U.S. patent application number 13/074469 was filed with the patent office on 2012-10-04 for polyamine polyamidoamine epihaloohydrin compositions and processes for preparing and using the same.
This patent application is currently assigned to KEMIRA OYJ. Invention is credited to Vladimir Grigoriev, Chen Lu, Danny Nguyen, Scott Rosencrance.
Application Number | 20120247697 13/074469 |
Document ID | / |
Family ID | 45977034 |
Filed Date | 2012-10-04 |
United States Patent
Application |
20120247697 |
Kind Code |
A1 |
Lu; Chen ; et al. |
October 4, 2012 |
Polyamine Polyamidoamine Epihaloohydrin Compositions and Processes
for Preparing and Using the Same
Abstract
Compositions of and processes for preparing a
polyamine-polyamidoamine-epihalohydrin resin generally include
reacting a first polyamine, a polyamidoamine, and an epihalohydrin
to form the polyamine-polyamidoamine-epihalohydrin (PPAE) resin,
wherein the polyamidoamine is prepared by reacting a polycarboxylic
acid or a polycarboxylic acid derivative with a second polyamine to
form the polyamidoamine, wherein a molar ratio of the polyamine to
the polycarboxylic acid is 1.05 to 2.0. The PPAE resin can be used
in an adhesive formulation for use in creping applications for
forming paper products such as tissue products.
Inventors: |
Lu; Chen; (Marietta, GA)
; Grigoriev; Vladimir; (Atlanta, GA) ; Nguyen;
Danny; (Norcross, GA) ; Rosencrance; Scott;
(Douglasville, GA) |
Assignee: |
KEMIRA OYJ
Helsinki
FI
|
Family ID: |
45977034 |
Appl. No.: |
13/074469 |
Filed: |
March 29, 2011 |
Current U.S.
Class: |
162/111 ;
524/106; 524/310; 524/317; 524/386; 524/387; 524/416; 524/503;
524/514; 524/538; 524/608; 528/332; 528/335 |
Current CPC
Class: |
C09J 163/00 20130101;
D21H 17/55 20130101; C08G 73/0286 20130101; B31F 1/12 20130101;
C09J 163/00 20130101; C08G 69/46 20130101; C08G 69/28 20130101;
B31F 1/12 20130101 |
Class at
Publication: |
162/111 ;
528/332; 524/608; 528/335; 524/538; 524/514; 524/503; 524/386;
524/387; 524/317; 524/310; 524/106; 524/416 |
International
Class: |
B31F 1/14 20060101
B31F001/14; C08L 77/06 20060101 C08L077/06; C08L 29/04 20060101
C08L029/04; C08K 3/32 20060101 C08K003/32; C08K 5/103 20060101
C08K005/103; C08K 5/11 20060101 C08K005/11; C08K 5/3445 20060101
C08K005/3445; C08G 69/28 20060101 C08G069/28; C08K 5/053 20060101
C08K005/053 |
Claims
1. A process for preparing a polyamine-polyamidoamine-epihalohydrin
resin comprising: reacting a polyamidoamine, a first polyamine, and
an epihalohydrin to form the polyamine-polyamidoamine-epihalohydrin
resin, wherein the polyamidoamine is prepared by a process
comprising reacting a polycarboxylic acid and/or a polycarboxylic
acid derivative with a second polyamine to form the polyamidoamine,
wherein a molar ratio of the second polyamine to the polycarboxylic
acid and/or polycarboxylic acid derivative is 1.05 to 2.0.
2. The process of claim 1, wherein reacting the first polyamine,
the polyamidoamine, and the epihalohydrin is conducted in an
aqueous media.
3. The process of claim 1, wherein the epihalohydrin is
epichlorohydrin.
