3 32 1774 ND 1.1 3.6
Example 2
Lab Biodehalogenation of an Acid-treated Polyaminopolyamide-epi
Resin and Accelerated Aging
[0203] Kymene.RTM. SLX2 wet-strength resin which is a
polyaminopolyamide-epi resin available from Hercules Incorporated
was obtained from the Lilla Edet, Sweden plant, and had a 13.5 wt %
total solids and a pH of 2.9. This Kymene.RTM. is designated as
Resin C. A 900 gram portion of Resin C was charged into a 4-necked,
round-bottomed flask equipped with an overhead stirrer and a
condenser. The pH was adjusted to 1.0 with 12.2 grams of 96%
sulfuric acid. The reaction mixture was heated to 50.degree. C.
with a water bath and maintained at 50.degree. C. Periodically,
aliquots were removed from the flask and submitted for GC analysis.
After 24 hours, the resin was cooled and had pH of 1.1, a total
solids of 14.9%. A 800 gram sample of this acid-treated resin was
charged into a 4-necked, round-bottomed flask equipped with an
overhead stirrer, a condenser, an air sparge and a pH meter. The pH
was adjusted to 5.8 with 66.5 grams of 20% aqueous sodium
hydroxide. To the mixture was added 80 grams of a blend of
microorganisms comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 6.9 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used were: Arthrobacter histidinolovorans (HK1) and
Agrobacterium tumefaciens (HK7). The flask was placed in a
30.degree. C. water bath and maintained at 30.degree. C. The pH was
maintained at 5.8 by periodic addition of 10% aqueous sodium
hydroxide. After 45 hours, an aliquot was removed and submitted for
GC analysis and the mixture was cooled to room temperature. A 190
gram portion was adjusted to pH 3.0 with 1.42 grams of 96% sulfuric
acid and 2.3 grams of biocide solution was added. [The biocide
solution consisted of 10% active Proxel.RTM. BD (from Zeneca
Biocides) and 1.67% potassium sorbate in deionized water.] The
resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 5.
TABLE-US-00006 TABLE 5 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius)
(hours) (ppm) (ppm) (ppm) 20 0 ND 1.1 ND 50 92 ND 1.1 1.0 50 164 ND
2.0 2.0 50 332 ND 1.3 2.0 32 332 ND 1.3 1.1 32 668 ND 1.1 1.4 32
1004 ND 1.3 1.9
Example 3
Crosslinking of Example 2 at 60.degree. C.
[0204] A 175 gram sample of the resin of Example 2 was charged into
a 4-necked, round-bottomed flask equipped with an overhead stirrer
and a condenser. The pH was adjusted to 10.5 with 6.7 grams of 20%
aqueous sodium hydroxide. The reaction mixture was heated to
60.degree. C. by placing the flask in a temperature controlled
water bath. The reaction mixture was maintained at 60.degree. C.
The Gardner-Holdt viscosity at 25.degree. C. was monitored. After
the Gardner-Holdt viscosity reached B (2.5 hours after base
addition), the reaction was quenched by the addition of 2.4 grams
of 96% sulfuric acid. The reaction mixture was allowed to cool to
25.degree. C. The pH was adjusted to 2.8 with an additional 0.12
grams of 96% sulfuric acid and 2.1 grams of biocide solution was
added. [The biocide solution consisted of 10% active Proxel.RTM. BD
(from Zeneca Biocides) and 1.67% potassium sorbate in deionized
water.] The resin had a total solids of 15.6 wt % and a Brookfield
viscosity of 95 cps (spindle #2 at 60 rpm using a Brookfield DV-II
viscometer at 25.degree. C.). The resin was subjected to
accelerated aging as described in Comparative Example 1. The
results are reported in Table 6. TABLE-US-00007 TABLE 6 Temp Time
1,3-DCP 2,3-DCP 3-CPD (Celsius) (hours) (ppm) (ppm) (ppm) 20 0 0.1
0.9 1.9 50 66 0.1 0.7 1.5 32 162 0.1 0.8 1.8 32 330 0.1 0.8 1.5 32
666 0.2 0.6 1.1
Example 4
Crosslinking of Example 2 at 50.degree. C.
[0205] A 175 gram sample of the resin of Example 2 was charged into
a 4-necked, round-bottomed flask equipped with an overhead stirrer
and a condenser. The pH was adjusted to 10.5 with 6.2 grams of 20%
aqueous sodium hydroxide. The reaction mixture was heated to
50.degree. C. by placing the flask in a temperature controlled
water bath. The reaction mixture was maintained at 50.degree. C.
The Gardner-Holdt viscosity at 25.degree. C. was monitored. An
additional 0.4 grams of 20% aqueous sodium hydroxide was added 3.3
hours after the base addition. After the Gardner-Holdt viscosity
reached B-C (4.5 hours after initial base addition), the reaction
was quenched by the addition of 2.3 grams of 96% sulfuric acid. The
reaction mixture was allowed to cool to 25.degree. C. The pH was
adjusted to 2.8 with an additional 0.19 grams of 96% sulfuric acid
and 1.9 grams of biocide solution was added. [The biocide solution
consisted of 10% active Proxel.RTM. BD (from Zeneca Biocides) and
1.67% potassium sorbate in deionized water.] The resin had a total
solids of 15.7 wt % and a Brookfield viscosity of 117 cps (spindle
#2 at 60 rpm using a Brookfield DV-II viscometer at 25.degree. C.).
The resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 7.
TABLE-US-00008 TABLE 7 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius)
(hours) (ppm) (ppm) (ppm) 20 0 0.5 0.9 2.4 50 53 0.6 0.9 2.3 32 175
0.4 0.8 1.4 32 360 0.5 0.9 1.6
Comparative Example 4
[0206] Kymene.RTM. ULX2 wet-strength resin which is a
polyaminopolyamide-epi resin available from Hercules Incorporated
(Wilmington, Del.) was obtained from the Lilla Edet, Sweden plant,
and had a 13.3 wt % total solids and a pH of 2.7. This resin is
designated as Resin D. Resin D was subjected to accelerated aging
as described in Comparative Example 1. The results are reported in
Table 8. TABLE-US-00009 TABLE 8 Temp Time 1,3-DCP 2,3-DCP 3-CPD
(Celsius) (hours) (ppm) (ppm) (ppm) 20 0 ND 0.4 7.6 50 24 ND 0.4
16.3 50 96 ND 0.5 28.8 50 168 ND 0.5 35.7 50 380 ND 0.5 45.9 32 167
ND 0.5 22.3 32 432 ND ND 34.9 32 864 ND 0.4 47.7
Example 5
Synthesis of a High-solids Polyaminopolyamide Resin Followed by
Acid-treatment and Biodehalogenation
[0207] A 1-L jacketed resin kettle was fitted with a condenser, a
pH meter, a temperature controlled circulating bath, an addition
funnel and a mechanical stirrer. To the kettle was added 749.76 g
of 51.2% aqueous poly(adipic acid-co-diethylenetriamine) (available
from Hercules Incorporated) and 209.9 g of water. The solution was
heated to 30.degree. C. and then 149.9 g of epichlorohydrin
(Aldrich, 99%) was added over about 3 minutes. The temperature was
allowed to increase to 35.degree. C. and was maintained at this
temperature. Two hours after the addition of the epichlorohydrin,
225 g of water was added and the temperature was raised to
50.degree. C. The Gardner-Holdt viscosity at 25.degree. C. was
monitored. After the Gardner-Holdt viscosity reached M, the
reaction was quenched by the addition 325 g of water containing
38.73 g of 96% sulfuric acid. The reaction mixture was allowed to
cool to 25.degree. C. The pH was adjusted to 2.8 with an additional
9.17 grams of 96% sulfuric acid and 75 grams of water was added.
The total solids content of this resin was 33.0% and 1687 grams of
resin was recovered. The resin was diluted to 25% solids with 539.8
grams of water. A 2-L jacketed resin kettle was fitted with a
condenser, a pH meter, a temperature controlled circulating bath
and a mechanical stirrer. To the kettle was added 1944 grams of
this resin and the pH was adjusted to 1.0 with 35.1 grams of 96%
sulfuric acid and the temperature was raised and maintained at
50.degree. C. After 24 hours, the reaction mixture was cooled to
21.degree. C. and the pH was adjusted from 1.1 to 2.8 with 202.1 g
of 10% aqueous sodium hydroxide. A 1440 gram sample of this resin
was adjusted to pH 5.8 with 176.4 grams of 10% aqueous sodium
hydroxide. To a 4-necked, round-bottomed flask equipped with an
overhead stirrer, a condenser, an air sparge and a pH meter was
charged 800 grams of this resin and 80.0 g of a blend of
microorganisms comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 6.9 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used were: Arthrobacter histidinolovorans (HK1) and
Agrobacterium tumefaciens (HK7). The flask was placed in a
30.degree. C. water bath and maintained at 30.degree. C. The pH was
maintained at 5.8 by periodic addition of 20% aqueous sodium
hydroxide. After 86 hours, the mixture was cooled to room
temperature and refrigerated.
Example 6
Crosslinking of Example 5
[0208] A 200 gram sample of the resin of Example 5 was charged into
a 4-necked, round-bottomed flask equipped with an overhead stirrer
and a condenser. The pH was adjusted to 9.1 with 6.0 grams of 20%
aqueous sodium hydroxide. The reaction mixture was heated to
60.degree. C. by placing the flask in a temperature controlled
water bath. The reaction mixture was maintained at 60.degree. C.
The Gardner-Holdt viscosity at 25.degree. C. was monitored. After
the Gardner-Holdt viscosity reached K-L (144 minutes after base
addition), the reaction was quenched by the addition of 2.8 grams
of 96% sulfuric acid in 30 grams of deionized water. The reaction
mixture was allowed to cool to 25.degree. C. and 98 grams of
additional deionized water was added. The pH was adjusted to 2.8
with an additional 0.28 grams of 96% sulfuric acid and 3.78 grams
of biocide solution was added. [The biocide solution consisted of
10% active Proxel.RTM. BD (from Zeneca Biocides) and 1.67%
potassium sorbate in deionized water.] The resin had a total solids
of 13.6%. The resin was subjected to accelerated aging as described
in Comparative Example 1. The results are reported in Table 9.
TABLE-US-00010 TABLE 9 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius)
(hours) (ppm) (ppm) (ppm) 20 0 ND 1.3 1.3 50 72 0.2 1.7 1.5 50 168
ND 1.3 2.0 50 336 ND 1.0 1.9 32 168 ND 1.6 1.7 32 336 ND 1.6 1.9 32
672 ND 1.9 2.5
Example 7
Handsheet Evaluation of Examples 2, 3, 4, 5, 6 and Comp. Example
4
[0209] Paper handsheets were prepared on a Noble and Wood handsheet
machine at pH 7.5 with 50:50 Rayonier bleached Kraft:Crown Vantage
bleached hardwood Kraft dry lap pulp refined to 500 mL Canadian
standard freeness. Sheets were generated having 40 lb/3000 sq. ft.
basis weight containing 0.5-1.0% of treated resin (based on the
solids of untreated resin). Handsheets were wet pressed to 33%
solids and dried on a drum drier at 230.degree. C. for 55 seconds
to give 3-5% moisture. Some of the handsheets were oven-cured at
80.degree. C. for 30 minutes. The paper was conditioned according
to TAPPI Method T-402 and tested. Dry tensile strength was
determined using TAPPI Method T-494. Wet tensile strength was
determined using TAPPI Method T-456 with a two hour soak time. Some
of the paper was natural aged by conditioning at greater than two
weeks at 50% relative humidity and at 23.degree. C. and then
tested. Dry tensile strength was determined using TAPPI Method
T-494. Wet tensile strength was determined using TAPPI Method T-456
with a two hour soak time. To measure CPD in paper products, five
grams of the paper product was extracted with water according to
the method described in European standard EN 647, dated October
1993. Then 5.80 grams of sodium chloride was dissolved into 20 ml
of water extract. The salted aqueous extract was transferred to a
20 gram capacity Extrelut column and allowed to saturate the column
for 15 minutes. After three washes of 3 ml ethyl acetate and
saturation of the column, the Extrelut column was eluted until 300
ml of eluent has been recovered in about 1 hour. The 300 ml of
ethyl acetate extract was concentrated to about 5 ml using a 500 ml
Kuderna-Danish concentrating apparatus (if necessary, further
concentrating was done by using a micro Kuderna-Danish apparatus).
The concentrated extract was analyzed by GC using a halogen
specific detector (XSD).
[0210] Results for oven-cured paper are reported in Table 10 and
for natural aged paper in Table 11. Although the acid treatment
reduces the effectiveness of the resin (Examples 2 and 5), most of
the effectiveness was recovered by adjusting the pH of the resin
with a base and allowing it to crosslink (Examples 3, 4 and 6).
TABLE-US-00011 TABLE 10 Oven-Cured Paper. Basis Wt. Normalized dry
wet % % of CPD in % tensile tensile wet/ Comp. Paper Example Added
pH lbs/in lbs/in dry Ex. 4 (ppb) Blank -- 7.5 18.50 0.52 3 11
<30 Comp. Ex. 4 0.50 7.5 25.15 4.86 19 100 -- Comp. Ex. 4 1.00
7.5 27.92 6.01 22 100 319 Example 4 0.50 7.5 24.39 4.40 18 91 --
Example 4 1.00 7.5 23.79 5.29 22 88 <30 Example 3 0.50 7.5 24.06
4.39 18 90 -- Example 3 1.00 7.5 26.15 5.30 20 88 <30 Example 6
0.50 7.5 26.08 4.59 18 94 -- Example 6 1.00 7.5 25.93 5.88 23 98 36
Example 2 0.50 7.5 22.70 2.94 13 61 -- Example 2 1.00 7.5 22.55
4.05 18 67 <30 Example 5 0.50 7.5 22.27 3.24 15 67 -- Example 5
1.00 7.5 23.38 4.46 19 74 39
[0211] TABLE-US-00012 TABLE 11 Natural Aged Paper Basis Wt.
Normalized dry wet % % of CPD in % tensile tensile wet/ Comp. Paper
Example Added pH lbs/in lbs/in dry Ex. 4 (ppb) Blank -- 7.5 19.87
0.64 3 14 -- Comp. Ex. 4 0.50 7.5 25.04 4.66 19 100 -- Comp. Ex. 4
1.00 7.5 26.28 5.67 22 100 330 Example 4 0.50 7.5 23.75 3.95 17 85
-- Example 4 1.00 7.5 26.61 5.03 19 89 <30 Example 3 0.50 7.5
24.05 4.02 17 86 -- Example 3 1.00 7.5 26.11 5.37 21 95 -- Example
6 0.50 7.5 23.58 4.27 18 92 -- Example 6 1.00 7.5 26.34 5.50 21 97
66 Example 2 0.50 7.5 21.60 2.60 12 56 -- Example 2 1.00 7.5 22.92
3.55 15 63 -- Example 5 0.50 7.5 21.61 3.03 14 65 -- Example 5 1.00
7.5 22.41 4.08 18 72 --
Comparative Example 5
Lab Biodehalogenation of a Polyaminopolyamide-epi Resin
[0212] A 400 gram sample of Resin C was charged into a 4-necked,
round-bottomed flask equipped with an overhead stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 11.19 grams of 20% aqueous sodium hydroxide. To the mixture
was added 40 g of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin.
This represents a starting value of cell concentration of from
about 10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 3.47
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 27480 ppm of urea, 4160
ppm of magnesium sulfate and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 46 hours, a sample was removed
and submitted for GC analysis, the mixture was cooled to room
temperature, the pH was adjusted to 2.8 with 2.58 g of 96% sulfuric
acid and 5.41 grams of biocide solution was added. [The biocide
solution consisted of 10% active Proxel.RTM. BD (from Zeneca
Biocides) and 1.67% potassium sorbate in deionized water.] The
resin had a total solids of 14.1 wt %.
Example 8
Lab Biodehalogenation of an Acid-treated Polyaminopolyamide-epi
Resin and Accelerated Aging
[0213] A 847 gram portion of Resin C was charged into a 4-necked,
round-bottomed flask equipped with an overhead stirrer and a
condenser. The pH was adjusted to 1.0 with 10.3 grams of 96%
sulfuric acid. The reaction mixture was heated to 80.degree. C.
with a water bath and maintained at 80.degree. C. -Periodically,
aliquots were removed from the flask and submitted for GC analysis.
After 3 hours, the resin was cooled and had pH of 1.1. The pH was
adjusted to 2.9 with 27.3 grams of 20% aqueous sodium hydroxide.
This resin had a total solids of 14.5%. A 400 gram sample of this
acid-treated resin was charged into a 4-necked, round-bottomed
flask equipped with an overhead stirrer, a condenser, an air sparge
and a pH meter. The pH was adjusted to 5.8 with 14.13 grams of 20%
aqueous sodium hydroxide. To the mixture was added 40 grams of a
blend of microorganisms comprising an inoculum from a
biodehalogenated polyaminopolyamide-epichlorohydrin resin. This
represents a starting value of cell concentration of from about
10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 3.47
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 27480 ppm of urea, 4160
ppm of magnesium sulfate and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 46 hours, a sample was removed
and submitted for GC analysis and the mixture was cooled to room
temperature.
Example 9
Crosslinking of Example 8 at 60.degree. C.
[0214] A 175 gram sample of the resin of Example 8 was charged into
a 4-necked, round-bottomed flask equipped with an overhead stirrer,
a condenser and a pH meter. The pH was adjusted to 10.5 with 5.94
grams of 20% aqueous sodium hydroxide. The reaction mixture was
heated to 60.degree. C. by placing the flask in a temperature
controlled water bath. The reaction mixture was maintained at
60.degree. C. The Gardner-Holdt viscosity at 25.degree. C. was
monitored. After the Gardner-Holdt viscosity reached B-C (2.5 hours
after base addition), the reaction was quenched by the addition of
2.1 grams of 96% sulfuric acid. The reaction mixture was allowed to
cool to 25.degree. C. The pH was adjusted to 2.8 with an additional
0.25 grams of 96% sulfuric acid and 2.1 grams of biocide solution
was added. [The biocide solution consisted of 10% active
Proxel.RTM. BD (from Zeneca Biocides) and 1.67% potassium sorbate
in deionized water.] The resin had a total solids of 15.4 wt %.
Example 10
Handsheet Evaluation of Examples 2, 4, 8, 9 and Comp. Examples 4
and 5
[0215] The procedure of Example 7 was used to evaluate Examples 2,
4, 8, 9 and Comp. Examples 4 and 5. Results for oven-cured paper
are reported in Table 12. The results with the two different acid
treatment conditions were similar (Example 4, pH 1.0 at 50.degree.