4. The process of claim 1, wherein the polycarboxylic acid and/or
the polycarboxylic acid derivative is selected from the group
comprising malonic acid, glutaric acid, adipic acid, azelaic acid,
citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid),
1,2,3,4 butanetetracarboxylic acid, nitrilotriacetic acid,
N,N,N',N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic
acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) and
1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), dimethyl
adipate, dimethyl malonate, diethyl malonate, dimethyl succinate,
dimethyl glutarate, diethyl glutarate, succinic anhydride, maleic
anhydride, N,N,N',N'-ethylenediaminetetraacetate dianhydride,
phthalic anhydride, mellitic anhydride, pyromellitic anhydride,
adipoyl chloride, glutaryl chloride, sebacoyl chloride, and
mixtures thereof.
5. The process of claim 1, wherein the first polyamine is selected
from the group consisting of ammonium, aliphatic amines, aromatic
amines, ethylene diamine (EDA), diethylenetriamine (DETA),
triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT),
N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP),
pentaethylenehexamine (PEHA), and mixtures thereof.
6. The process of claim 1, wherein the second polyamine is selected
from the group consisting of diethylenetriamine (DETA),
triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT),
N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP),
pentaethylenehexamine (PEHA), and mixtures thereof.
7. The process of claim 1, wherein the first and second polyamines
are the same.
8. The process of claim 1, wherein the first and second polyamines
are different.
9. The process of claim 1, wherein the ratio of EPI mass (g) over
PA mass (g) is greater than about 1.499x-0.007, where N is the
ratio of EPI sites (mole) over the product of RSV (dL/g) and PA
mass (g).
10. The process of claim 1, wherein the first polyamine to the
polyamidoamine is at a weight ratio of 1:100 to 100:1.
11. The process of claim 1, wherein the
polyamine-polyamidoamine-epihalohydrin resin has a weight average
molecular weight of 350 Daltons (Da) to 10 million Da.
12. The process of claim 1, wherein the
polyamine-polyamidoamine-epihalohydrin resin has a rewettability
ratio of 5 to 100.
13. The process of claim 1, wherein the
polyamine-polyamidoamine-epihalohydrin resin has an insolubility
percentage of 5 to 100%.
14. A process for forming a creped paper product comprising:
applying an adhesive formulation comprising a
polyamine-polyamidoamine-epihalohydrin resin to a drying surface,
wherein the polyamine-polyamidoamine-epihalohydrin resin has a
rewettability ratio of 5 to 100, and an insolubility percentage of
5 to 100%, and wherein the polyamidoamine is prepared by a process
comprising reacting a polycarboxylic acid and/or a polycarboxylic
acid derivative with a second polyamine to form the polyamidoamine,
wherein a molar ratio of the second polyamine to the polycarboxylic
acid and/or polycarboxylic acid derivative is 1.05 to 2.0; pressing
a paper web against the drying surface to effect adhesion of the
paper web to the surface; and dislodging the paper web from the
drying surface by contact with a doctor blade to form the creped
paper product.
15. The process of claim 14, wherein the creped paper product is an
article selected from the group consisting of facial tissue, bath
tissue, wipes, paper towels, paper napkins, filter papers, and
coffee filters.
16. The process of claim 14, wherein the epihalohydrin is
epichlorohydrin.
17. A composition comprising a
polyamine-polyamidoamine-epihalohydrin resin, wherein the
polyamidoamine is prepared by a process comprising reacting a
polycarboxylic acid and/or a polycarboxylic acid derivative with a
second polyamine to form the polyamidoamine, wherein a molar ratio
of the second polyamine to the polycarboxylic acid and/or
polycarboxylic acid derivative is 1.05 to 2.0.
18. The composition of claim 17, wherein the
polyamine-polyamidoamine-epihalohydrin resin has a rewettability
ratio of 5 to 100.
19. The composition of claim 17, wherein the
polyamine-polyamidoamine-epihalohydrin resin has an insolubility
percentage of 5 to 100%.
20. The composition of claim 17, wherein the epihalohydrin is
epichlorohydrin.
21. The composition of claim 17, wherein the polycarboxylic acid
and/or the polycarboxylic acid derivative is selected from the
group comprising malonic acid, glutaric acid, adipic acid, azelaic
acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic
acid), 1,2,3,4 butanetetracarboxylic acid, nitrilotriacetic acid,
N,N,N',N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic
acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) and
1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), dimethyl
adipate, dimethyl malonate, diethyl malonate, dimethyl succinate,
dimethyl glutarate, diethyl glutarate, succinic anhydride, maleic
anhydride, N,N,N',N'-ethylenediaminetetraacetate dianhydride,
phthalic anhydride, mellitic anhydride, pyromellitic anhydride,
adipoyl chloride, glutaryl chloride, sebacoyl chloride, and
mixtures thereof.
22. The composition of claim 17, wherein the
polyamine-polyamidoamine-epihalohydrin resin has a weight average
molecular weight of 350 Daltons (Da) to 10 million Da.
23. The composition of claim 17, wherein the polyamine of the
polyamine-polyamidoamine-epihalohydrin resin and the second
polyamine are selected from the group consisting of
diethylenetriamine (DETA), triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA),
bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine
(MBAPA), aminoethyl-piperazine (AEP), pentaethylenehexamine (PEHA),
and mixtures thereof, wherein the polyamine and the second
polyamine are the same or different.
24. The composition of claim 17, wherein the polyamine of the
polyamine-polyamidoamine-epihalohydrin resin is at a weight ratio
to the polyamidoamine of 1:100 to 100:1.
25. The composition of claim 17, further comprising water.
26. The composition of claim 25, further comprising a co-adhesive,
a plasticizer, a phosphate, a release aid, or mixtures thereof.
27. The composition of claim 26, wherein the co-adhesive is
selected from the group consisting of polyvinyl alcohol, polyamine
epichlorohydrin, polyamidoamine, polyamidoamine epichlorohydrin,
polyvinylamine, polyethyleneimine, polymethacrylamide, poly(acrylic
acid), poly(methacrylic acid), poly(hydroxyethyl acrylate),
poly(hydroxyethyl methacrylate), poly(n-vinyl pyrrolidinone),
poly(ethylene oxide), hydroxyethyl cellulose, hydroxypropyl
cellulose, guar gum, starch, agar, chitosan, alginic acid,
carboxymethyl cellulose, silylated polyamidoamines
polyvinylamine/N-vinylformamide, polyethyeleneimine, glyoxylated
polyacrylamide, and mixtures thereof.
28. The composition of claim 26, wherein the plasticizer is
selected from the group consisting of glycerol, sorbitol and
polyethylene glycol.
29. The composition of claim 26, wherein the release aid is
selected from the group consisting of mineral oil, vegetable oil,
polyethylene glycol monoester, polyethylene glycol diester,
ethoxylated polyethylene glycol, fatty acid imidazolinium
surfactant, and mixtures thereof.
30. The composition of claim 26, wherein the phosphate is selected
from the group consisting of monoammonium phosphate and diammonium
phosphate.
Description
BACKGROUND
[0001] The present disclosure generally relates to polymers that
are useful in papermaking processes. More particularly, the present
disclosure relates to polyamine-polyamidoamine-epihalohydrin
compositions, methods of manufacture, and their use.
[0002] The creping application generally includes scraping a dried
paper web from a drying cylinder (e.g., a Yankee dryer) by the use
of a creping doctor blade. The creping action puts very small folds
or accordions in the sheet to impart a fine, rippled texture to the
sheet, which also increases the bulk, softness and absorbency of
the sheet. Creping can occur when the sheet is almost completely
dry, that is, 92 to 98% solids or when the sheet is wetter, around
70-85% solids. If the machine is designed to crepe at high dryness,
it is referred to as a "dry crepe" machine. Dry creping has the
greatest effect on sheet properties because the sheet is more
firmly attached to the Yankee surface. If the machine is designed
to crepe when the sheet is still somewhat wet, it is called a "wet
crepe" machine.