C. for 24 hours compared to Example 9, pH 1.0 at 80.degree. C. for
3 hours). Although the acid treatment reduces the effectiveness of
the resin (Example 8), most of the effectiveness was recovered by
adjusting the pH of the resin with a base and allowing it to
crosslink (Example 9). TABLE-US-00013 TABLE 12 Basis Wt. Normalized
dry wet % % of CPD in % tensile tensile wet/ Comp. Paper Example
Added pH lbs/in lbs/in dry Ex. 4 (ppb) Blank -- 7.5 21.15 0.65 3 16
<30 Comp. Ex. 4 0.50 7.5 22.74 4.18 18 100 Comp. Ex. 4 1.00 7.5
27.22 6.00 22 100 344 Example 4 0.50 7.5 25.26 4.43 18 106 Example
4 1.00 7.5 26.97 5.44 20 91 <30 Comp. Ex. 5 0.50 7.5 23.59 4.59
19 110 Comp. Ex. 5 1.00 7.5 23.63 5.44 23 91 269 Example 8 0.50 7.5
21.50 2.86 13 68 Example 8 1.00 7.5 23.32 4.16 18 69 36 Example 9
0.50 7.5 24.38 4.48 18 107 Example 9 1.00 7.5 24.48 5.13 21 85
<30
Example 11
Acid Test
[0216] The amount of CPD producing species can be estimated using
the following test. A portion of resin to be tested was charged
into a bottle containing a magnetic stirrer. The pH was adjusted to
1.0 with 96% sulfuric acid. The bottle was capped and placed in a
50.degree. C. water bath and maintained at 50.degree. C. with
stirring. Periodically, aliquots were removed from the bottle and
submitted for GC analysis. The CPD produced after 24 hours is used
to estimate the amount of CPD producing species. This test clearly
shows the reduction in the CPD-producing species (Examples 1-6
compared to Resins A-D from Comparative Examples in Table 13,
reported in wet basis of the resin). TABLE-US-00014 TABLE 13 12.1
Time GC 1,3-DCP 2,3-DCP 3-CPD Resin (hours) detector (ppm) (ppm)
(ppm) Resin A 0 FID ND 1 10 Resin A 6 FID ND 1 82 Resin A 24 FID ND
1 204 Resin A 96 FID ND 2 203 Resin A 168 FID ND 1 205 Resin B 0
FID 475 ND 181 Resin B 6 FID 483 ND 357 Resin B 24 FID 459 ND 473
Resin C 0 FID 830 2 356 Resin C 2 FID 834 2 482 Resin C 6 FID 833 2
541 Resin C 24 FID 828 2 755 Example 1 24 XSD ND 0.9 13.9 Example 1
192 XSD ND 0.9 17.7 Example 2 0 XSD ND 0.1 ND Example 2 24 XSD ND
1.3 4.5 Example 2 48 XSD ND 1.2 6.8 Example 3 0 XSD 0.1 0.8 2.1
Example 3 24 XSD 0.1 0.8 2.1 Example 3 48 XSD 0.1 0.8 2.3 Example 4
0 XSD 0.5 0.9 1.9 Example 4 24 XSD 0.6 0.9 4.3 Example 4 48 XSD 0.6
1.0 4.7 Resin D 0 FID ND 1 13 Resin D 2 FID ND ND 50 Resin D 6 FID
ND ND 115 Resin D 24 FID ND ND 242 Resin D 50 FID ND ND 290 Example
5 0 FID ND 5 4 Example 5 24 FID ND 4 25 Example 5 48 FID ND 3 32
Example 6 0 XSD 0.1 1.7 1.0 Example 6 24 XSD 0.1 1.8 8.9 Example 6
48 XSD ND 1.7
Example 12
Preparation of Endcapped Polyaminoamide Prepolymer
[0217] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 33.18 g hexanoic acid (caproic acid, 0.2856 mole)
dropwise through an addition funnel, followed by 417.55 g adipic
acid (2.857 mole) through a powder funnel while stirring the
reaction mixture. The temperature of the reaction mixture was
maintained below 125.degree. C. by controlling the rate at which
the adipic acid was added to the reaction. The temperature was
raised to 170.degree. C. and maintained there for 4 hours. A vacuum
of 7.5'' water was applied throughout this period. During this time
distillate was removed through the-Dean-Stark trap. The total
amount of distillate removed was 105 mL. The theoretical amount of
distillate was 108 mL (6.0 moles water). A volume of 640 mL of hot
water (.about.70.degree. C.) was cautiously added to the product
which was stirred until the prepolymer was dissolved. After cooling
to room temperature the product was bottled. The total solids of
this product was 50.51 wt % and the reduced specific viscosity
(RSV) was 0.1088 dL/g measured in 1.0N NH.sub.4Cl at 2.0%.
[0218] The amine number and acid number were determined by
titration.
[0219] Amine number titrations were performed as follows: This
method is used for the determination of total amine content of
polyaminoamide prepolymers. The sample is dissolved in a 1:1
ethylene glycol-isopropanol mixture. The resulting solution is
titrated potentiometrically with 1 N hydrochloric acid using a
combination pH electrode available from Beckman Instruments, Inc.,
2500 Harbor Blvd., Fullerton, Calif. 92634, Cat. No. 39537, or
equivalent, and an automatic titrator, equipped with a 20 mL buret.
More specifically, 3 to 4 grams of sample, weighed to the nearest
0.0001 g, in duplicate, are added into a 100-150 mL beaker
containing a small stirring bar, such as a magnetic stirring bar
having a 1-1/2'' length. A 1:1 ethylene glycol-isopropanol mixture
(prepared by combining, in a container, 1 liter of ethylene glycol,
laboratory grade, available from VWR Scientific, Cat. No. JTL715,
or Fisher Scientific, Cat. No. E177, or equivalent, with 1 liter of
isopropanol, e.g., isopropyl alcohol (2-propanol), laboratory
grade, available from VWR Scientific, Cat. No. VW3250, or
equivalent) is added to the beaker. Place the beaker on a magnetic
stirrer, such as a magnetic stirrer available from VWR Scientific
Co., and stir to dissolve. To expedite dissolution, place the
beaker on a steam bath or in a heated water bath. Insert the
electrode in the solution and set up the titrator for mV
titrations. Set the rate of titration at approximately 2 mL/min.
Titrate the sample solution potentiometrically with standardized 1
N HCl solution (prepared by adding approximately 400 mL of 1:1
ethylene glycol-isopropanol to a 1 liter volumetric flask, adding
92 mL of concentrated hydrochloric acid, such as, hydrochloric
acid, concentrated, reagent grade, available from VWR Scientific,
Cat. No. VW31 10, or equivalent, mixing thoroughly, allowing the
solution to cool to room temperature, and diluting to volume with
1:1 ethylene glycol-isopropanol, which is standardized using 2 to 3
grams of tri(hydroxymethyl)aminomethane (THAM), while maintaining
mixing, but avoiding splashing the sample on the sides of the
beaker. Determine the volume of titrant consumed at the equivalence
point, which is the midpoint of the major inflection (NOTE: For
example, when the sample size is 3.5 grams, approximately 7.2 mL of
1.16 N HCl is consumed to reach the equivalence point. Calculate
the amine concentration in the sample, as meq/g, on a dry basis,
using Equation 4. V .times. .times. 2 .times. N .times. 100 W
.times. .times. 2 .times. TS = meq .times. / .times. g .times.
.times. total .times. .times. amines Eq .times. .times. ( 4 )
##EQU1## where:
[0220] V2=volume of titrant consumed by the sample, mL
[0221] N=normality of the titrant
[0222] W2=weight of sample, g
[0223] TS=% total solids of prepolymer sample
[0224] Acid number titrations are performed as follows:
[0225] Examine the sample visually. If the sample has begun to
crystallize and appears hazy, gently warm the sample in a container
in a warm water bath or over an oven or steam bath until it is
clear and homogeneous. Mix well before weighing.
[0226] Weigh two 5-g portions of sample, to the nearest 0.0001 g,
into separate beakers or flasks. Add neutralized ethyl alcohol
(such as, denatured ethyl alcohol, 90%--available from VWR
Scientific, Cat. No. VW0470, or Fisher Scientific, Cat. No. A995-4,
or equivalent, which is neutralized to a faint pink phenolphthalein
end point with 0.1 N alcoholic KOH solution using a phenolphthalein
indicator solution, 1%) to each in an amount of 60-100 mL so as to
cover the electrode, and stir or swirl to dissolve the sample.
Insert the electrode (a combination pH electrode, such as available
from Beckman Instruments, Inc., 2500 Harbor Blvd., Fullerton,
Calif. 92634, Cat. No. 39537, or equivalent) into the solution and
turn on the stirrer to maintain a mild vortex of stirred solution,
and using an automatic titrator equipped with a 20 mL buret and
stirrer, titrate each sample with 0.1 N alcoholic KOH past the
inflection endpoint, and determine the volume of titrant consumed
at the midpoint of the inflection, measuring the titration volume
to 0.01 mL.) Typical titration parameters for a Metrohm titrator
are: titration rate=2 mL/min for a 20 mL buret and recorder
range=pH 14 full scale. Calculate the acid concentration in the
samples as meq/g, on a dry basis, using Equation 5. V .times. N
.times. 100 Ws .times. TS = meq .times. / .times. g .times. .times.
Acid Eq .times. .times. ( 5 ) ##EQU2## where:
[0227] N=normality of KOH titrant
[0228] V=volume of KOH titrated to the end point
[0229] Ws=weight of prepolymer sample, g
[0230] TS=% total solids of prepolymer sample
[0231] This material had an amine number of 5.25 meq/g and an acid
number of 0.356 meq/g, determined as described above.
[0232] The reduced specific viscosity (RSV) of the prepolymer is
determined by utilizing a 2 wt % solution of the polymer in 1 N
ammonium chloride (obtained by adding 53.5+/-0.1 g of NH.sub.4Cl to
a 1 liter container, and diluting to volume with distilled water)
at 25.degree. C. using a Ubbelohde viscometer, i.e., Ubbelohde
Viscometer tubes, No. 1, with Viscometer Constant C=0.01, available
from Visco Systems, Yonkers, N.Y., or Schott, Hofheim, Germany, or
Brinkmann Instruments, Westbury, N.Y. Flow times of the 2 wt %
polymer solution and the ammonium chloride pure solvent are
measured and the relative viscosity (Nrel) calculated. The reduced
viscosity is calculated from the relative viscosity. This method is
based on ASTM D446.
Example 13
Preparation of Endcapped Polyaminoamide Prepolymer
[0233] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 294.78 g diethylenetriamine (DETA, 2.8947 mole) and
12.86 g ethanolamine (monoethanolamine, MEA). To this reactor was
added 438.42 g adipic acid (3.00 mole) through a powder funnel
while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 170.degree. C. and maintained there for 4
hours, a vacuum of 7.5'' water was applied throughout this period.
During this time distillate was removed through the Dean-Stark
trap. The total amount of distillate removed was 102 mL. The
theoretical amount of distillate was 108 mL (6.0 moles water), a
volume of 640 mL of hot water (.about.70.degree. C.) was cautiously
added to the product which was stirred until the prepolymer was
dissolved. After cooling to room temperature the product was
bottled. The total solids of this product was 51.56 wt % and the
RSV was 0.1263 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This
material had an amine number of 5.25 meq/g and an acid number of
0.330 meq/g, determined by titration as previously described.
Example 14
Preparation of Endcapped Polyaminoamide Prepolymer
[0234] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 28.25 g 2,2-dimethylolpropionic acid (DMPA,
2,2-bis(hydroxymethyl)propionic acid; 0.2106 mole) followed by
423.03 g adipic acid (2.8947 mole) through a powder funnel while
stirring the reaction mixture. The temperature of the reaction
mixture was maintained below 125.degree. C. by controlling the rate
at which the adipic acid was added to the reaction. The temperature
was raised to 170.degree. C. and maintained there for 4 hours, a
vacuum of 7.5'' water was applied throughout this period. During
this time distillate was removed through the Dean-Stark trap. The
total amount of distillate removed was 96 mL. The theoretical
amount of distillate was 108 mL (6.0 moles water), a volume of 650
mL of hot water (.about.70.degree. C.) was cautiously added to the
product which was stirred until the prepolymer was dissolved. After
cooling to room temperature the product was bottled. The total
solids of this product was 51.00 wt % and the RSV was 0.1377 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. This material had an amine
number of 5.50 meq/g and an acid number of 0.38 meq/g, determined
by titration as previously described.
Example 15
Preparation of Endcapped Polyaminoamide Prepolymer
[0235] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 26.99 g cyclohexane-carboxylic acid (0.2106 mole)
followed by 423.03 g adipic acid (2.8947 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 170.degree. C. and maintained there for 4
hours, a vacuum of 7.5'' water was applied throughout this period.
During this time distillate was removed through the Dean-Stark
trap. The total amount of distillate removed was 95 mL. The
theoretical amount of distillate was 108 mL (6.0 moles water), a
volume of 650 mL of hot water (.about.70.degree. C.) was cautiously
added to the product which was stirred until the prepolymer was
dissolved. After cooling to room temperature the product was
bottled. The total solids of this product was 47.98 wt % and the
RSV was 0.1186 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This
material had an amine number of 5.36 meq/g and an acid number of
0.27 meq/g, determined by titration as previously described.
Example 16
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0236] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 150.degree. C. and maintained there for 1
hour. During this time 15 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 160.degree. C.
and maintained there for 1 hour. During this time an additional 50
mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 170.degree. C. and maintained there
for 1 hour. During this time an additional 25 mL distillate was
removed through the Dean-Stark trap. At this point, 19.38 g (0.15
mole) of 1-(2-aminoethyl)piperazine was added to the reactor. The
temperature was then raised to 180.degree. C. and maintained there
for 2 hours. During the two hour cook at 180.degree. C. a vacuum of
10'' Hg was maintained in the reactor. During this time an
additional 35 mL distillate was removed through the Dean-Stark
trap, a volume of 640 mL of hot water (.about.70.degree. C.) was
then cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 49.60 wt
% and the RSV was 0.1008 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.67 meq/g and an acid
number of 0.0685 meq/g, determined by titration as previously
described.
Example 17
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0237] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 150.degree. C. and maintained there for 1
hour. During this time 20 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 160.degree. C.
and maintained there for 1 hour. During this time an additional 60
mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 170.degree. C. and maintained there
for 1 hour. During this time an additional 25 mL distillate was
removed through the Dean-Stark trap. At this point, 15.48 g (0.15
mole) of DETA was added to the reactor. The temperature was then
raised to 180.degree. C. and maintained there for 2 hours. During
the two hour cook at 180.degree. C. a vacuum of 10'' Hg was
maintained in the reactor. During this time an additional 10 mL
distillate was removed through the Dean-Stark trap, a volume of 640
mL of hot water (.about.70.degree. C.) was then cautiously added to
the product which was stirred until the prepolymer was dissolved.
After cooling to room temperature the product was bottled. The
total solids of this product was 49.33 wt % and the RSV was 0.0977
dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This material had an
amine number of 5.92 meq/g and an acid number of 0.0203 meq/g,
determined by titration as previously described.
Example 18
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0238] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 150.degree. C. and maintained there for 1
hour. During this time 15 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 160.degree. C.
and maintained there for 1 hour. During this time an additional 60
mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 170.degree. C. and maintained there
for 1 hour. During this time an additional 30 mL distillate was
removed through the Dean-Stark trap. At this point, 15.48 g (0.15
mole) of DETA was added to the reactor. The temperature was
maintained at 170.degree. C. for an additional hour. During this
period an additional 5 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 180.degree. C.
and maintained there for 2 hours. During the two hour cook at
180.degree. C. a vacuum of 10'' Hg was maintained in the reactor.
During this time an additional 35 mL distillate was removed through
the Dean-Stark trap, a volume of 640 mL of hot water
(.about.70.degree. C.) was then cautiously added to the product
which was stirred until the prepolymer was dissolved. After cooling
to room temperature the product was bottled. The total solids of
this product was 49.65 wt % and the RSV was 0.1071 dL/g, determined
in 1.0N NH.sub.4Cl at 2.0%. This material had an amine number of
5.86 meq/g and an acid number of 0.0201 meq/g, determined by
titration as previously described.
Example 19
Preparation of Polyaminopolyamide-Epichlorohydrin (PAE) Resin from
Endcapped Polyaminoamide Prepolymer
[0239] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 213.75 g endcapped
polyaminoamide prepolymer from Example 9 and 240.00 g deionized
(DI) water. To this stirred solution was quickly added 37.01 g
epichlorohydrin (0.40 mole). The reaction temperature was
maintained at 38-40.degree. C. for 2 hours. At this point 162 g of
DI dilution water was added to the reaction and the reaction was
heated to 60.degree. C. When the reaction temperature reached
60.degree. C. a solution of 1.32 g concentrated sulfuric acid in
15.7 g DI water was added. The viscosity of the reaction mixture
was monitored by the use of Gardner-Holt tubes. After 128 minutes
at 60.degree. C. a Gardner-Holt viscosity of "J" was attained, a
solution of 5.28 g concentrated sulfuric acid in 125 g DI water was
added to terminate the reaction. An additional 518 g DI water was
added when the resin was transferred to a bottle. The pH of the
resin solution was adjusted to 2.70 using concentrated sulfuric
acid. The total solids of this resin was 11.40 wt % and the RSV was
0.6004 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%.
Example 20
Preparation of PAE Resin from Endcapped Polyaminoamide
Prepolymer
[0240] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 213.33 g endcapped
polyaminoamide prepolymer from Example 10 and 235.00 g deionized
(DI) water. To this stirred solution was quickly added 37.01 g
epichlorohydrin (0.40 mole). The reaction temperature was
maintained at 38-40.degree. C. for 2 hours. At this point 162 g of
DI dilution water was added to the reaction and the reaction was
heated to 60.degree. C. When the reaction temperature reached
60.degree. C. a solution of 1.32 g concentrated sulfuric acid in
15.7 g DI water was added. The viscosity of the reaction mixture
was monitored by the use of Gardner-Holt tubes. After 50 minutes at
55.degree. C. a Gardner-Holt viscosity of "M" was attained, a
solution of 5.28 g concentrated sulfuric acid in 125 g DI water was
added to terminate the reaction. An additional 518 g DI water was
added when the resin was transferred to a bottle. The pH of the
resin solution was adjusted to 2.70 using concentrated sulfuric
acid. The total solids of this resin was 11.91 wt % and the RSV was
0.6612 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%.
Example 21
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Glutaric Acid and DETA
[0241] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 324.99 g diethylenetriamine (DETA, 3.15 mole). To this
reactor was added 396.36 g glutaric acid (3.00 mole) through a
powder funnel while stirring the reaction mixture over a period of
one hour. The temperature increased from 23.4.degree. C. to
134.8.degree. C. during the addition of glutaric acid to the
reactor. The temperature was raised to 170.degree. C. and was held
at this temperature for 4 hours while distillate was collected in
the Dean-Stark trap. A total of 105 mL distillate were collected in
the Dean-Stark trap during this time. At this point heating was
discontinued and a volume of 610 mL of hot water (.about.70.degree.
C.) was then cautiously added to the product which was stirred
until the prepolymer was dissolved. After cooling to room
temperature the product was bottled. The total solids of this
product was 48.17 wt % and the RSV was 0.1688 dL/g, determined in
1.0N NH.sub.4Cl at 2.0%. This material had an amine number of 5.90
meq/g and an acid number of 0.30 meq/g, determined by titration as
previously described. The acid endgroup concentration was
determined to be 2.09% from the carbon 13 NMR spectrum (See Example
60).
Example 22
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Glutaric Acid and DETA
[0242] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 332.73 g diethylenetriamine (DETA, 3.225 mole). To
this reactor was added 396.36 g glutaric acid (3.00 mole) through a
powder funnel while stirring the reaction mixture over a period of
25 minutes. The temperature increased from 21.9.degree. C. to
128.7.degree. C. during the addition of glutaric acid to the
reactor. The temperature was raised to 170.degree. C. and was held
at this temperature for 4 hours while distillate was collected in
the Dean-Stark trap. A total of 103 mL distillate were collected in
the Dean-Stark trap during this time. At this point heating was
discontinued and a volume of 610 mL of hot water (.about.70.degree.
C.) was then cautiously added to the product which was stirred
until the prepolymer was dissolved. After cooling to room
temperature the product was bottled. The total solids of this
product was 47.43 wt % and the RSV was 0.1373 dL/g, determined in
1.0N NH.sub.4Cl at 2.0%. This material had an amine number of 6.14
meq/g and an acid number of 0.20 meq/g, determined by titration as
previously described. The acid endgroup concentration was
determined to be 2.60% from the carbon 13 NMR spectrum (see Example
60).
Example 23
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Glutaric Acid and DETA
[0243] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 332.73 g diethylenetriamine (DETA, 3.225 mole). To
this reactor was added 396.36 g glutaric acid (3.00 mole) through a
powder funnel while stirring the reaction mixture over a period of
19 minutes. The temperature increased from 21.3.degree. C. to
134.8.degree. C. during the addition of glutaric acid to the
reactor. The temperature was raised to 185.degree. C. and was held
at this temperature for 4 hours while distillate was collected in
the Dean-Stark trap. A total of 115 mL distillate were collected in
the Dean-Stark trap during this time. At this point heating was
discontinued and a volume of 610 mL of hot water (.about.70.degree.
C.) was then cautiously added to the product which was stirred
until the prepolymer was dissolved. After cooling to room
temperature the product was bottled. The total solids of this
product was 49.69 wt % and the RSV was 0.1699 dL/g, determined in
1.0N NH.sub.4Cl at 2.0%. This material had an amine number of 6.22
meq/g and an acid number of 0.13 meq/g, determined by titration as
previously described. The acid endgroup concentration was
determined to be 1.35% from the carbon 13 NMR spectrum (see Example
60).
Example 24
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA
[0244] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added 480.51 g dimethyl glutarate (3.00 mole)
through an addition funnel while stirring the reaction mixture. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 105 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 100 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
30 mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 185.degree. C. and maintained there
for 4 hours. During this time an additional 15 mL distillate was
removed through the Dean-Stark trap. At this point heating was
discontinued and the reaction was allowed to cool to 150.degree. C.
When the temperature had reached 150.degree. C., a volume of 610 mL
of hot water (.about.70.degree. C.) was then cautiously added to
the product which was stirred until the prepolymer was dissolved.
After cooling to room temperature the product was bottled. The
total solids of this product was 47.92 wt % and the RSV was 0.1450
dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This material had an
amine number of 6.93 meq/g and an acid number of 0.16 meq/g,
determined by titration as previously described. The acid endgroup
concentration was determined to be 0.99% from the carbon 13 NMR
spectrum (see Example 60).
Example 25
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA
[0245] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 348.20 g diethylenetriamine (DETA, 3.375 mole). To
this reactor was added 480.51 g dimethyl glutarate (3.00 mole)
through an addition funnel while stirring the reaction mixture. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux 0 the condenser configuration was changed to distill through
a Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1 hours while distillate was collected in the Dean-Stark
trap. A total of 65 mL distillate were collected in the Dean-Stark
trap during this time. The temperature was then raised to
120.degree. C. and maintained there for 30 minutes. During this
time an additional 60 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
110 mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 185.degree. C. and maintained there
for 4 hours. During this time an additional 13 mL distillate was
removed through the Dean-Stark trap. At this point heating was
discontinued and the reaction was allowed to cool to 170.degree. C.
When the temperature had reached 170.degree. C., a volume of 610 mL
of hot water (.about.70.degree. C.) was then cautiously added to
the product which was stirred until the prepolymer was dissolved.
After cooling to room temperature the product was bottled. The
total solids of this product was 51.05 wt % and the RSV was 0.1230
dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This material had an
amine number of 6.91 meq/g and an acid number of 0.12 meq/g,
determined by titration as previously described. The acid endgroup
concentration was determined to be 0.66% from the carbon 13 NMR
spectrum (see Example 60).
Example 26
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Post-addition of DETA
[0246] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 322.97 g diethylenetriamine (DETA, 3.1305 mole). To
this reactor was added 480.51 g dimethyl glutarate (3.00 mole)
through an addition funnel while stirring the reaction mixture. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 85 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 115 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
33 mL distillate was removed through the Dean-Stark trap. An
additional 13.46 g DETA (0.1305 moles) was then added to the
reactor and the temperature was raised to 185.degree. C. and
maintained there for 4 hours. During this time an additional 23 mL
distillate was removed through the Dean-Stark trap. At this point
heating was discontinued and the reaction was allowed to cool to
150.degree. C. When the temperature had reached 150.degree. C., a
volume of 610 mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 48.22 wt
% and the RSV was 0.1515 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 6.43 meq/g and an acid
number of 0.12 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
0.85% from the carbon 13 NMR spectrum (see Example 60).
Example 27
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Adipate and DETA with Post-addition of DETA
[0247] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 322.97 g diethylenetriamine (DETA, 3.1305 mole). To
this reactor was added 522.60 g dimethyl adipate (3.00 mole)
through an addition funnel while stirring the reaction mixture. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours with this configuration. No distillate was
collected in the Dean-Stark trap during this time. The temperature
was then raised to 120.degree. C. and maintained there for 30
minutes. During this time 88 mL distillate was collected in the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
132 mL distillate was removed through the Dean-Stark trap. An
additional 13.46 g DETA (0.1305 moles) was then added to the
reactor and the temperature was raised to 185.degree. C. and
maintained there for 4 hours. During this time an additional 60 mL
distillate was removed through the Dean-Stark trap. At this point
heating was discontinued and the reaction was allowed to cool to
150.degree. C. When the temperature had reached 150.degree. C., a
volume of 610 mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 48.84 wt
% and the RSV was 0.1074 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 6.25 meq/g and an acid
number of 0.12 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
3.76% from the carbon 13 NMR spectrum (see Example 60).
Example 28
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Post-addition of DETA
[0248] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added 480.51 g dimethyl glutarate (3.00 mole)
through an addition funnel while stirring the reaction mixture. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 95 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 103 mL distillate was removed through the
Dean-Stark trap. The temperature 0 was then raised to 150.degree.
C. and maintained there for 45 minutes. During this time an
additional 35 mL distillate was removed through the Dean-Stark
trap. An additional 13.46 g DETA (0.1305 moles) was then added to
the reactor and the temperature was raised to 190.degree. C. and
maintained there for 4 hours. During this time an additional 17 mL
distillate was removed through the Dean-Stark trap. At this point
heating was discontinued and the reaction was allowed to cool to
150.degree. C. When the temperature had reached 150.degree. C., a
volume of 610 mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 48.17 wt
% and the RSV was 0.1458 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 6.25 meq/g and an acid
number of 0.10 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
1.18% from the carbon 13 NMR spectrum (see Example 60.
Example 29
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Added Sulfuric Acid
[0249] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added dropwise 29.24 g of a 25% aqueous solution
of sulfuric acid. The temperature rose from 21.2.degree. C. to
36.5.degree. C. during the addition of the sulfuric acid. Then a
quantity of 480.51 g dimethyl glutarate (3.00 mole) was added to
the reactor through an addition funnel while stirring the reaction
mixture. The reaction mixture's temperature had dropped to
25.6.degree. C. by the end of the dimethyl glutarate addition. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 145 mL distillate were collected 0 in
the Dean-Stark trap during this time. The temperature was then
raised to 120.degree. C. and maintained there for 30 minutes.
During this time an additional 85 mL distillate was removed through
the Dean-Stark trap. The temperature was then raised to 150.degree.
C. and maintained there for 45 minutes. During this time an
additional 33 mL distillate was removed through the Dean-Stark
trap. The temperature of the reaction was then increased to
185.degree. C. and maintained there for 4 hours. During this time
an additional 17 mL distillate was removed through the Dean-Stark
trap. At this point heating was discontinued and the reaction was
allowed to cool to 150.degree. C. When the temperature had reached
150C, a volume of 610 mL of hot water (.about.70.degree. C.) was
then cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 46.30 wt
% and the RSV was 0.1674 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.83 meq/g and an acid
number of 0.32 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
0.73% from the carbon 13 NMR spectrum (see Example 60).
Example 30
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Added Sulfuric Acid
[0250] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added dropwise 58.48 g of a 25% aqueous solution
of sulfuric acid. The temperature rose from 21.3.degree. C. to
60.0.degree. C. during the addition of the sulfuric acid. Then a
quantity of 480.51 g dimethyl glutarate (3.00 mole) was added to
the reactor through an addition funnel while stirring the reaction
mixture. The reaction mixture's temperature had dropped to
38.6.degree. C. by the end of the dimethyl glutarate addition. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through
0a Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 180 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 60 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
30 mL distillate was removed through the Dean-Stark trap. The
temperature of the reaction was then increased to 185.degree. C.
and maintained there for 4 hours. During this time an additional 25
mL distillate was removed through the Dean-Stark trap. At this
point heating was discontinued and the reaction was allowed to cool
to 150.degree. C. When the temperature had reached 150.degree. C.,
a volume of 610 mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 47.99 wt
% and the RSV was 0.1653 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.58 meq/g and an acid
number of 0.65 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
0.47% from the carbon 13 NMR spectrum (see Example 60).
Example 31
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Added Sulfuric Acid
[0251] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer Was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added dropwise 58.48 g of a 25% aqueous solution
of sulfuric acid. The temperature rose from 21.6.degree. C. to
57.0.degree. C. during the addition of the sulfuric acid. Then a
quantity of 480.51 g dimethyl glutarate (3.00 mole) was added to
the reactor through an addition funnel while stirring the reaction
mixture. The reaction mixture's temperature had dropped to
36.9.degree. C. by the end of the dimethyl glutarate addition. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 170 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 60 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
35 mL distillate was removed through the Dean-Stark trap. The
temperature of the reaction was then increased to 190.degree. C.
and maintained there for 4 hours. During this time an additional 23
mL distillate was removed through the Dean-Stark trap. At this
point heating was discontinued and the reaction was allowed to cool
to 175.degree. C. When the temperature had reached 175.degree. C.,
a volume of 610 mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 48.27 wt
% and the RSV was 0.1735 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.84 meq/g and an acid
number of 0.54 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
0.44% from the carbon 13 NMR spectrum (see Example 60).
Example 32
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Added Sulfuric Acid
[0252] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added dropwise 116.96 g of a 25% aqueous solution
of sulfuric acid. The temperature rose from 22.1.degree. C. to
78.6.degree. C. during the addition of the sulfuric acid. Then a
quantity of 480.51 g dimethyl glutarate (3.00 mole) was added to
the reactor through an addition funnel while stirring the reaction
mixture. The reaction mixture's temperature had dropped to
53.7.degree. C. by the end of the dimethyl glutarate addition. The
temperature was raised to 100.degree. C. and the reaction was
refluxed at this temperature for 1 hour. At the end of the one hour
reflux the condenser configuration was changed to distill through a
Dean-Stark trap. The reaction was held at 100.degree. C. for an
additional 1.5 hours while distillate was collected in the
Dean-Stark trap. A total of 195 mL distillate were collected in the
Dean-Stark trap during this time. The temperature was then raised
to 120.degree. C. and maintained there for 30 minutes. During this
time an additional 65 mL distillate was removed through the
Dean-Stark trap. The temperature was then raised to 150.degree. C.
and maintained there for 45 minutes. During this time an additional
40 mL distillate was removed through the Dean-Stark trap. The
temperature of the reaction was then increased to 185.degree. C.
and maintained there for 4 hours. During this time an additional 38
mL distillate was removed through the Dean-Stark trap. At this
point heating was discontinued and the reaction was allowed to cool
to 160.degree. C. When the temperature had reached 160.degree. C.,
a volume of 610mL of hot water (.about.70.degree. C.) was then
cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 49.44 wt
% and the RSV was 0.1716 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.48 meq/g and an acid
number of 1.03 meq/g, determined by titration as previously
described. The acid endgroup concentration was determined to be
0.17% from the carbon 13 NMR spectrum (see Example 60).
Example 33
Preparation of Amine-terminated Polyaminoamide Prepolymer from
Dimethyl Glutarate and DETA with Added sulfuric Acid
[0253] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 336.43 g diethylenetriamine (DETA, 3.2661 mole). To
this reactor was added dropwise 29.42 g of concentrated sulfuric
acid. The temperature rose from 20.8.degree. C. to 51.4.degree. C.
during the addition of the sulfuric acid. Then a quantity of 480.51
g dimethyl glutarate (3.00 mole) was added to the reactor through
an addition funnel while stirring the reaction mixture. The
reaction mixture's temperature had dropped to 37.8.degree. C. by
the end of the dimethyl glutarate addition. The temperature was
raised to 100.degree. C. and the reaction was refluxed at this
temperature for 1 hour. At the end of the one hour reflux the
condenser configuration was changed to distill through a Dean-Stark
trap. The reaction was held at 100.degree. C. for an additional 1.5
hours while distillate was collected in the Dean-Stark trap. A
total of 110 mL distillate were collected in the Dean-Stark trap
during this time. The temperature was then raised to 120.degree. C.
and maintained there for 30 minutes. During this time an additional
95 mL distillate was removed through the Dean-Stark trap. The
temperature was then raised to 150.degree. C. and maintained there
for 45 minutes. During this time an additional 35 mL distillate was
removed through the Dean-Stark trap. The temperature of the
reaction was then increased to 185.degree. C. and maintained there
for 4 hours. During this time an additional 18 mL distillate was
removed through the Dean-Stark trap. At this point heating was
discontinued and the reaction was allowed to cool to 167.degree. C.
When the temperature had reached 167.degree. C., a volume of 610 mL
of hot water (.about.70.degree. C.) was then cautiously added to
the product which was stirred until the prepolymer was dissolved.
After cooling to room temperature the product was bottled. The
total solids of this product was 49.64 wt % and the RSV was 0.1622
dL/g, determined in 1.0N NH.sub.4Cl at 2.0%. This material had an
amine number of 5.22 meq/g and an acid number of 1.05 meq/g,
determined by titration as previously described. The acid endgroup
concentration was determined to be 0.38% from the carbon 13 NMR
spectrum (see Example 60).
Example 34
Preparation of PAE Resin from Amine-terminated Polyaminoamide
Prepolymer of Example 24
[0254] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 199.89 g amine terminated
polyaminoamide prepolymer from Example 24 and 120.00 g deionized
(DI) water. The pH of this solution was adjusted to 9.5 by adding
3.34 g of concentrated sulfuric acid. To this stirred solution was
quickly added 43.95 g epichlorohydrin (0.475 mole). The temperature
of the reaction was held at 38-42.degree. C. for two hours. At the
end of the 2 hours the pH of the reaction had dropped to 7.91. At
this point 177.00 g DI water were added to the reaction and the pH
was adjusted to 7.0 by the addition of 4.46 g of concentrated
sulfuric acid. The reaction temperature was then increased to
60.degree. C. When the reaction temperature reached 60.degree. C.
the viscosity of the reaction mixture was monitored by the use of
Gardner-Holt tubes. After 92 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The pH had dropped to
5.75 at this point. A quantity of 185.00 g DI dilution water was
added and the temperature was maintained at 60.degree. C. while
continuing to monitor the viscosity using Gardner-Holt tubes. A
Gardner-Holt viscosity of "H" was attained after an additional 86
minutes and heating of the reaction was discontinued. The pH of the
reaction was 5.31 at this point. A solution of 5.28 g concentrated
sulfuric acid in 125 g DI water was added to terminate the
reaction. An additional 240 g DI water was added when the resin was
transferred to a bottle. The pH of the resin solution was adjusted
to 2.70 using 5.28 g concentrated sulfuric acid. The total solids
of this resin was 13.86 wt % and the RSV was 0.4958 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. The Brookfield viscosity of
the product was 57.5 cps (spindle #2 at 60 rpm using a Brookfield
DV-II viscometer at 25.degree. C.). Analysis for epichlorohydrin
hydrolysis products showed 1,3-dichloro-2-propanol (DCP) at 353 ppm
and 3-chloro-1,2-propanediol (CPD) at 186 ppm.
Example 35
Preparation of PAE Resin from Amine-terminated Polyaminoamide
Prepolymer Made from Dimethyl Glutarate and DETA with Post-addition
of DETA of Example 28
[0255] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 198.85 g amine terminated
polyaminoamide prepolymer from Example 28 and 120.00 g deionized
(DI) water. The pH of this solution was adjusted to 9.5 by adding
3.10 g of concentrated sulfuric acid. To this stirred solution was
quickly added 46.27 g epichlorohydrin (0.50 mole). The temperature
of the reaction was held at 38-42.degree. C. for two hours. At the
end of the 2 hours the pH of the reaction had dropped to 7.65. At
this point 177.00 g DI water were added to the reaction and the pH
was adjusted to 7.25 by the addition of 1.85 g of concentrated
sulfuric acid. The reaction temperature was then increased to
60.degree. C. When the reaction temperature reached 60.degree. C.
the viscosity of the reaction mixture was monitored by the use of
Gardner-Holt tubes. After 60 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The pH had dropped to
6.03 at this point. A quantity of 185.00 g DI dilution water was
added and the temperature was maintained at 60.degree. C. while
continuing to monitor the viscosity using Gardner-Holt tubes. A
Gardner-Holt viscosity of "H" was attained after an additional 37
minutes and heating of the reaction was discontinued. The pH of the
reaction was 5.55 at this point. A solution of 5.28 g concentrated
sulfuric acid in 125 g DI water was added to terminate the
reaction. An additional 240 g DI water was added when the resin was
transferred to a bottle. The pH of the resin solution was adjusted
to 2.70 using 1.48 g concentrated sulfuric acid. The total solids
of this resin was 13.84 wt % and the RSV was 0.7053 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. The Brookfield viscosity of
the product was 105 cps (spindle #2 at 60 rpm using a Brookfield
DV-II viscometer at 25.degree. C.). Analysis for epichlorohydrin
hydrolysis products showed 1,3-dichloro-2-propanol (DCP) at 581 ppm
and 3-chloro-1,2-propanediol (CPD) at 252 ppm.
Example 36
Preparation of PAE Resin from Amine-terminated Polyaminoamide
Prepolymer Made from Dimethyl Glutarate and DETA with Added
Sulfuric Acid of Example 32
[0256] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 203.28 g amine terminated
polyaminoamide prepolymer from Example 32 and 120.00 g deionized
(DI) water. The pH of this solution was adjusted to 9.25 by adding
1.75 g of concentrated sulfuric acid. To this stirred solution was
quickly added 46.27 g epichlorohydrin (0.50 mole). The temperature
of the reaction was held at 38-42.degree. C. for two hours. At the
end of the 2 hours the pH of the reaction had dropped to 7.40. At
this point 177.00 g DI water were added to the reaction and the pH
was adjusted to 7.01 by the addition of 1.80 g of concentrated
sulfuric acid. The reaction temperature was then increased to
60.degree. C. When the reaction temperature reached 60.degree. C.
the viscosity of the reaction mixture was monitored by the use of
Gardner-Holt tubes. After 60 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The pH had dropped to
5.89 at this point. A quantity of 185.00 g DI dilution water was
added and the temperature was maintained at 60.degree. C. while
continuing to monitor the viscosity using Gardner-Holt tubes. A
Gardner-Holt viscosity of "H" was attained after an additional 37
minutes and heating of the reaction was discontinued. The pH of the
reaction was 5.53 at this point. A solution of 5.28 g concentrated
sulfuric acid in 125 g DI water was added to terminate the
reaction. An additional 240 g DI water was added when the resin was
transferred to a bottle. The pH of the resin solution was adjusted
to 2.70 using 6.87 g concentrated sulfuric acid. The total solids
of this resin was 14.22 wt % and the RSV was 0.7505 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. The Brookfield viscosity of
the product was 87.5 cps (spindle #2 at 60 rpm using a Brookfield
DV-II viscometer at 25.degree. C.). Analysis for epichlorohydrin
hydrolysis products showed 1,3-dichloro-2-propanol (DCP) at 806 ppm
and 3-chloro-1,2-propanediol (CPD) at 315 ppm.
Example 37
Preparation of PAE Resin from Amine-terminated Polyaminoamide
Prepolymer Made from Dimethyl Glutarate and DETA with Added
Sulfuric Acid of Example 32
[0257] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 203.28 g amine terminated
polyaminoamide prepolymer from Example 32 and 120.00 g deionized
(DI) water. The pH of this solution was adjusted to 9.25 by adding
1.23 g of concentrated sulfuric acid. To this stirred solution was
quickly added 50.89 g epichlorohydrin (0.55 mole). The temperature
of the reaction was held at 38-42.degree. C. for two hours. At the
end of the 2 hours the pH of the reaction had dropped to 7.41. At
this point 194.00 g DI water were added to the reaction and the pH
was adjusted to 7.13 by the addition of 1.10 g of concentrated
sulfuric acid. The reaction temperature was then increased to
60.degree. C. When the reaction temperature reached 60.degree. C.
the viscosity of the reaction mixture was monitored by the use of
Gardner-Holt tubes. After 70 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The pH had dropped to
5.92 at this point. A quantity of 208.00 g DI dilution water was
added and the temperature was maintained at 60.degree. C. while
continuing to monitor the viscosity using Gardner-Holt tubes. A
Gardner-Holt viscosity of "H" was attained after an additional 51
minutes and heating of the reaction was discontinued. The pH of the
reaction was 5.62 at this point. A solution of 5.00 g concentrated
sulfuric acid in 125 g DI water was added to terminate the
reaction. An additional 240 g DI water was added when the resin was
transferred to a bottle. The pH of the resin solution was adjusted
to 2.70 using 1.12 g concentrated sulfuric acid. The total solids
of this resin was 14.08 wt % and the RSV was 0.6151 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. The Brookfield viscosity of
the product was 67.5 cps (spindle #2 at 60 rpm using a Brookfield
DV-II viscometer at 25.degree. C.). Analysis for epichlorohydrin
hydrolysis products showed 1,3-dichloro-2-propanol (DCP) at 1,317
ppm and 3-chloro-1,2-propanediol (CPD) at 390 ppm.
Example 38
Preparation of PAE Resin from Amine-terminated Polyaminoamide
Prepolymer Made from Dimethyl Glutarate and DETA of Example 25
[0258] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 184.7 g amine terminated
polyaminoamide prepolymer from Example 25 and 130.00 g deionized
(DI) water. The pH of this solution was adjusted to 9.25 by adding
4.42 g of concentrated sulfuric acid. To this stirred solution was
quickly added 55.52 g epichlorohydrin (0.60 mole). The temperature
of the reaction was held at 38-42.degree. C. for two hours. At the
end of the 2 hours the pH of the reaction had dropped to 7.27. At
this point 206 g DI water were added to the reaction. The reaction
temperature was then increased to 60.degree. C. When the reaction
temperature reached 60.degree. C. the viscosity of the reaction
mixture was monitored by the use of Gardner-Holt tubes. After 154
minutes at 60.degree. C. the Gardner-Holt viscosity had only
increased to "C". In order to speed up the reaction 2.92 g of 20%
NaOH was added to bring the pH from 5.48 to 5.78. The viscosity
increased to "E" 25 minutes after the pH adjustment. A quantity of
210.00 g DI dilution water was added and the temperature was
maintained at 60.degree. C. while continuing to monitor the
viscosity using Gardner-Holt tubes. After 71 minutes the
Gardner-Holt viscosity had only gone to "D" and was not increasing.
The pH was adjusted form 5.41 to 5.62 by the addition of 1.94 g of
20% NaOH. A Gardner-Holt viscosity "H" was attained after an
additional 32 minutes and heating of the reaction was discontinued.
The pH of the reaction was 5.51 at this point. A solution of 5.28 g
concentrated sulfuric acid in 125 g DI water was added to terminate
the reaction. An additional 240 g DI water was added when the resin
was transferred to a bottle. The pH of the resin solution was
adjusted to 2.70 using 0.85 g concentrated sulfuric acid. The total
solids of this resin was 13.29 wt % and the RSV was 0.7173 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. The Brookfield viscosity of
the product was 70 cps (spindle #2 at 60 rpm using a Brookfield
DV-II viscometer at 25.degree. C.). Analysis for epichlorohydrin
hydrolysis products showed 1,3-dichloro-2-propanol (DCP) at 852 ppm
and 3-chloro-1,2-propanediol (CPD) at 272 ppm.
Example 39
Biodehalogenation and Acid Test of the PAE Resin of Example 36
[0259] A 332.86 gram sample of the PAE resin of Example 36 and
133.14 g deionized water were charged into a one liter 4-necked,
round-bottomed flask equipped with an overhead stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 6.13 grams of 20% aqueous sodium hydroxide. To the mixture was
added 36.98 g of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin.
This represents a starting value of cell concentration of from
about 10.sup.5 to about 10.sup.6 cells/ml. This starting value
corresponds to a final treatment level of about 10.sup.9 cells/ml
as the process proceeds. The inoculum was added, together with 6.93
grams of a nutrient solution. (The nutrient solution consisted of
8026 ppm of potassium dihydrogen phosphate, 24780 ppm of urea, 4160
ppm of magnesium sulfate and 840 ppm of calcium chloride in tap
water.) The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 48 hours, a sample was removed
and submitted for GC analysis, the mixture was cooled to room
temperature, the pH was adjusted to 2.8 with 2.58 g of 96% sulfuric
acid and 5.41 grams of biocide solution was added. [The biocide
solution consisted of 10% active Proxel.RTM. BD (from Zeneca
Biocides) and 1.67% potassium sorbate in deionized water.] The
resin had a total solids of 13.44 wt %.
[0260] The sample was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin, DCP or CPD.
[0261] A 150.84 g sample of the biodehalogenated resin was placed
in an 8 oz. glass jar and the pH was adjusted to 1.0 with 3.61 g
concentrated sulfuric acid. The jar was placed in a 50.degree. C.
water bath for 24 hours while being stirred with a magnetic
stirrer. The sample was then cooled to room temperature and
adjusted to pH 2.81 with 3.86 g of 30% NaOH solution. This material
was analyzed for epichlorohydrin and epichlorohydrin hydrolysis
products by GC as described previously. The analysis showed no
detectable epichlorohydrin, 0.23 ppm 1,3-DCP, 0.47 ppm 2,3-DCP and
2.62 ppm CPD.
Example 40
Papermaking with the Biodehalogenated PAE Resin of Example 39
[0262] Paper handsheets were prepared on a Noble and Wood handsheet
machine at pH 7.5 with 50:50 Rayonier bleached Kraft:Crown Vantage
bleached hardwood Kraft dry lap pulp refined to 500 mL Canadian
standard freeness. Sheets were generated having 40 lb/3000 sq. ft.
basis weight containing 1.0% of the biodehalogenated resin of
Example 39. Handsheets were wet pressed to 33% solids and dried on
a drum drier at 230.degree. C. for 55 seconds to give 3-5%
moisture. Some of the handsheets were oven-cured at 80.degree. C.
for 30 minutes. The paper was conditioned according to TAPPI Method
T-402 and tested. Dry tensile strength was determined using TAPPI
Method T-494. Wet tensile strength was determined using TAPPI
Method T-456 with a two hour soak time. Some of the paper was
natural aged by conditioning at greater than two weeks at 50%
relative humidity and at 23.degree. C. and then tested. Dry tensile
strength was determined using TAPPI Method T-494. Wet tensile
strength was determined using TAPPI Method T-456 with a two hour
soak time. To measure CPD in paper products, five grams of the
paper product was extracted with water according to the method
described in European standard EN 647, dated October 1993. Then
5.80 grams of sodium chloride was dissolved into 20 ml of water
extract. The salted aqueous extract was transferred to a 20 gram
capacity Extrelut column and allowed to saturate the column for 15
minutes. After three washes of 3 ml ethyl acetate and saturation of
the column, the Extrelut column was eluted until 300 ml of eluent
has been recovered in about 1 hour. The 300 ml of ethyl acetate
extract was concentrated to about 5 ml using a 500 ml Kudema-Danish
concentrating apparatus (if necessary, further concentrating was
done by using a micro Kudema-Danish apparatus). The concentrated
extract was analyzed by GC using a halogen specific detector
(XSD).
[0263] The oven-cured paper gave a wet tensile strength value of
5.68 lb/in and the naturally aged paper had a wet tensile strength
value of 4.99 lb/in. The oven cured sample was analyzed for
epichlorohydrin and epichlorohydrin hydrolysis products and was
found to contain no epichlorohydrin or DCP and 113 ppb of CPD. This
compares to 638 ppb CPD for Comparative Example 4 (see Table
10).
Example 41
Biodehalogenation and Acid Test of the PAE Resin of Example 37
[0264] A 520.00 gram sample of the PAE resin of Example 37 was
charged into a one liter 4-necked, round-bottomed flask equipped
with an overhead stirrer, a condenser, an air sparge and a pH
meter. The pH was adjusted to 5.8 with 8.62 grams of 20% aqueous
sodium hydroxide. To the mixture was added 60.00 g of a blend of
microorganisms comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 6.93 grams of a nutrient
solution. (The nutrient solution consisted of 8,026 ppm of
potassium dihydrogen phosphate, 24,780 ppm of urea, 4,160 ppm of
magnesium sulfate and 840 ppm of calcium chloride in tap water.)
The microorganisms used were: Arthrobacter histidinolovorans (HK1)
and Agrobacterium tumefaciens (HK7). The flask was placed in a
30.degree. C. water bath and maintained at 30.degree. C. The pH was
maintained at 5.8 by periodic addition of 20% aqueous sodium
hydroxide. After 48 hours, a sample was removed and submitted for
GC analysis, the mixture was cooled to room temperature, the pH was
adjusted to 2.8 with 1.40 g of 96% sulfuric acid and 7.41 grams of
biocide solution was added. [The biocide solution consisted of 10%
active Proxel.RTM. BD (from Zeneca Biocides) and 1.67% potassium
sorbate in deionized water.] The resin had a total solids of 11.76
wt %.
[0265] The sample was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin, DCP or CPD and
1.05 ppm of 2,3-DCP.
[0266] A 151.47 g sample of the biodehalogenated resin was
subjected to the acid test by placing it in an 8 oz. glass jar and
the pH was adjusted to 1.0 with 1.88 g concentrated sulfuric acid.
The jar was placed in a 50.degree. C. water bath for 24 hours while
being stirred with a magnetic stirrer. The sample was then cooled
to room temperature and adjusted to pH 2.60 with 4.15 g of 30% NaOH
solution. This material was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin or 1,3-DCP, 0.57
ppm 2,3-DCP and 5.53 ppm CPD.
Example 42
Papermaking with the Biodehalogenated PAE Resin of Example 41
[0267] Paper handsheets were prepared on a Noble and Wood handsheet
machine at pH 7.5 with 50:50 Rayonier bleached Kraft:Crown Vantage
bleached hardwood Kraft dry lap pulp refined to 500 mL Canadian
standard freeness. Sheets were generated having 40 lb/3000 sq. ft.
basis weight containing 1.0% of the biodehalogenated resin of
Example 41. Handsheets were wet pressed to 33% solids and dried on
a drum drier at 230.degree. C. for 55 seconds to give 3-5%
moisture. Some of the handsheets were oven-cured at 80.degree. C.
for 30 minutes. The paper was conditioned according to TAPPI Method
T-402 and tested. Dry tensile strength was determined using TAPPI
Method T-494. Wet tensile strength was determined using TAPPI
Method T-456 with a two hour soak time. Some of the paper was
natural aged by conditioning at greater than two weeks at 50%
relative humidity and at 23.degree. C. and then tested. Dry tensile
strength was determined using TAPPI Method T-494. Wet tensile
strength was determined using TAPPI Method T-456 with a two hour
soak time. To measure CPD in paper products, five grams of the
paper product was extracted with water according to the method
described in European standard EN 647, dated October 1993. Then
5.80 grams of sodium chloride was dissolved into 20 ml of water
extract. The salted aqueous extract was transferred to a 20 gram
capacity Extrelut column and allowed to saturate the column for 15
minutes. After three washes of 3 ml ethyl acetate and saturation of
the column, the Extrelut column was eluted until 300 ml of eluent
has been recovered in about 1 hour. The 300 ml of ethyl acetate
extract was concentrated to about 5 ml using a 500 ml Kudema-Danish
concentrating apparatus (if necessary, further concentrating was
done by using a micro Kudema-Danish apparatus). The concentrated
extract was analyzed by GC using a halogen specific detector
(XSD).
[0268] The oven-cured paper gave a wet tensile strength value of
5.76 lb/in and the naturally aged paper had a wet tensile strength
value of 5.43 lb/in. The oven cured sample was analyzed for
epichlorohydrin and epichlorohydrin hydrolysis products and was
found to contain no epichlorohydrin or DCP and 133 ppb of CPD. This
compares to 638 ppb CPD for Comparative Example 4 (see Table
10).
Example 43
Biodehalogenation and Acid Test of the PAE Resin of Example 34
[0269] A 400.00 gram sample of the PAE resin of Example 34 and 148
g deionized water were charged into a one liter 4-necked,
round-bottomed flask equipped with an overhead stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 7.80 grams of 20% aqueous sodium hydroxide. To the mixture was
added 46.20 g of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin.
This represents a starting value of cell concentration of from
about 10.sup.5 to about 10.sup.6cells/ml. This starting value
consisted of 8,026 ppm of potassium dihydrogen phosphate, 24,780
ppm of urea, 4,160 ppm of magnesium sulfate and 840 ppm of calcium
chloride in tap water. The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 48 hours, a sample was removed
and submitted for GC analysis, the mixture was cooled to room
temperature, the pH was adjusted to 2.23 with 96% sulfuric acid and
7.41 grams of biocide solution was added. [The biocide solution
consisted of 10% active Proxel.RTM. BD (from Zeneca Biocides) and
1.67% potassium sorbate in deionized water.] The resin had a total
solids of 10.45 wt %.
[0270] The sample was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin, 1,3-DCP or CPD
and 0.56 ppm of 2,3-DCP.
[0271] A 150.01 g sample of the biodehalogenated resin was
subjected to the acid test by placing it in an 8 oz. glass jar and
the pH was adjusted to 1.0 with 2.33 g concentrated sulfuric acid.
The jar was placed in a 50.degree. C. water bath for 24 hours while
being stirred with a magnetic stirrer. The sample was then cooled
to room temperature and adjusted to pH 2.83 with 5.47 g of 30% NaOH
solution. This material was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin or 1,3-DCP, 0.39
ppm 2,3-DCP and 2.7 ppm CPD.
Example 44
Biodehalogenation and Acid Test of the PAE Resin of Example 35
[0272] A 359.20 gram sample of the PAE resin of Example 35 and
137.9 g deionized water were charged into a one liter 4-necked,
round-bottomed flask equipped with an overhead stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 6.66 grams of 20% aqueous sodium hydroxide. To the mixture was
added 46.20 g of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin.
This represents a starting value of cell concentration of from
about 10.sup.5 to about 10.sup.6 cells/ml. This starting value
consisted of 8,026 ppm of potassium dihydrogen phosphate, 24,780
ppm of urea, 4,160 ppm of magnesium sulfate and 840 ppm of calcium
chloride in tap water. The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 48 hours, a sample was removed
and submitted for GC analysis, the mixture was cooled to room
temperature, the pH was adjusted to 2.8 with 96% sulfuric acid and
7.41 grams of biocide solution was added. [The biocide solution
consisted of 10% active Proxel.RTM. BD (from Zeneca Biocides) and
1.67% potassium sorbate in deionized water.] The resin had a total
solids of 10.65 wt %.
[0273] The sample was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin, 1,3-DCP or CPD
and 0.46 ppm of 2,3-DCP.
[0274] A 150.05 g sample of the biodehalogenated resin was
subjected to the acid test by placing it in an 8 oz. glass jar and
the pH was adjusted to 1.0 with 2.24 g concentrated sulfuric acid.
The jar was placed in a 50.degree. C. water bath for 24 hours while
being stirred with a magnetic stirrer. The sample was then cooled
to room temperature and adjusted to pH 2.81 with 5.38 g of 20% NaOH
solution. This material was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin or 1,3-DCP, 0.49
ppm 2,3-DCP and 3.27 ppm CPD.
Example 45
Biodehalogenation and Acid Test of the PAE Resin of Example 38
[0275] A 400.00 gram sample of the PAE resin of Example 38 and
131.6 g deionized water were charged into a one liter 4-necked,
round-bottomed flask equipped with an overhead stirrer, a
condenser, an air sparge and a pH meter. The pH was adjusted to 5.8
with 7.26 grams of 20% aqueous sodium hydroxide. To the mixture was
added 46.20 g of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin.
This represents a starting value of cell concentration of from
about 10.sup.5 to about 10.sup.6 cells/ml. This starting value
consisted of 8,026 ppm of potassium dihydrogen phosphate, 24,780
ppm of urea, 4,160 ppm of magnesium sulfate and 840 ppm of calcium
chloride in tap water. The microorganisms used were: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
20% aqueous sodium hydroxide. After 48 hours, a sample was removed
and submitted for GC analysis, the mixture was cooled to room
temperature, the pH was adjusted to 2.73 with 2.23 g 96% sulfuric
acid and 7.41 grams of biocide solution was added. [The biocide
solution consisted of 10% active Proxel.RTM. BD (from Zeneca
Biocides) and 1.67% potassium sorbate in deionized water.] The
resin had a total solids of 10.45 wt %. The sample was analyzed for
epichlorohydrin and epichlorohydrin hydrolysis products by GC as
described previously. The analysis showed no detectable
epichlorohydrin, 1,3-DCP or CPD and 0.63 ppm of 2,3-DCP.
[0276] A 150.02 g sample of the biodehalogenated resin was
subjected to the acid test by placing it in an 8 oz. glass jar and
the pH was adjusted to 1.0 with 2.19 g concentrated sulfuric acid.
The jar was placed in a 50.degree. C. water bath for 24 hours while
being stirred with a magnetic stirrer. The sample was then cooled
to room temperature and adjusted to pH 2.81 with 4.97 g of 30% NaOH
solution. This material was analyzed for epichlorohydrin and
epichlorohydrin hydrolysis products by GC as described previously.
The analysis showed no detectable epichlorohydrin or 1,3-DCP, 0.58
ppm 2,3-DCP and 3.95 ppm CPD.
Example 46
Preparation of PAE Resin from Endcapped Polyaminoamide
Prepolymer
[0277] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 219.71 g endcapped
polyaminoamide prepolymer from Example 11 and 235.00 g deionized
(DI) water. To this stirred solution was quickly added 37.01 g
epichlorohydrin (0.40 mole). The reaction temperature was
maintained at 38-40.degree. C. for 2 hours. At this point 162 g of
DI dilution water was added to the reaction and the reaction was
heated to 55.degree. C. When the reaction temperature reached
55.degree. C. a solution of 1.32 g concentrated sulfuric acid in
15.7 g DI water was added. The viscosity of the reaction mixture
was monitored by the use of Gardner-Holt tubes. After 50 minutes at
60.degree. C. a Gardner-Holt viscosity of "I" to "J" was attained,
a solution of 5.28 g concentrated sulfuric acid in 125 g DI water
was added to terminate the reaction. An additional 518 g DI water
was added when the resin was transferred to a bottle. The pH of the
resin solution was adjusted to 2.70 using concentrated sulfuric
acid. The total solids of this resin was 12.72 wt % and the RSV was
0.6248 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%.
Example 47
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0278] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 215.00 g polyaminoamide
prepolymer from Example 12 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 1.65 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 47 minutes at 60.degree. C. a
Gardner-Holt viscosity of "L" was attained, a solution of 5.28 g
concentrated sulfuric acid in 125 g DI water was added to terminate
the reaction. An additional 518 g DI water was added when the resin
was transferred to a bottle. The pH of the resin solution was
adjusted to 2.70 using concentrated sulfuric acid. The total solids
of this resin was 12.31 wt % and the RSV was 0.5966 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%.
Example 48
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0279] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 215.00 g polyaminoamide
prepolymer from Example 12 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 1.98 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 60 minutes at 60.degree. C. a
Gardner-Holt viscosity of "I" was attained, a solution of 5.28 g
concentrated sulfuric acid in 125 g DI water was added to terminate
the reaction. An additional 518 g DI water was added when the resin
was transferred to a bottle. The pH of the resin solution was
adjusted to 2.67 using concentrated sulfuric acid. The total solids
of this resin was 11.82 wt % and the RSV was 0.6360 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%.
Example 49
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0280] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 214.78 g polyaminoamide
prepolymer from Example 18 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 2.64 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 75 minutes at 60.degree. C. a
Gardner-Holt viscosity of "I" to "J" was attained, a solution of
5.28 g concentrated sulfuric acid in 125 g DI water was added to
terminate the reaction. An additional 518 g DI water was added when
the resin was transferred to a bottle. The pH of the resin solution
was adjusted to 2.74 using concentrated sulfuric acid. The total
solids of this resin was 12.01 wt % and the RSV was 0.5214 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%.
Example 50
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0281] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 216.18 g polyaminoamide
prepolymer from Example 17 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 2.64 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 98 minutes at 60.degree. C. a
Gardner-Holt viscosity of "J" was attained, a solution of 5.28 g
concentrated sulfuric acid in 125 g DI water was added to terminate
the reaction. An additional 518 g DI water was added when the resin
was transferred to a bottle. The pH of the resin solution was
adjusted to 2.72 using concentrated sulfuric acid. The total solids
of this resin was 11.82 wt % and the RSV was 0.7517 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%.
Example 51
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0282] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 214.78 g polyaminoamide
prepolymer from Example 18 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 2.64 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 74 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The reaction was then
diluted with 259 g DI water. The temperature was maintained at
60.degree. C. while continuing to monitor the viscosity with
Gardner-Holt tubes. After an additional 19 minutes at 60.degree.
C., the reaction mixture had achieved a Gardner-Holt viscosity of
"G" to "H", a solution of 5.28 g concentrated sulfuric acid in 125
g DI water was then added to terminate the reaction. An additional
259 g DI water was added when the resin was transferred to a
bottle. The pH of the resin solution was adjusted to 2.73 using
concentrated sulfuric acid. The total solids of this resin was
12.20 wt % and the RSV was 0.7159 dL/g, determined in 1.0N
NH.sub.4Cl at 2.0%.
Example 52
Preparation of PAE Resin from Polyaminoamide Prepolymer Prepared by
the Post-added Amine Method
[0283] A 1000 mL 4-necked flask fitted with condenser, thermocouple
and mechanical stirrer was charged with 216.18 g polyaminoamide
prepolymer from Example 17 and 256.00 g deionized (DI) water. To
this stirred solution was quickly added 41.64 g epichlorohydrin
(0.45 mole). The reaction temperature was maintained at
38-40.degree. C. for 2 hours. At this point 162 g of DI dilution
water was added to the reaction and the reaction was heated to
60.degree. C. When the reaction temperature reached 60.degree. C. a
solution of 2.64 g concentrated sulfuric acid in 15.7 g DI water
was added. The viscosity of the reaction mixture was monitored by
the use of Gardner-Holt tubes. After 102 minutes at 60.degree. C. a
Gardner-Holt viscosity of "E" was attained. The reaction was then
diluted with 259 g DI water. The temperature was maintained at
60.degree. C. while continuing to monitor the viscosity with
Gardner-Holt tubes. After an additional 34 minutes at 60.degree.
C., the reaction mixture had achieved a Gardner-Holt viscosity of
"H", a solution of 5.28 g concentrated sulfuric acid in 125 g DI
water was added to terminate the reaction. An additional 259 g DI
water was added when the resin was transferred to a bottle. The pH
of the resin solution was adjusted to 2.65 using concentrated
sulfuric acid. The total solids of this resin was 12.11 wt % and
the RSV was 0.7491 dL/g, determined in 1.0N NH.sub.4Cl at 2.0%.
Example 53
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0284] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 170.degree. C. and maintained there for 2
hours. During this time 105 mL distillate was removed through the
Dean-Stark trap. At this point, 15.48 g (0.15 mole) of DETA was
added to the reactor. The temperature was then raised to
180.degree. C. and maintained there for 2 hours. During this time
an additional 10 mL distillate was removed through the Dean-Stark
trap, a volume of 640 mL of hot water (.about.70.degree. C.) was
then cautiously added to the product which was stirred until the
prepolymer was dissolved. After cooling to room temperature the
product was bottled. The total solids of this product was 48.71 wt
% and the RSV was 0.1129 dL/g, determined in 1.0N NH.sub.4Cl at
2.0%. This material had an amine number of 5.85 meq/g and an acid
number of 0.144 meq/g, determined by titration as previously
described.
Example 54
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0285] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 170.degree. C. and maintained there for 2
hours. During this time 100 mL distillate was removed through the
Dean-Stark trap. At this point, 15.48 g (0.15 mole) of DETA was
added to the reactor. The temperature was then raised to
180.degree. C. and maintained there for 2 hours. During the two
hour cook at 180.degree. C. a vacuum of 10'' Hg was maintained in
the reactor. During this time an additional 15 mL distillate was
removed through the Dean-Stark trap, a volume of 640 mL of hot
water (.about.70.degree. C.) was then cautiously added to the
product which was stirred until the prepolymer was dissolved. After
cooling to room temperature the product was bottled. The total
solids of this product was 50.15 wt % and the RSV was 0.1042 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. This material had an amine
number of 5.94 meq/g and an acid number of 0.0818 meq/g, determined
by titration as previously described.
Example 55
Preparation of Polyaminoamide Prepolymer Using Post-added Amine
Method
[0286] a 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 309.51 g diethylenetriamine (DETA, 3.00 mole). To this
reactor was added 438.42 g adipic acid (3.00 mole) through a powder
funnel while stirring the reaction mixture. The temperature of the
reaction mixture was maintained below 125.degree. C. by controlling
the rate at which the adipic acid was added to the reaction. The
temperature was raised to 170.degree. C. and maintained there for 2
hours. During this time 93 mL distillate was removed through the
Dean-Stark trap. At this point, 15.48 g (0.15 mole) of DETA was
added to the reactor. The temperature was then raised to
180.degree. C. and maintained there for 2 hours. During the two
hour cook at 180.degree. C. a vacuum of 15'' Hg was maintained in
the reactor. During this time an additional 35 mL distillate was
removed through the Dean-Stark trap, a volume of 640 mL of hot
water (.about.70.degree. C.) was then cautiously added to the
product which was stirred until the prepolymer was dissolved. After
cooling to room temperature the product was bottled. The total
solids of this product was 49.02 wt % and the RSV was 0.1020 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0%. This material had an amine
number of 6.00 meq/g and an acid number of 0.0449 meq/g, determined
by titration as previously described.
Example 56
Biodehalogenation--General Procedure for the Lab Scale
Biodehalogenation of Polyaminoamide-epichlorohydrin and
Polyamine-epichlorohydrin Wet Strength Resins in Batch Mode
1) Preparation of Preculture of HKC on Kymene.RTM. 617
[0287] 50 mls of Kymene.RTM. 617 was adjusted to a pH value of 5.8
by the addition of 25% w/w sodium hydroxide solution. To this was
then added 0.5 mls of a nutrient package (consisting of 33 g of
urea; 5 g of potassium dihydrogen phosphate; 5.0 g of magnesium
sulphate heptahydrate and 1.0 g of calcium chloride monohydrate
dissolved in 1 liter of demineralized water), and 100 .mu.l of 10%
sterile yeast extract solution (from Difco). This mixture was then
transferred to a 250 ml Erlenmeyer flask. To this was then added
0.25mls of HKC stock. The flask was then placed in an orbital
shaker (200-250 rpm), and the material allowed to incubate at
30.degree. C. for twenty four hours.
2) Biodehalogenation of Polyaminoamide-epichlorohydrin Wet Strength
Resin
[0288] 25 mls of the polyaminoamide-epichlorohydrin resin was
adjusted to a pH value of 5.8 by the addition of 25% w/w sodium
hydroxide solution. To this was then added 0.25 mls of a nutrient
package (consisting of 33 g of urea; 5 g of potassium dihydroge-n
phosphate; 5.0 g of magnesium sulphate heptahydrate and 1.0 g of
calcium chloride monohydrate dissolved in 1 liter of water), 100
.mu.l of 10% yeast extract solution and 5 mls of sterilized water.
This mixture was then transferred to a 250 ml Erlenmeyer flask and
then inoculated with 1 ml of the Kymene.RTM. 617 pre-culture
prepared in the procedure above . The flask was then placed in an
orbital shaker (200-250 rpm), and the material allowed to incubate
at 30.degree. C. for forty eight hours.
[0289] After forty eight hours, the resin was transferred to a 50ml
falcon tube and then pH adjusted to a value of 2.8 by the dropwise
addition of 96% w/w sulphuric acid. 53 .mu.l of potassium sorbate
solution (94mg/ml) and 50 .mu.l of Proxel.RTM. BD (from Zeneca
Biocides) were then added to the resin, and the sample thoroughly
mix by a high shear mixer.
Example 57
Effect of Carboxylic Acid Group Content of Polyaminoamide Polymer
on Reformation of CPD in Wet Strength Resin Solution
[0290] To 686.0 g (6.65 moles) of diethylenetriamine, in a two
liter flange flask equipped with thermocouple, overhead mechanical
stirrer and Dean & Stark column with condensor, was added a
total of 1023.0 g (7.0 moles) of adipic. The adipic acid was added
in small portions to the flask over approximately one hour, the
temperature being maintained at less than 120.degree. C. during
this time. The reaction mixture is then heated to 155.degree. C.
over a 45 minute period at which point a large amount of
condensation water is produced in the reaction flask. This water is
produced, condensed and collected in the Dean & Stark
throughout the remainder of the reaction. The reaction mixture is
then maintained at a temperature of 155.degree. C. for one hour and
then heated to 170.degree. C. over a one hour period. It was then
maintained at 170.degree. C. Two hundred minutes after the addition
of the adipic acid the reaction mixture was killed by the addition
of 800 g of water and cooled to 55.degree. C. After dismantling of
the equipment and transferring the polyaminoamide polymer solution
to a five litre beaker, a further 600 g of water was added and
mixed in. The acid number of the prepolymer was determined to be
0.70meq/dry gram of polymer (PREPOLYMER 1).
[0291] A second polyaminoamide prepolymer was prepared according to
the procedure described above with the exception that 940.3 g (6.43
moles) of adipic acid was added to 670.6 g (6.50 moles) of
diethylenetriamine and the reaction was maintained at 170.degree.
C. for an extra sixty minutes before killing with 800 g of water.
The acid number of the prepolymer was determined to be 0.36meq/dry
gram of prepolymer (PREPOLYMER 2).
[0292] These two polymers, and blends of these polymers, were then
converted to polyaminoamide-epichlorohydrin resins by the following
general procedure.
[0293] To 505 g of 30% solids polymer solution (151.5 g dry
polymer), charged to a one litre flask equipped with thermocouple,
overhead mechanical stirrer and condensor, and at a temperature of
25.degree. C., was added 60.9 g of epichlorohydrin as quickly as
possible. The ensuing exotherm, raised the temperature to
40.degree. C. An ice/water bath was applied to prevent the
temperature exceeding a value of 40.degree. C. Once the exotherm
had subsided, the temperature was maintained at 40.degree. C. Two
hours and forty five minutes after the addition of epichlorohydrin,
the reaction mixture was diluted with 387.7 g of water. Heat was
then applied to raise the temperature to 70.degree. C. over a forty
five minute period. Twenty minutes into the heating up step, a
mixture of `x`d of 96.0% w/w sulphuric acid in 25 g of water was
added. Heating was then continued until 70.degree. C. had been
attained. The reaction was then maintained at this temperature. The
viscosity of the reaction mixture was monitored by periodic
measurement of the Gardner-Holt viscosity at 25.degree. C. When the
reaction mixture had reached a Gardner-Holt viscosity of H+, a
solution of 6 g of 96.0% w/w sulphuric acid in 200 g of water was
added to kill the reaction. The reaction mixture was then cooled to
25.degree. C., and then diluted further by the addition of 383.7 g
of water. Finally the pH of the resin was adjusted to 2.7 by
further dropwise addition of 96.0% w/w sulphuric acid.
[0294] The resins prepared are summarized in the Table 14 below.
TABLE-US-00015 TABLE 14 dry basis dry basis (db) (db) Pre- (parts
by (parts by polymer wt.) of wt.) of acid no. `X` g of Time at
Resin PRE- PRE- (meq/dry 96% w/w 70.degree. C. No. POLYMER 1
POLYMER 2 g) H.sub.2SO.sub.4 (min) 1 100 -- 0.70 -- 101 2 75 25
0.62 1.5 108 3 50 50 0.56 2.5 108 4 25 75 0.48 4.0 145 5 -- 100
0.36 5.9 177
[0295] The resins prepared were then biodehalogenated in batch
mode, according the procedures described in Example 56. These
dehalogenated samples were placed in a 50.degree. C. air convection
oven and aged for two weeks. 3 ml aliquots of each sample were
taken after one and two weeks at 50.degree. C., and the CPD content
of the resin was determined, according to the procedure described
in Comparative Example 1.
[0296] The results are summarized in the Table 15 below.
TABLE-US-00016 TABLE 15 CPD after CPD after CPD after Prepolymer
dehalogenation dehalogenation dehalogenation Resin acid no. before
50.degree. C. and one week and two weeks at No. (meq/dry g) aging
at 50.degree. C. 50.degree. C. 1 0.70 <1 ppm 25 ppm 41 ppm 2
0.62 <1 ppm 24 ppm 36 ppm 3 0.56 <1 ppm 26 ppm 36 ppm 4 0.48
<1 ppm 19 ppm 24 ppm 5 0.36 1 ppm 17 ppm 25 ppm
Example 58
Preparation of a Polyamidoamide Epichlorohydrin Resin Starting from
a Polyaminoamide Prepolymer with a Low Level of Residual Carboxylic
Acid Group Functionality
[0297] To 433.3 g (4.2 moles) of diethylenetriamine, in a one liter
flange flask equipped with thermocouple, overhead mechanical
stirrer and Dean & Stark column with condensor, was added a
total of 438.4 g (3.0 moles) of adipic acid. The adipic acid was
added in small portions to the flask over approximately one hour,
the temperature being maintained at less than 120.degree. C. during
this time. The reaction mixture is then heated to 155.degree. C.
over a 45 minute period at which point a large amount of
condensation water is produced in the reaction flask. This water is
produced, condensed and collected in the Dean & Stark
throughout the remainder of the reaction. The reaction mixture is
then maintained at a temperature of 155.degree. C. for one hour and
then heated to 170.degree. C. over a one hour period. It was then
maintained at 170.degree. C. for a further two hours and forty five
minutes. At this point in the reaction, 82.2 g of condensate water
has been collected and the acid number of the polymer was 0.21
meq/g, as determined by titration with alcoholic potassium
hydroxide solution. Further heating at 170.degree. C. produced a
further 3.5 g of condensate water and reduced the acid number to
0.07 meq/g.
[0298] 151.5 g of the dry polymer produced in the above
description, was dissolved in 353.5 g of water to produce a 30%
polymer solids solution. The temperature of this solution was
25.degree. C. To this polymer solution was added 60.9 g (0.658
moles) of epichlorohydrin as quickly as possible. After epi
addition the temperature began to rise due to the initial reaction
exotherm, a cooling water bath was applied to prevent the
temperature rising above 40.degree. C. Once the exotherm has
subsided, the temperature was maintained at 40.degree. C. Two hours
and forty five minutes after epi addition, the reaction mixture was
diluted to 21.5% total solids by the addition of 422 g of water.
The reaction mixture was then heated to 70.degree. C. over a forty
five minute period. Twenty minutes into the heating period, when
the temperature is approximately 55.degree. C., 8.0 g (0.078 moles)
of 96% sulphuric acid was added to the reaction mixture to reduce
the pH to a value of 7.1. Heating was maintained until the reaction
temperature has reached 70.degree. C. It was then maintained at
this temperature for ninety five minutes. After this period of time
at 70.degree. C., the pH of the reaction had a value of 6.0. It was
raised to a value of 6.5 by the addition of 12.5 g of 25% w/w
sodium hydroxide solution. Forty five minutes after the addition of
base, the reaction mixture was killed by the addition of 5.0 g of
96% sulphuric acid mixed in 200 g of water, a further 18.9 g of 96%
sulphuric acid was then added to adjust the pH to a value of 2.7.
This was then diluted to 15% total solids by the addition of 408 g
of water. This wet strength resin was then biodehalogenated in
batch mode according to the procedure described in Example 56.
Example 59
Handsheet Evaluation of Example 58 to Show Low CPD Reformation in
Paper in Comparison to Kymene.RTM. ULX2 Control
[0299] This example shows how paper made with the resin prepared in
example 58 results in a significant reduction of the CPD found on
paper as compared to paper made with a Kymene.RTM. ULX2
control.
[0300] PAPER MAKING
[0301] Pulp was made from a 50/50 hardwood/softwood mixture
(Scogcell Birch TCF, Encel Pine TCF). Process water of 100 ppm
CaCO.sub.3 hardness, 50 ppm CaCO.sub.3 alkalinity and pH 6.8-7.0
was used for stock preparation. Paper was made at ambient
temperature. Refining was carried out on a Hollander beater at
2.07% consistency for 22 minutes with 12 kg of weight to a freeness
of 31.degree.SR.
[0302] Handsheets were made on a Noble&Wood Handsheet Paper
Machine to a grammage of 100 gsm. The dry content after wet press
was 32.4%. The contact time on the drying cylinder was 75 sec at
105.degree. C., the sheet was dried to a final moisture content of
4.3%.
[0303] Both the experimental and control resins were added at 1%
and 2% db. CPD content of the paper was measured by the procedure
as described in Example 7. The results are summarized in Table 16.
TABLE-US-00017 TABLE 16 CPD in paper CPD in paper at 1 wt % db at 2
wt % db resin Resin sample code resin addition addition Kymene
.RTM. ULX2 221 ppb 407 ppb Example 58 58 ppb 104 ppb
Example 60
Preparation and Evaluation of a Polyamidoamide Epichlorohydrin
Resin Starting from a Polyaminoamide Prepolymer with a Low Level of
Residual Carboxylic Acid Group Functionality
[0304] Into a 350 liter stainless steel reactor was charged 80.0 kg
(775.4 moles) of diethylenetriamine. After sparging the reactor
with nitrogen, 107.9 kg (738.5 moles) of adipic acid was added to
the reactor at an approximate rate of 2.7 kg per minute. Rate of
addition was chosen such as to maintain the temperature below
120.degree. C. After addition of the adipic acid, the reactor was
heated to a temperature of 150.degree. C., by controlled
application of high pressure steam (9 bar) and hot oil (temperature
of 180.degree. C.). Once 150.degree. C. had been attained, heating
was maintained to raise the temperature further. Between
150.degree. C. and 160.degree. C., the reaction mixture began to
froth and bubble for a few minutes, which then subsided. After
this, condensate water appeared in the distillation system of the
reactor, and the temperature fell back to 155.degree. C. The
reaction mixture was then heated to 170.degree. C. as quickly as
possible using the maximum heating settings for the reactor. During
this heating up period, condensate water continued to be collected
in the distillation system of the reactor. The reactor reached a
temperature of 170.degree. C. ninety five minutes after the first
condensate water had been collected. 81.8% of the theoretical
condensate water had been collected at this time. The temperature
of the reactor was then maintained at 170.degree. C. for 90
minutes. After this holding period, 91.8% of the theoretical
condensate water had been collected. The temperature was then
raised to 178.degree. C., this temperature being achieved in
seventy five minutes. Once the temperature had reached 178.degree.
C., 94% of the theoretical condensate water had been collected. The
reactor was then maintained at a temperature between 178.degree. C.
and 180.degree. C. for six hours, at the end of which 99.3% of the
theoretical condensate water had been collected. The reaction
mixture was then `killed` by the addition of 86.9 kg of water.
After cooling to 90.degree. C., the polymer solution was discharged
to a holding tank and diluted further by the addition of 74.4 kg of
water. The acid number of this polymer solution was determined to
be 0.14 meq/dry gram of polymer using .sup.13C NMR analysis as
follows:
[0305] Charge a known amount of prepolymer at 0.75 g.+-.0.001 g (on
a dry basis) into a 2 ml Eppendorf tube. Add approximately 0.2 g of
water, followed by 0.2 g of deuterium oxide (D.sub.2O) and then
thoroughly mix, to produce a 65 wt % viscous polymer solution. Add
to this solution about a known amount of formic acid solution at
0.1 g.+-.0.01 g, followed by 2-3 drops of neat acetonitrile.
Thoroughly mix and transfer the sample to a dry NMR tube.
[0306] The following spectral parameters are can be used for a
Varian Gemini 2000, 300 MHZ NMR Spectrometer (available from Varian
B. V., Boerhavenplein 7, 4624 VT Bergen op Zoom, the Netherlands)
in automated acquisition mode. TABLE-US-00018 Resonance Frequency
300.105 MHZ (.sup.1H decoupling) 75.469 MHZ (.sup.13C) # Data
Points Acquired 15360 Acquisition Time 409.3 microseconds
Relaxation Delay 2.0 seconds Pulse Width 16.7 microseconds Number
of Scans 2048 Spectral Width 18761.7 Hz Line Broadening 3.18 Hz
Probe Temperature Room Temp. (21.degree. C.)
[0307] The spectrum is integrated between 160 ppm and 190 ppm, with
the following assignments being made to the major signals in this
region.
[0308] Polymer acid group, .delta.=182.2-182.5 ppm
[0309] Polymer amide groups, .delta.=177-176 ppm
[0310] Formic acid carboxyl group, .delta.=170.3 ppm
[0311] The acid number of the polymer is then determined from
knowledge of the integral of the polymer acid peak; the integral of
the formic acid peak; the mass of polymer added and the molarity
and mass of formic acid solution added. The following equation can
be used to calculate the acid number: Integral ( formic .times.
.times. acid ) * mass .times. .times. of .times. .times. dry
.times. .times. polymer Integral ( polymer .times. .times. acid
.times. .times. groups ) * mass .times. .times. of .times. .times.
formic .times. .times. acid .times. .times. solution .times. *
molarity .times. .times. of .times. .times. formic .times. .times.
acid .times. .times. solution ##EQU3##
Example
[0312] By NMR: 19.26 * 0.7487 .times. .times. g 2.45 * 0.1163
.times. .times. g * 7.3 .times. M = 0.144 .times. .times. meq
.times. / .times. g ##EQU4## By titration: 3.33 .times. .times. mls
* 0.100 .times. N * 100 4.9893 * 50.5 .times. .times. % = 0.132
.times. .times. meq .times. / .times. g ##EQU5## 3.61 .times.
.times. mls * 0.100 .times. N * 100 5.0650 * 50.5 .times. .times. %
= 0.141 .times. .times. meq .times. / .times. g ##EQU5.2## Average
Value 0.137 meq/g
[0313] Into a 350 liter stainless steel reactor, 67.6 kg of the
polymer solution, prepared in the above procedure, was charged
followed by 46.0 kg of water to prepare a 30% total solids polymer
solution. The temperature of this solution was 22.degree. C. To
this polymer solution, 16.0 kg (172.9 moles) of epichlorohydrin was
added over a one minute period. The exothermic reaction which then
ensued, raised the temperature of 40.degree. C. in 15 minutes.
Cooling water was then applied to the reactor to maintain the
temperature at 40.degree. C. Two hours after the addition of the
epichlorohydrin, a mixture of 1.33 kg of 96% w/w sulphuric acid
dissolved in 92.9 kg of water was added to the reactor as quickly
as possible. The temperature of the reactor was then raised to
70.degree. C. by the application of hot water (85.degree. C.) to
the heating coils of the reactor. This temperature was achieved in
thirty five minutes. The reactor was then maintained at 70.degree.
C. for one hour and forty five minutes, at which point the reaction
mixture was killed by the addition of a mixture of 1.6 kg of 96%
w/w sulphuric acid dissolved in 22.5 kg of water. The reaction
mixture was then cooled to 30.degree. C. by the application of cold
water to the heating coils. After attaining this temperature, the
mixture was discharged to a holding tank and then diluted further
by the addition of 150 kg of water. The pH of the mixture was then
adjusted to a value of 2.6 by the addition of 340 g of 96% w/w
sulphuric acid.
[0314] 100 mls of the resin was then biodehalogenated in batch mode
according the procedures described earlier in Example 56, specific
weights and measures being adjusted to the larger scale.
[0315] Paper was made with this dehalogenated
polyaminoamide-epichlorohydrin wet strength resin, according the
procedures described in Example 59. Paper was also made with
Kymene.RTM. ULX2 for comparative purposes. The wet strength of
these papers, after oven curing (80.degree. C. for thirty minutes)
and conditioning at 23.degree. C. and 50% relative humidity for
twenty four hours, were evaluated according to the procedures
described in Example 7. CPD in the paper samples were also
determined according to the procedures also described in Example 7.
The results of this evaluation are summarized in the Table 17
below. TABLE-US-00019 TABLE 17 % db addn wet tensile (kNm.sup.-1)
CPD in paper (ppb) Example 60 1.0 1.488 59 Kymene .RTM. 1.0 1.292
149 ULX2
Example 61
Preparation of Polyaminoamide Prepolymer Using Excess Amine
Method
[0316] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 324.99 g diethylenetriamine (DETA, 3.15 mole). To this
reactor was added 480.51 g dimethyl glutarate (3.00 mole) through
an addition funnel while stirring the reaction mixture. The
temperature was raised to 160.degree. C. and maintained there for 4
hours. During this time 225 mL distillate was removed through the
Dean-Stark trap. The product was isolated as the melt in an
aluminum pari. A solution of 244.61 g of the solid prepolymer was
mixed with 244.61 g water to form an aqueous solution. The total
solids of this solution was 47.54 wt % and the RSV was 0.1287 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0% as described previously. This
material had an amine number of 6.18 meq/g and an acid number of
0.168 meq/g, determined by titration as previously described.
Example 62
Preparation of Polyaminoamide Prepolymer Using Excess Amine
Method
[0317] A 1000 mL resin kettle fitted with condenser, Dean-Stark
trap, thermocouple, addition funnel and mechanical stirrer was
charged with 324.99 g diethylenetriamine (DETA, 3.15 mole). To this
reactor was added 480.51 g dimethyl glutarate (3.00 mole) through
an addition funnel while stirring the reaction mixture. The
temperature was raised to 170.degree. C. and maintained there for 4
hours. During this time 268 mL distillate was removed through the
Dean-Stark trap. The product was isolated as the melt in an
aluminum pan, a solution of 316.18 g of the solid prepolymer was
mixed with 316.18 g water to form an aqueous solution. The total
solids of this solution was 45.20 wt % and the RSV was 0.1289 dL/g,
determined in 1.0N NH.sub.4Cl at 2.0% as described previously. This
material had an amine number of 6.28 meq/g and an acid number of
0.111 meq/g, determined by titration as previously described.
Example 63
Biodehalogenation and Handsheet Evaluation of Examples 49 and
50
[0318] A sample of 752.15 g of the resin of Example 49 was adjusted
to pH 5.8 with 14.41 grams of 20% aqueous sodium hydroxide. To the
mixture was added 85.17 grams of a blend of microorganisms
comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 6.93 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used were: Arthrobacter histidinolovorans (HK1) and
Agrobacterium tumefaciens (HK7). The flask was placed in a
30.degree. C. water bath and maintained at 30.degree. C. The pH was
maintained at 5.8 by periodic addition of 20% aqueous sodium
hydroxide. After 48 hours, a sample was removed and submitted for
GC analysis and the mixture was cooled to room temperature.
[0319] The resin of Example 50 was treated in a similar manner
using a 753.43 g sample of the resin that was adjusted to pH 5.8
with 13.43 g of 20% aqueous sodium hydroxide and to which was added
85.21 grams of a blend of microorganisms comprising an inoculum
from a biodehalogenated polyaminopolyamide-epichlorohydrin resin
and 6.93 grams of a nutrient solution.
[0320] The procedures outlined in Example 7 were used to prepare
and test paper containing the biodehalogenated resins. Only
oven-aged samples were prepared. The results of paper testing and
analysis for 3-CPD are shown in the Table 18 below. TABLE-US-00020
TABLE 18 Testing of Oven-Aged Handsheets Dry Wet 3-CPD in Basis Wt.
Tensile Tensile paper Sample Add-on (#/ream) (#/inch) (#/inch)
(ppb) Blank -- 39.5 14.38 0.39 n.d. Kymene .RTM. ULX2 1% 40.4 21.03
4.39 244 Biodehalogenated 1% 39.1 22.19 4.72 74 Ex. 49
Biodehalogenated 1% 39.7 20.31 4.50 89 Ex. 50
Example 64
Lab Biodehalogenation of a Modified pH Treated
Polyaminopolyamide-epi Resin and Accelerated Aging
[0321] A 250 g portion of Resin B (see Comparative Example 2) was
charged into a bottle containing a magnetic stirrer. The pH was
adjusted to 6.0 with 31.5 g of 4% aqueous sodium hydroxide. An
aliquot was removed from the bottle and submitted for GC analysis.
The bottle was capped and placed in a 50.degree. C. water bath and
maintained at 50 C. After 6 hours, an aliquot was removed from the
bottle and submitted for GC analysis. A 225 gram sample of this
resin was charged into a 3-necked, round-bottomed flask equipped
with a magnetic stirrer, a condenser, an air sparge and a pH meter.
The pH was adjusted to 5.8 with 10% aqueous sodium hydroxide. To
the mixture was added 112.5 g of a blend of microorganisms
comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 2.7 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used had the following composition: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
10% aqueous sodium hydroxide. After 48 hours, a sample was removed
and submitted for GC analysis. The mixture was cooled to room
temperature and the pH was adjusted to 3.0 with 10% sulfuric acid.
The resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 19.
[0322] This treatment resulted in about a 49-52% reduction in CPD
reformation in the resin relative to an untreated control
(Comparative Example 2) and about a 73% reduction relative to
commercially obtained Kymene.RTM. ULX2 wet-strength resin
(Comparative Example 1). TABLE-US-00021 TABLE 19 Temp Time 1,3-DCP
2,3-DCP 3-CPD (Celsius) (hours) (ppm) (ppm) (ppm) 20 0 ND 0.5 0.1
50 70 0.3 0.6 6.7 50 89 0.3 0.6 7.7 50 112 0.3 0.6 8.4 50 161 0.9
1.5 14.3 50 233 0.3 0.5 10.0 50 328 0.3 0.5 10.1 32 65 0.3 0.5 1.4
32 89 0.3 0.5 1.9 32 160 0.3 0.5 3.1 32 328 0.2 0.5 3.9 32 496 0.2
0.5 1.4 32 664 0.3 0.5 8.9 32 832 0.2 0.5 8.7 32 1170 0.3 0.6 10.2
32 1504 0.3 0.6 10.9
Example 65
Lab Biodehalogenation of a Modified pH Treated
Polyaminopolyamide-epi Resin and Accelerated Aging
[0323] A 140 g portion of Resin B (see Comparative Example 2) was
charged into a bottle containing a magnetic stirrer. The pH was
adjusted to 5.8 with 17.4 g of 4% aqueous sodium hydroxide. The
bottle was capped and placed in a 30.degree. C. water bath and
maintained at 30.degree. C. Periodically, aliquots were removed
from the bottle and submitted for GC analysis. After 7 days, the
resin was diluted to 10 wt % solids. A 130 gram sample of this
resin was charged into a 3-necked, round-bottomed flask equipped
with a magnetic stirrer, a condenser, an air sparge and a pH meter.
The pH was adjusted to 5.8 with 10% aqueous sodium hydroxide. To
the mixture was added 65 g of a blend of microorganisms comprising
an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 1.6 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used had the following composition: Arthrobacter
histidinolovorans (HK1) and Agrobacterium tumefaciens (HK7). The
flask was placed in a 30.degree. C. water bath and maintained at
30.degree. C. The pH was maintained at 5.8 by periodic addition of
10% aqueous sodium hydroxide. After 28 hours, the mixture was
cooled to room temperature and the pH was adjusted to 3.0 with 10%
sulfuric acid. A sample was removed and submitted for GC analysis.
The resin was subjected to accelerated aging as described in
Comparative Example 1. The results are reported in Table 20.
TABLE-US-00022 TABLE 20 Temp Time 1,3-DCP 2,3-DCP 3-CPD 3-CPD * 1.3
(Celsius) (hours) (ppm) (ppm) (ppm) (ppm) 20 0 ND 0.5 0.0 0.0 50 22
ND 0.4 2.7 3.5 50 46 ND 0.5 4.4 5.7 50 138 ND 0.5 8.0 10.4 50 210
ND 0.5 8.8 11.5 32 22 ND 0.4 0.3 0.4 32 46 ND 0.4 0.9 1.2 32 186 ND
0.4 2.5 3.3 32 353 ND 0.4 4.2 5.4 32 521 ND 0.4 5.4 7.0 32 857 ND
0.4 6.5 8.5 32 1312 ND 0.4 8.6 11.2
[0324] When corrected for the dilution of the resin, this treatment
resulted in a 41% reduction in CPD reformation in the resin
relative to an untreated control (Comparative Example 2) and about
a 68% reduction relative to commercially obtained Kymene.RTM. ULX2
(Comparative Example 1).
Comparative Example 6
Base-Treatment of Kymene.RTM. ULX2 Wet-strength Resin
[0325] Resin D (see Comparative Example 4) after refrigeration for
one month had non-detectable 1,3-DCP, 0.5 ppm of 2,3-DCP and 11.3
ppm of CPD. To 127.4 g (wet basis) of Resin D in a glass bottle was
added 15.9 g of deionized water. Magnetic stirring was started and
the solution was heated to 55.degree. C. with a water bath fitted
with a Cole-Parmer Polystat.RTM. temperature controller. The pH was
monitored with a Beckman 10 pH meter connected to an automatic
temperature compensator and a Ross pH electrode, sure flow. The pH
meter was calibrated daily with pH 7 and 10 buffer solutions. To
the resin solution at 55.degree. C. was injected 17.6 g (16.0 mL)
of 10% (wt/wt) aqueous sodium hydroxide. (This gave a solution with
10 wt % resin solids). The peak pH was 10.9. The pH was 10.5 after
5 minutes at which time the resin was cooled rapidly to room
temperature and analyzed by gas chromatography (GC). This analysis
showed non-detectable 1,3-DCP, 0.2 ppm of 2,3-DCP and 0.3 ppm of
CPD.
Example 66
Handsheet Evaluation of Comparative Example 6
[0326] The procedure of Example 7 was used to evaluate Comparative
Example 6. Results for oven-cured paper are reported in Table 21
with respect to that previously indicated for Examples 2-6 and
Comparative Example 4. TABLE-US-00023 TABLE 21 Oven-Cured Paper.
Basis Wt. Normalized dry wet % % of CPD in % tensile tensile wet/
Comp. Paper Example Added pH lbs/in lbs/in dry Ex. 4 (ppb) Blank --
7.5 18.50 0.52 3 11 <30 Comp. Ex. 4 0.50 7.5 25.15 4.86 19 100
-- Comp. Ex. 4 1.00 7.5 27.92 6.01 22 100 319 Example 4 0.50 7.5
24.39 4.40 18 91 -- Example 4 1.00 7.5 23.79 5.29 22 88 <30
Example 3 0.50 7.5 24.06 4.39 18 90 -- Example 3 1.00 7.5 26.15
5.30 20 88 <30 Example 6 0.50 7.5 26.08 4.59 18 94 -- Example 6
1.00 7.5 25.93 5.88 23 98 36 Example 2 0.50 7.5 22.70 2.94 13 61 --
Example 2 1.00 7.5 22.55 4.05 18 67 <30 Example 5 0.50 7.5 22.27
3.24 15 67 -- Example 5 1.00 7.5 23.38 4.46 19 74 39 Comp. Ex. 6
0.50 7.5 22.74 3.91 17 80 -- Comp. Ex. 6 1.00 7.5 24.22 4.86 20 81
<30
Example 67
pH Modified Treated Polyaminopolyamide-epi Resin
[0327] A 129.5 g portion of Resin D (see Comparative Example 4) was
charged into a bottle containing a magnetic stirrer. The pH was
adjusted to 6.0 with 2.81 g of 20% aqueous sodium hydroxide. The
bottle was capped and placed in a 30.degree. C. water bath and
maintained at 30.degree. C. Periodically, aliquots were removed
from the bottle and submitted for GC analysis. After 5 days, the
resin was cooled to room temperature and used as an additive for
papermaking.
[0328] The procedure of Examples 7 and 10 was used to evaluate this
sample. Results for oven-cured paper are reported in Table 22 along
with the other previously indicated Examples and Comparative
Examples. The base treatment of this Example reduced the CPD in the
paper compared to the untreated resin (Comparative Example 4).
TABLE-US-00024 TABLE 22 Basis Wt. Normalized dry wet % of CPD in %
tensile tensile wet/ Comp. Paper Example Added pH lbs/in lbs/in dry
Ex. 4 (ppb) Blank -- 7.5 21.15 0.65 3 16 <30 Comp. Ex. 4 0.50
7.5 22.74 4.18 18 100 Comp. Ex. 4 1.00 7.5 27.22 6.00 22 100 344
Example 4 0.50 7.5 25.26 4.43 18 106 Example 4 1.00 7.5 26.97 5.44
20 91 <30 Comp. Ex. 5 0.50 7.5 23.59 4.59 19 110 Comp. Ex. 5
1.00 7.5 23.63 5.44 23 91 269 Example 8 0.50 7.5 21.50 2.86 13 68
Example 8 1.00 7.5 23.32 4.16 18 69 36 Example 9 0.50 7.5 24.38
4.48 18 107 Example 9 1.00 7.5 24.48 5.13 21 85 <30 Example 67
0.50 7.5 23.42 4.76 20 114 Example 67 1.00 7.5 25.85 5.81 22 97
246
Example 68
Reduction of CPD Release on Paper by Base Treatment of Kymene.RTM.
ULX2
[0329] The following example shows that CPD release from
Kymene.RTM. ULX2 can be reduced dramatically by base-treating the
resin prior to use. A sample of base-treated Kymene.RTM. ULX2 was
prepared in the following way:
[0330] Kymene.RTM. ULX2 wet-strength resin, which is a
polyaminopolyamide-epi resin available from Hercules Incorporated
(Wilmington, Del.) was obtained from the Voreppe, France plant. In
a 100 ml three neck flask equipped with a magnetic stirrer, 50 ml
of Kymene.RTM. ULX2 were heated on a waterbath to 55.degree. C.
while stirred. 3 g of a 25% NaOH solution in demineralized water
were added at once (0.0028 Mol of base/dry g of resin). Immediately
after addition of the base, the reaction mixture was cooled to room
temperature and the pH was adjusted to pH 2.6 with 96% w/w
sulphuric acid. The product was used to make handsheets on the same
day.
Paper Making
[0331] Pulp was made from a 50/50 hardwood/softwood mixture
(Scogcell Birch TCF, Encel Pine TCF). Process water of 100 ppm
CaCO3 hardness, 50 ppm CaCO3 alkalinity and pH 6.8-7.0 was used for
stock preparation. Paper was made at ambient temperature. Refining
was carried out on a Hollander beater at 2.07% consistency for 22
minutes with 12 kg of weight to a freeness of 31.degree.SR.
[0332] Handsheets were made on a Noble&Wood Handsheet Paper
Machine to a grammage of 100 gsm. The dry content after wet press
was 32.4%. The contact time on the drying cylinder was 75 sec at
105.degree. C., the sheet was dried to a final moisture content of
4.3%. All experimental and control resins were added at 1% and 2%
db. CPD content of the paper was measured as described in Example
7. The results are summarized in Table 23. TABLE-US-00025 TABLE 23
CPD in paper at 1% CPD in paper at 2% Resin sample db resin
addition db resin addition Kymene .RTM. ULX2 221 ppb 407 ppb
control Example 68 <30 ppb 36 ppb
Example 69
Reduction of CPD Release on Paper by Base Treatment of Kymene.RTM.
ULX2
[0333] 280 ml of Kymene.RTM. ULX2 obtained from the Voreppe, France
plant were placed in a 500 ml three neck flask equipped with a
magnetic stirrer and condensor. The solution was under stirring
warmed to 30.degree. C. in a waterbath. 16.9 g of a 25% NaOH
solution in demineralized water were added to the resin solution.
After 30 min of reaction, the mixture was cooled back o room
temperature and acidified with 96% w/w sulphuric acid to a final pH
of 2.6. The product was used to make handsheets on the same day.
Papermaking was carried out as described in Example 68. CPD content
of the paper was measured as described in Example 7. The results
are summarized in Table 24. TABLE-US-00026 TABLE 24 CPD in paper at
1% CPD in paper at 2% Resin sample db resin addition db resin
addition Kymene .RTM. ULX2 221 ppb 407 ppb control Example 69
<30 ppb <30 ppb
Example 70
Reduction of CPD Release on Paper by Acid Treatment of Kymene.RTM.
617
[0334] Kymene.RTM. 617 wet-strength resin which is a
polyaminopolyamide-epi resin available from Hercules Incorporated
(Wilmington, Del.) was obtained from the Zwijndrecht, Netherlands
plant. 40 ml of this resin were acidified with 96% w/w sulfuric
acid to a final pH of 1. The sample was stored in an oven at
50.degree. C. for 24 h. Then the sample pH was adjusted to 5.8 with
30% w/w NaOH and the sample was biodehalogenated in batch mode as
described in Example 56.
[0335] The biodehalogenated sample was used to make handsheets as
described in Example 68. The CPD levels in the handsheets were
measured as described in Example 7. The results are summarized in
Table 25. TABLE-US-00027 TABLE 25 CPD in paper at CPD in paper at
1% 2% db resin Resin sample db resin addition addition Kymene .RTM.
ULX2 221 ppb 407 ppb control Example 70 74 ppb 138 ppb
Example 71
Reduction of CPD Release on Paper by Application of a
Biodehalogenated, Polyamine-epichlorohydrin Wet Strength Resin not
Containing Acid End Groups
[0336] Resin Synthesis: To a one liter flange flask equipped with
thermocouple, overhead mechanical stirrer, condensor and pH meter,
was charged 195.8 g (2.116 moles) of epichlorohydrin. To this was
added 211.0 g of water. This mixture was then stirred at 150 rpm.
To this mixture was slowly added 148.8 g (0.896 moles) of 70%
hexamethylenediamine solution. The resulting exotherm raised the
temperature to 35.degree. C. The application of an ice/water batch
to the reactor prevented the temperature from increasing further.
After one hour, all of the hexamethylenediamine solution had been
added. The stirrer speed was increased to 200 rpm and the
temperature of the reactor raised to 80.degree. C. over a twenty
minute period. Once at 80.degree. C. the reaction mixture was
maintained at this temperature. The pH of the reaction mixture was
periodically measured, as to was the development of viscosity by
monitoring the Gamer-Holt viscosity at 25.degree. C. After two and
a half hours at 80.degree. C., the reaction mixture had a pH of
5.2. This was increased to a value of 5.8 by the addition of 15 g
of 25% w/w sodium hydroxide solution. After the addition of aqueous
base, the viscosity of the reaction mixture began to increase. When
a Gardner-Holt Viscosity of `T` had been attained, one hour after
the addition of base, the reaction mixture was diluted by the
addition of 96.2 g of water. The Gardner-Holt viscosity was
determined to be `I` after dilution. The reaction mixture was
quickly restored to 80.degree. C. and then maintained at thus
temperature. Forty minutes after this dilution step, the reaction
mixture had attained a Gardner-Holt Viscosity of `T` again. The
reaction was then killed by the addition of a mixture of 5.1 g of
96% w/w sulphuric acid in 137 g of water. The mixture was then
cooled to 25.degree. C. and the pH of the resin adjusted to a value
of 2.7 by the addition of 6.0 g of 96% w/w sulphuric acid.
[0337] Biodehalogenation: 1) Preparation of preculture of HKC on
Kymene.RTM. 617
[0338] 50 mls of Kymene(D 617 was adjusted to a pH value of 5.8 by
the addition of 25% w/w sodium hydroxide solution. To this was then
added 0.5 mls of a nutrient package (consisting of 33 g of urea; 5
g of potassium dihydrogen phosphate; 5.0 g of magnesium sulphate
heptahydrate and 1.0 g of calcium chloride monohydrate dissolved in
1 liter of demineralized water), and 100 .mu.l of 10% sterile yeast
extract solution (from Difco). This mixture was then transferred to
a 250 ml Erlenrmeyer flask. To this was then added 0.25 mls of HKC
stock. The flask was then placed in an orbital shaker (200-250
rpm), and the material allowed to incubate at 30.degree. C. for
twenty four hours.
[0339] 2) Biodehalogenation of polyamine-epichlorohydrin wet
strength resin
[0340] The resin above was diluted to 13% solids with water and 500
mls of this polyamine-epichlorohydrin resin was adjusted to a pH
value of 5.8 by the addition of 25% w/w sodium hydroxide solution.
To this was then added 5 mls of a nutrient package (consisting of
33 g of urea; 5 g of potassium dihydrogen phosphate; 5.0 g of
magnesium sulphate heptahydrate and 1.0 g of calcium chloride
monohydrate dissolved in 1 liter of water) and 2 ml of 10% yeast
extract solution. Glycerol was added to the resin to a final
concentration of 5 mM to enhance growth of the HKC. This mixture
was then transferred to a sterile 5 l Erlenmeyer flask and then
inoculated with 20 ml of the Kymene.RTM. 617 pre-culture prepared
in the procedure above. The flask was then placed in an orbital
shaker (200-250 rpm), and the material allowed to incubate at
30.degree. C. for 72 hours.
[0341] After 72 hours, the resin was transferred to a 1 liter
plastic bottle and then pH adjusted to a value of 2.8 by the
dropwise addition of 96% w/w sulphuric acid. 1060 .mu.l of
potassium sorbate solution (94 mg/ml) and 1 ml of Proxel.RTM. BD
(from Zeneca Biocides) were then added to the resin, and the sample
thoroughly mix by a high shear mixer.
[0342] Papermaking: The sample which was prepared and
biodehalogenated as described above was tested for CPD reformation
in handsheets as described in Example 68. The results are
summarized in Table 26. TABLE-US-00028 TABLE 26 CPD in paper at CPD
in paper at 1% 2% db resin Resin sample code db resin addition
addition Kymene .RTM. ULX2 221 ppb 407 ppb control Example 71 33
ppb <30 ppb
Example 72
Reduction of CPD Release on Paper by Application of a
Biodehalogenated, Acid-free Wet Strength Resin Based on Kymene.RTM.
736
[0343] To a one liter flange flask equipped with thermocouple,
overhead mechanical stirrer, condensor and pH meter, was charged
195.8 g (2.116 moles) of epichlorohydrin. To this was added 211.0 g
of water. This mixture was then stirred at 150 rpm. To this mixture
was slowly added 148.8 g (0.896 moles) of 70% hexamethylenediamine
solution. The resulting exotherm raised the temperature to
35.degree. C. The application of an ice/water batch to the reactor
prevented the temperature from increasing further. After one hour,
all of the hexamethylenediamine solution had been added. The
stirrer speed was increased to 200 rpm and the temperature of the
reactor raised to 80.degree. C. over a twenty minute period. Once
at 80.degree. C. the reaction mixture was maintained at this
temperature. The pH of the reaction mixture was periodically
measured, as to was the development of viscosity by monitoring the
Gamer-Holt viscosity at 25.degree. C. After two and a half hours at
80.degree. C., the reaction mixture had a pH of 5.2. This was
increased to a value of 5.8 by the addition of 15 g of 25% w/w
sodium hydroxide solution. After the addition of aqueous base, the
viscosity of the reaction mixture began to increase. When a
Gardner-Holt Viscosity of `T` had been attained, one hour after the
addition of base, the reaction mixture was diluted by the addition
of 96.2 g of water. The Gardner-Holt viscosity was determined to be
`I` after dilution. The reaction mixture was quickly restored to
80.degree. C. and then maintained at this temperature. Forty
minutes after this dilution step, the reaction mixture had attained
a Gardner-Holt Viscosity of `T` again. The reaction was then killed
by the addition of a mixture of 5.1 g of 96% w/w sulphuric acid in
137 g of water. The mixture was then cooled to 25.degree. C. and
the pH of the resin adjusted to a value of 2.7 by the addition of
6.0 g of 96% w/w sulphuric acid.
[0344] 171 g of this resin was diluted to 13% total solids and then
biodehalogenated in batch mode according to the procedure described
earlier in Example 71 with the following modifications: 1) 5 mM of
glycerol was added to the polyamine-epichlorohydrin resin; 2) 20
mls of preculture were used to inoculate the resin; 3) the resin
was incubated for 72 h at 30.degree. C.
[0345] The dehalogenated resin was then aged at 50.degree. C. and
CPD reformation was checked, according to the procedures described
earlier. The results are summarized in the table below.
TABLE-US-00029 CPD after CPD after dehalogenation dehalogenation
CPD after before and one week at dehalogenation and 50.degree. C.
ageing 50.degree. C. two weeks at 50.degree. C. Example 72 <1
ppm <1 ppm 2 ppm
Example 73
Example of Base treatment(s) of Kymene.RTM. SLX on Subsequent
Reformation of CPD in the Biodehalogenated Resin
[0346] 250 g of Kymene.RTM. SLX obtained from Hercules Incorporated
was charged to a 500 ml flange flask, fitted with overhead stirrer,
thermocouple, condensor and pH meter. The stirrer was set to 400
rpm, and the reaction heated to 50.degree. C. with a hot water
bath. Once at 50.degree. C., the pH was adjusted from a value of
2.8 to 9.0 by the addition of 10.3 g of 25% w/w sodium hydroxide
solution. The reaction mixture was then maintained at these
temperature and pH conditions for 12 minutes. pH was maintained by
the further dropwise addition of aqueous base as required (a
further 0.7 g was needed to do this). The reaction mixture was then
cooled to 25.degree. C. and the pH adjusted to a value of 5.8 by
the addition of 1.6 g of 96% w/w sulphuric acid, ready for
biodehalogenation.
[0347] A second batch of Kymene.RTM. SLX was base treated in a
similar manner to the procedure described above except that the
reaction mixture was heated to a temperature of 40.degree. C., and
maintained at pH 9 and 40.degree. C. for forty five minutes.
[0348] The two base treated resins were then biodehalogenated in
batch mode, according to the procedure described earlier. The
untreated base resin was also biodehalogenated in batch mode, as
described in Example 56.
[0349] The three dehalogenated resins were then aged at 50.degree.
C. and the CPD reformation determined, as described in Example 1.
The results of this ageing study are summarized Table 27 below.
TABLE-US-00030 TABLE 27 Base treat- CPD after CPD after CPD after
ment dehalogenation dehalogenation dehalogenation condi- before
50.degree. C. and one week and two weeks Resin tions ageing at
50.degree. C. at 50.degree. C. Kymene .RTM. -- <1 ppm 29 ppm 32
ppm SLX Base 50.degree. C., <1 ppm 27 ppm 40 ppm treated 1 pH
9.0, 12 minutes Base 40.degree. C., <1 ppm 23 ppm 27 ppm treated
2 pH 9.0, 45 minutes
Comparative Example 7
[0350] Kymene.RTM. ULX2 wet-strength resin, a
polyaminopolyamide-epi resin which contains less than about 5 ppm
of DCP and less than about 50 ppm of CPD and is available from
Hercules Incorporated (Wilmington, Del.), was obtained from the
Voreppe, France plant, and had a total solids of 13.6 wt % and a pH
of 2.7. This Kymene.RTM. is designated as Resin E. This resin was
stored in a cold room (4.degree. C.) for long-term storage. This
resin is not CPD storage stable, even when stored in the cold
room.
Comparative Example 8
Aging of a Polyaminopolyamide-epichlorohydrin (epi) Resin
(Control)
[0351] Kymene.RTM. ULX2 wet-strength resin, a
polyaminopolyamide-epi resin which contains less than about 5 ppm
of DCP and less than about 50 ppm of CPD and is available from
Hercules Incorporated (Wilmington, Del.), was obtained from the
Lilla Edet, Sweden plant, and had a total solids of 13.4 wt % and a
pH of 3.1. This Kymene.RTM. is designated as Resin F. This resin
was stored in a cold room (4.degree. C.) for long-term storage.
This resin is not CPD storage stable, even when stored in the cold
room (see Table 28), as determined by GC analysis. TABLE-US-00031
TABLE 28 Temp Time 1,3-DCP 2,3-DCP 3-CPD (Celsius) (hours) (ppm)
(ppm) (ppm) 4 0 ND 0.45 15.8 4 864 ND 0.43 26.1 4 7350 ND 0.49
63.2
Comparative Example 9
[0352] Kymene.RTM. ULX2 wet-strength resin, a
polyaminopolyamide-epi resin which contains less than about 5 ppm
of DCP and less than about 50 ppm of CPD and is available from
Hercules Incorporated (Wilmington, Del.), was obtained from the
Lilla Edet, Sweden plant (Lot 25G9), and had a total solids of 13.3
wt % and a pH of 3.2. This Kymene.RTM. is designated as Resin G.
This resin was stored in a cold room (4.degree. C.) for long-term
storage. This resin is not CPD storage stable, even when stored in
the cold room.
Comparative Example 10
[0353] The amount of CPD producing species in Resin F were
estimated using the following acid test. A portion of resin to be
tested was charged into a bottle containing a magnetic stirrer. The
pH was adjusted to 1.0 with 96% sulfuric acid. The bottle was
capped and placed in a 50.degree. C. water bath and maintained at
50.degree. C. with stirring. Periodically, aliquots were removed
from the bottle and submitted for GC analysis. The CPD produced
after 24 hours is used to estimate the amount of CPD producing
species. See Table 29 for results. TABLE-US-00032 TABLE 29 Temp
Time 1,3-DCP 2,3-DCP 3-CPD (Celsius) (hours) (ppm) (ppm) (ppm) 50 4
ND ND 203.9 50 24 ND ND 306 50 70 ND ND 309
Example 74
General Procedure for Screening Activity of Resins and Evaluating
Reaction Conditions
[0354] A portion of Resin F was charged into a container with a
stirrer. The pH was adjusted with 20% aqueous sodium hydroxide and
a portion of enzyme was added. The container was closed to minimize
evaporation of water. The container was placed in a
temperature-controlled water bath and maintained at the desired
temperature. Periodically, an aliquot was removed from the bottle
and submitted for GC analysis as previously described. pH was
measured in a similar manner as described in Comparative Example 6.
The results are reported in Table 30. For pH values having one
digit, the pH value is the initial pH, and for pH values having two
digits, the pH was maintained by addition of the sodium hydroxide
solution. It is noted that Alcalase, Resinase A, Palatase, Lipolase
100L, Novocor AD, and Flavourzyme were obtained from Novo Nordisk
BioChem, North America, Inc. Franklinton, North Carolina, and
Lipase M was obtained from Alamo, USA, Corp., Lombard, Ill., and
were used as received (except the Flavourzyme was used as a 10%
dilution in water, and the Lipase M was used as a 5% dilution in
water). TABLE-US-00033 TABLE 30 Enzyme Temp Time 1,3-DCP 2,3-DCP
3-CPD Amt. (g) Amt. (g) Enzyme pH (.degree. C.) (hours) (ppm) (ppm)
(ppm) Resin E 160.0 0.00 No enzyme 7 40 1 ND 0.61 12.7 160.0 0.00
No enzyme 7 40 3 ND 0.56 17.2 160.0 0.00 No enzyme 7 40 6 ND 0.67
23.8 140.0 1.00 Resinase A 7 40 1 ND 0.51 11.0 140.0 1.00 Resinase
A 7 40 2 ND 0.56 11.1 140.0 1.00 Resinase A 7 40 3 ND 0.51 11.7
140.0 1.00 Resinase A 7 40 6 ND 0.57 17.6 140.0 1.00 Palatase 7 40
1 ND 0.65 10.0 140.0 1.00 Palatase 7 40 2 ND 0.59 10.5 140.0 1.00
Palatase 7 40 3 ND 0.61 13.0 140.0 1.00 Palatase 7 40 6 ND 0.59
12.9 Resin F 120 0.90 Lipolase 100L 6 40 1 ND ND 26.5 120 0.90
Lipolase 100L 6 40 6 ND 0.46 28.5 120 0.90 Lipolase 100L 6 40 24 ND
0.55 30.2 120 0.90 Lipolase 100L 7 40 1 ND ND 27.2 120 0.90
Lipolase 100L 7 40 6 ND ND 34.5 120 0.90 Lipolase 100L 7 40 24 ND
ND 22 120 0.00 None (control) 7 40 1 ND 0.47 27.8 120 0.00 None
(control) 7 40 6 ND 0.38 37.6 120 0.00 None (control) 7 40 24 ND
0.38 28.3 120 0.90 Novocor AD 7 40 1 ND 0.45 30.4 120 0.90 Novocor
AD 7 40 6 ND ND 36.9 120 0.90 Novocor AD 7 40 24 ND 0.54 31.8 120
0.90 Novocor AD 6 40 1 ND 0.45 26.3 120 0.90 Novocor AD 6 40 6 ND
ND 33.5 120 0.90 Novocor AD 6 40 24 ND ND 40 160 1.15 Novocor AD 5
40 1 ND 0.44 38.3 160 1.15 Novocor AD 5 40 6 ND 0.47 39.4 160 1.15
Novocor AD 5 40 24 ND 0.37 32.6 160 1.15 Novocor AD 5 40 46 ND 0.44
39.1 160 1.15 Novocor AD 4 40 1 ND 0.59 30.6 160 1.15 Novocor AD 4
40 6 ND 0.39 37.4 160 1.15 Novocor AD 4 40 24 ND 0.37 36.8 160 1.15
Novocor AD 4 40 46 ND 0.45 35.7 160 1.15 Novocor AD 4 40 166 ND
0.58 51.8 160 1.15 Novocor AD 3 40 1 ND 0.51 30.7 160 1.15 Novocor
AD 3 40 6 ND 0.37 38.7 160 1.15 Novocor AD 3 40 24 ND 0.44 47.6 160
1.15 Novocor AD 3 40 46 ND 0.50 42.4 160 1.15 Novocor AD 3 40 166
ND 0.47 59.6 160 1.15 Novocor AD 6 50 1 ND 0.35 33.0 160 1.15
Novocor AD 6 50 6 ND ND 31.1 160 0.00 no enzyme 5 40 1 ND 0.40 34.7
160 0.00 no enzyme 5 40 6 ND 0.55 28.7 160 0.00 no enzyme 5 40 24
ND 0.52 41.3 120 1.80 5% Lipase M 7 40 1 ND 0.46 40.7 120 1.80 5%
Lipase M 7 40 6 ND 0.41 42.3 120 1.80 5% Lipase M 7 40 24 ND 0.37
46.2 120 0.90 10% Flavourzyme 7 40 1 ND 0.51 40.1 120 0.90 10%
Flavourzyme 7 40 6 ND 0.35 41.0 120 0.90 10% Flavourzyme 7 40 24 ND
0.54 46.6 120 0.90 Resinase A 7 40 1 ND 0.52 41.0 120 0.90 Resinase
A 7 40 6 ND 0.48 50.6 120 0.90 Resinase A 7 40 24 ND 0.52 43.3 120
0.90 Alcalase 7 40 1 ND 0.4 153 120 0.90 Alcalase 7 40 6 ND ND 259
120 0.90 Alcalase 7 40 24 ND ND 342 30.0 0.00 No enzyme 7 40 0 ND
ND 50.4 30.0 0.00 No enzyme 7 40 6 ND ND 57.3 30.0 0.00 No enzyme 7
40 24 ND ND 69.9 30.0 0.25 Alcalase 7 40 0 ND ND 148 30.0 0.25
Alcalase 7 40 6 ND ND 212 30.0 0.25 Alcalase 7 40 24 ND ND 318
Resin G 30.0 0.25 Alcalase 7 40 0 ND ND 89 30.0 0.25 Alcalase 7 40
6 ND ND 146 30.0 0.25 Alcalase 7 40 24 ND ND 193 Resin F 30.0 0.25
Alcalase 6 40 0 ND 1 66 30.0 0.25 Alcalase 6 40 6 ND ND 77 30.0
0.25 Alcalase 6 40 24 ND ND 148 30.0 0.25 Alcalase 8 40 0 ND ND 226
30.0 0.25 Alcalase 8 40 6 ND ND 331 120.0 0.00 No enzyme 3 50 4 ND
ND 49.9 120.0 0.00 No enzyme 3 50 24 ND ND 59.7 120.0 0.00 No
enzyme 3 50 70 ND ND 111 60.0 0.50 Alcalase 8 50 1 ND ND 208.9 60.0
0.50 Alcalase 8 50 2 ND ND 241.9 60.0 0.50 Alcalase 8 50 4 ND ND
237.2 60.0 0.50 Alcalase 7 50 1 ND 0.87 59.9 60.0 0.50 Alcalase 7
50 2 ND 0.47 54.8 60.0 0.50 Alcalase 7 50 4 ND 0.50 63.1 60.0 0.50
Alcalase 7 50 6 ND ND 61.5 60.0 0.50 Alcalase 7 30 1 ND ND 260.4
60.0 0.50 Alcalase 7 30 2 ND ND 237.6 60.0 0.50 Alcalase 7 30 4 ND
ND 325.0 60.0 0.50 Alcalase 7 30 6 ND ND 332.9 30.0 0.25 Alcalase 8
40 1 ND ND 208.5 30.0 0.25 Alcalase 8 40 6 ND ND 330.2 30.0 0.00 No
enzyme 8 40 1 ND ND 62.0 30.0 0.00 No enzyme 8 40 6 ND ND 64.9 30.0
0.00 No enzyme 7 40 1 ND 0.6 70.1 30.0 0.00 No enzyme 7 40 6 ND
0.53 72.8 30.0 0.00 No enzyme 7 40 26 ND 0.45 64.2 90.0 0.75
Alcalase 8.5 30 0 ND ND 107.5 90.0 0.75 Alcalase 8.5 30 1 ND ND
204.7 90.0 0.75 Alcalase 8.5 30 2 ND ND 249.4 90.0 0.75 Alcalase
8.5 30 4 ND ND -- 90.0 0.75 Alcalase 8.5 30 6 ND ND 319.2 90.0 0.75
Alcalase 9.0 30 0 ND ND 94.9 90.0 0.75 Alcalase 9.0 30 1 ND ND
196.6 90.0 0.75 Alcalase 9.0 30 2 ND ND 260.3 90.0 0.75 Alcalase
9.0 30 4 ND ND 299.8 90.0 0.75 Alcalase 9.0 30 6 ND ND 331.4 90.0
0.75 Alcalase 8.0 30 0 ND ND 123.3 90.0 0.75 Alcalase 8.0 30 1 ND
ND 237.1 90.0 0.75 Alcalase 8.0 30 2 ND ND 257.4 90.0 0.75 Alcalase
8.0 30 4 ND ND 349.7 90.0 0.75 Alcalase 8.0 30 6 ND ND 364.0 90.0
0.75 Alcalase 9.5 30 0 ND ND 119.6 90.0 0.75 Alcalase 9.5 30 1 ND
ND 218.7 90.0 0.75 Alcalase 9.5 30 2 ND ND 233.7 90.0 0.75 Alcalase
9.5 30 4 ND ND 306.2 90.0 0.75 Alcalase 9.5 30 6 ND ND 303.4 90.0
0.75 Alcalase 8.0 20 0 ND ND 107.5 90.0 0.75 Alcalase 8.0 20 1 ND
ND 197.8 90.0 0.75 Alcalase 8.0 20 2 2.78 ND 253.1 90.0 0.75
Alcalase 8.0 20 4 ND ND 375.7 90.0 0.75 Alcalase 8.0 20 6 ND ND
437.9 90.0 0.75 Alcalase 9.0 20 0 ND 0.52 113.7 90.0 0.75 Alcalase
9.0 20 1 ND ND 200.9 90.0 0.75 Alcalase 9.0 20 2 ND ND 283.1 90.0
0.75 Alcalase 9.0 20 4 ND ND 371.4 90.0 0.75 Alcalase 9.0 20 6 ND
ND 410.9 90.0 0.68 Lipolase 100L 8.0 30 0 ND ND 75.1 90.0 0.68
Lipolase 100L 8.0 30 1 ND ND 69.4 90.0 0.68 Lipolase 100L 8.0 30 2
ND ND 72.7 90.0 0.68 Lipolase 100L 8.0 30 4 ND ND 72.7 90.0 0.68
Lipolase 100L 8.0 30 6 ND ND 75.4 90.0 0.68 Resinase A 8.0 30 0 ND
ND 71.6 90.0 0.68 Resinase A 8.0 30 1 ND ND 70.8 90.0 0.68 Resinase
A 8.0 30 2 ND ND 73.1 90.0 0.68 Resinase A 8.0 30 4 ND ND 73.7 90.0
0.68 Resinase A 8.0 30 6 ND ND 69.4 90.0 1.36 5% Lipase M 8.0 30 0
ND ND 58.2 90.0 1.36 5% Lipase M 8.0 30 1 ND ND 46.0 90.0 1.36 5%
Lipase M 8.0 30 2 ND ND 60.4 90.0 1.36 5% Lipase M 8.0 30 4 ND ND
74.0 90.0 1.36 5% Lipase M 8.0 30 6 ND ND 69.8 90.0 0.68 10%
Flavourzyme 8.0 30 0 ND ND 52.0 90.0 0.68 10% Flavourzyme 8.0 30 1
ND ND 61.7 90.0 0.68 10% Flavourzyme 8.0 30 2 ND ND 71.1 90.0 0.68
10% Flavourzyme 8.0 30 4 ND ND 70.3 90.0 0.68 10% Flavourzyme 8.0
30 6 ND ND 72.3
Comparative Example 10
[0355] As controls, the general procedure for screening activity of
resins and evaluating reaction conditions was repeated, but without
added enzyme: A portion of Resin F was charged into a container
with a stirrer. The pH was adjusted with 20% aqueous sodium
hydroxide. The container was closed to minimize evaporation of
water. The container was placed in a temperature-controlled water
bath and maintained at the desired temperature. Periodically, an
aliquot was removed from the bottle and submitted for GC analysis.
The results are reported in Table 30. There are several comparative
examples because of reaction condition changes and because Resin F
is not CPD storage stable. This Table contains numerous comparative
examples (reactions without enzyme--designated no enzyme) which
were conducted chronologically close to the examples.
Example 75
Synthesis of a Polyaminopolyamide-epi Resin Followed by
Enzyme-treatment and Biodehalogenation
[0356] A 3-L round-bottom flask was fitted with a condenser, a pH
meter, a temperature controlled circulating bath, an addition
funnel and a mechanical stirrer. To the flask was added 717.57 g of
53.3% aqueous poly(adipic acid-co-diethylenetriamine) (available
from the Hercules Incorporated, Zwijndrecht, Netherlands plant) and
557.43 g of water. The solution was adjusted to 25.degree. C. and
then 170.08 g of epichlorohydrin (Aldrich, 99%) was added over
about 1 minute. The temperature was allowed to increase to
40.degree. C. and was maintained at this temperature. 2.75 hours
after the addition of the epichlorohydrin, 1042.2 g of water and
7.825 g of 96% sulfuric acid was added. The temperature was raised
to 70.degree. C. over 0.75 hour. The Gardner-Holdt viscosity at
25.degree. C. was monitored. After the Gardner-Holdt viscosity
reached H, the reaction was quenched by the addition 150 g of water
containing 18.5 g of 96% sulfuric acid. The reaction mixture was
allowed to cool to 25.degree. C. The pH was adjusted to 2.7 with an
additional 1.60 g of 96% sulfuric acid and 127 grams of water was
added. The total solids content of this resin was 21.0% and the
Brookfield viscosity was 147 cps.
[0357] A 1-L round-bottom flask was fitted with a condenser, a pH
meter, a temperature controlled circulating bath and a mechanical
stirrer. To the flask was added 321.42 g of the above 21.0%
polyaminopolyamide-epi resin (stored at 4.degree. C. for two
months) and 178.57 g of water (to give 13.5% solids). The pH was
raised to 8.0 with 11.16 g of 30% aqueous sodium hydroxide and then
4.17 g of Alcalase (available from Novo Nordisk, used as received).
A 6.60 g aliquot of the reaction mixture was removed and analyzed
by GC. The temperature was raised to 40.0.degree. C. and maintained
at 40.0.degree. C. Aliquots (6.60 g each) were removed and analyzed
by GC (see Table 31). The pH was allowed to drop throughout the
course of the reaction, without adjustment. After 6 hours, the
temperature was reduced to 30.0.degree. C. and a 22.77 g, sample
was removed. The pH of the remaining resin was lowered from 6.98 to
5.8 with 1.80 g of 96% sulfuric acid, an air sparge was placed to
contact the resin solution and then 55.56 g of a blend of
microorganisms comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 4.32 grams of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used were: Arthrobacter histidinolovorans (HK1) and
Agrobacterium tumefaciens (HK7). The temperature was maintained at
30.degree. C. and the pH was maintained at 5.8 by periodic addition
of 20% aqueous sodium hydroxide. After 48 hours, the mixture was
cooled to room temperature and the pH was adjusted to 2.8 with 2.71
g of 96% sulfuric acid and and 5.04 g of biocide solution was
added. [The biocide solution consisted of 10% active Proxel.RTM. BD
(from Zeneca Biocides) and 1.67% potassium sorbate in deionized
water.]. The resin had a total solids of 16.9 wt. % and had a
Brookfield viscosity of 33 cps.
[0358] The amount of CPD producing species of this were estimated
using the following test. A portion of resin to be tested was
charged into a bottle containing a magnetic stirrer. The pH was
adjusted to 1.0 with 96% sulfuric acid. The bottle was capped and
placed in a 50.degree. C. water bath and maintained at 50.degree.
C. with stirring. Periodically, aliquots were removed from the
bottle and submitted for GC analysis. The CPD produced after 24
hours is used to estimate the amount of CPD producing species. See
Table 31 for results. TABLE-US-00034 TABLE 31 Resin Temp Time epi
1,3-DCP 2,3-DCP 3-CPD Information pH (.degree. C.) (hours) (ppm)
(ppm) (ppm) (ppm) 21% resin, no enzyme 2.7 23 0.0 8 1595 ND 419
13.5% resin, enzyme 8.0 23 0.083 8 1014 ND 395 13.5% resin, enzyme
7.5 40 1.0 30 977 ND 451 13.5% resin, enzyme 7.2 40 2.0 39 947 ND
546 13.5% resin, enzyme 7.0 40 4.0 40 937 ND 636 13.5% resin,
enzyme 6.8 40 6.0 39 932 ND 653 Biodehalogenated resin -- -- -- ND
ND 1.00 0.2 Acid test 1.0 50 23 ND ND 0.69 12.6 Acid test 1.0 50 23
ND ND 0.74 13.7
Example 76
Handsheet Evaluation of Enzyme Treated Example 75 and Comparative
Example 4
[0359] The procedure of Example 7 was used to evaluate Example 75
and Comparative Example 4. Results for oven-cured paper are
reported in Table 32. TABLE-US-00035 TABLE 32 Oven-Cured Paper.
Basis Wt. Normalized dry wet % % of CPD in % tensile tensile wet/
Comp. Paper Example Added pH lbs/in lbs/in dry Ex. 4 (ppb) Blank --
7.5 17.78 0.63 4 17 <30 Example 75 0.25 7.5 22.90 4.13 18 115 --
Example 75 0.50 7.5 24.28 5.36 22 119 -- Example 75 1.00 7.5 25.41
6.03 24 112 57 Comp. Ex. 4 0.25 7.5 21.18 3.60 17 100 -- Comp. Ex.
4 0.50 7.5 21.94 4.50 21 100 -- Comp. Ex. 4 1.00 7.5 23.00 5.38 23
100 366
Example 77
Enzyme-treatment of a Polyaminopolyamide-epi Resin Followed by
Biodehalogenation
[0360] A 1-L round-bottom flask was fitted with a condenser, a pH
meter, a temperature controlled circulating bath and a mechanical
stirrer. To the flask was added 452.64 g of PPD D-1026 (a 23.9%
solids Kymene.RTM. SLX2 polyaminopolyamide-epi resin available from
Hercules Incorporated) and 347.36 g of water (to give 13.5%
solids). A 6 g aliquot was removed and analyzed by GC. The pH was
raised to 8.0 with 21.60 g of 30% aqueous sodium hydroxide and a 6
g aliquot was removed and analyzed by GC. Then 6.67 g of Alcalase
(available from Novo Nordisk, used as received). A 6 g aliquot of
the reaction mixture was removed and analyzed by GC. The
temperature was raised to 40.0.degree. C. and maintained at
40.0.degree. C. Additional aliquots (6 g) were removed and analyzed
by GC (see Table 32). The pH was allowed to drop throughout the
course of the reaction, without adjustment. After 6 hours, the
temperature was reduced to 30.0.degree. C. and a 23.51 g sample was
removed. The pH of the remaining resin (760 g) was lowered from
6.98 to 5.8 with 2.15 g of 96% sulfuric acid, an air sparge was
placed to contact the resin solution and then 84.44 g of a blend of
microorganisms comprising an inoculum from a biodehalogenated
polyaminopolyamide-epichlorohydrin resin. This represents a
starting value of cell concentration of from about 10.sup.5 to
about 10.sup.6 cells/ml. This starting value corresponds to a final
treatment level of about 10.sup.9 cells/ml as the process proceeds.
The inoculum was added, together with 6.64 g of a nutrient
solution. (The nutrient solution consisted of 8026 ppm of potassium
dihydrogen phosphate, 27480 ppm of urea, 4160 ppm of magnesium
sulfate and 840 ppm of calcium chloride in tap water.) The
microorganisms used were: Arthrobacter histidinolovorans (HK1) and
Agrobacterium tumefaciens (HK7). The temperature was maintained at
30.degree. C. and the pH was maintained at 5.8 by periodic addition
of 20% aqueous sodium hydroxide. After 48 hours, the mixture was
cooled to room temperature and the pH was adjusted to 2.8 with 4.63
g of 96% sulfuric acid and and 10.2 g of biocide solution was
added. [The biocide solution consisted of 10% active Proxel.RTM. BD
(from Zeneca Biocides) and 1.67% potassium sorbate in deionized
water.]. The resin had a total solids of 14.2 wt. % and had a
Brookfield viscosity of 145 cps.
[0361] The amount of CPD producing species of this were estimated
using the following test. A portion of resin to be tested was
charged into a bottle containing a magnetic stirrer. The pH was
adjusted to 1.0 with 96% sulfuric acid. The bottle was capped and
placed in a 50.degree. C. water bath and maintained at 50.degree.
C. with stirring. Periodically, aliquots were removed from the
bottle and submitted for GC analysis. The CPD produced after 24
hours is used to estimate the amount of CPD producing species. See
Table 33 for results. TABLE-US-00036 TABLE 33 Resin Temp Time epi
1,3-DCP 2,3-DCP 33-CPF Information pH (.degree. C.) (hours) (ppm)
(ppm) (ppm) (ppm) 13.5% resin, no enzyme 2.9 19 0.0 ND 694.4 1.59
310.1 13.5% resin, no enzyme 8.0 22 0.0 5.7 647.2 1.52 290.4 13.5%
resin, enzyme 8.0 21 0.083 ND 674.5 ND 387.7 13.5% resin, enzyme
7.5 40 1.0 14.5 650.6 ND 475.4 13.5% resin, enzyme 7.3 40 2.0 21.1
618.4 ND 513.6 13.5% resin, enzyme 7.1 40 4.0 17.1 619.6 ND 536.2
13.5% resin, enzyme 7.0 40 6.0 21.8 561.3 ND 486.8 Biodehalogenated
resin -- -- -- ND ND 0.68 0.15 Acid Test 1.0 50 24 ND ND 0.68
12.1
[0362] Although the invention has been described with reference to
particular means, materials and embodiments, it is to be understood
that the invention is not limited to the particulars disclosed, and
extends to all equivalents within the scope of the claims.
* * * * *