[0003] Adhesion of the sheet to the drying cylinder is an important
aspect of the creping process since it determines how the sheet
crepes at the doctor blade. Sheet adhesion is generally controlled
through application of an adhesive formulation onto the Yankee
dryer surface. The creping process typically involves applying the
creping adhesive, generally in the form of an aqueous solution or
dispersion, to a drying surface for the web. Typically, this
surface is the surface of a rotating heated creping cylinder, such
as the Yankee dryer discussed above. The paper web is then adhered
to the indicated surface and later dislodged from the surface with
a creping device, e.g., using a doctor blade. The impact of the web
against the creping device ruptures some of the fiber-to-fiber
bonds within the web, causing the web to wrinkle or pucker. In this
regard, fibrous webs, particularly paper webs, are conventionally
subjected to the creping process in order to give them desirable
textual characteristics, such as softness and bulk. It is well
known that the use of adhesive formulations can provide improved
product quality and better control of the papermaking process.
[0004] Drying cylinders such as the Yankee dryer are often operated
under quite different temperature conditions, ranging from
90.degree. C. to 130.degree. C. Recent trends have the creping
conditions moving towards high temperature and/or low sheet
moisture. Under high temperature conditions, "rewettability" of the
applied adhesive is critical to impart the adhesion of the sheet to
the Yankee dryer. Rewettability refers to the ability of a dry
adhesive film on the dryer to absorb water once in contact with the
wet paper sheet. The adhesive is typically sprayed on the Yankee
coating continuously. However, the majority of the adhesion occurs
by means of the adhesive deposited in previous passes. If the
adhesive absorbs greater amounts of water in contact with the
sheet, the adhesive will be softer, resulting in a more intimate
contact with the sheet and providing increased adhesion between the
sheet and the dryer.
[0005] The solubility of the adhesive film in water is another
essential property affecting adhesion. The wet sheet before the
Yankee dryer typically contains
[0006] 60% or more water. During the contact between the wet sheet
and the Yankee dryer, water from the sheet may wash off a portion
of the deposited adhesive coating, negatively impacting the
efficiency of the creping process. In order to form a durable
enough coating on the Yankee surface, relatively low water
solubility (high insolubility) is often required for the adhesive
film to withstand the wash-off at the point of contact with the wet
sheet.
[0007] Polyamidoamine epichlorohydrin resins (PAE resins) have been
applied in the manufacture of paper for a variety of applications.
For example, PAE resins are widely used as strength additives to
increase the paper wet strength. PAE resins are also the most
common adhesives used in the creping process for producing tissue
and towel products.
[0008] Conventional PAE resins are typically produced in a two step
reaction. In the first step, a polyamidoamine is prepared by
condensation of near equi-molar amounts of a polyamine and a
polycarboxylic acid or polycarboxylic acid derivative. The
polyamidoamine that is formed is then reacted with epichlorohydrin
in an aqueous solution to produce the PAE resin. The detailed
synthesis is well known and is documented in numerous patents,
e.g., U.S. Pat. Nos. 2,926,116, and 7,175,740.
[0009] Much research has been carried out to develop modified PAE
resins with improved performance for various applications. U.S.
Pat. No. 3,951,921 describes a cationic water soluble resin
consisting essentially of a PAE base resin having epoxide moieties
and a nitrogen compound in an amount at least stoichiometrically
equivalent to the epoxide moieties of the base resin. The nitrogen
compounds are ammonia, ethyl amine, dimethyl amine and
hydroxylamine. U.S. Pat. No. 4,287,110 describes a PAE resin made
form a polyamidoamine and an excess polyamine wherein the molar
ratio of dicarboxylic acid to polyamine is 1:1 to 1:2. U.S. Pat.
No. 5,338,807 is generally directed to a creping aid composition
including a polyamide reaction product of an polyamide of a
polycarbonxylic acid or of the ester of an aliphatic dicarboxylic
acid and methyl bis(3-aminopropyl)amine with epichlorohydrin in a
mole ratio of the polyamide to the epichlorohydrin between about
1:0.1 and about 1:0.33. U.S. Pat. No. 5,382,323 is generally
directed to a creping aid of a polyamidoamine crosslinked with a
multifunctional aldehyde. US Pat. Pub. No. 2008/0255320 is
generally directed to a PAE resin made from a polyamidoamine with
an excess polyamine, wherein the molar ratio of polyamine to
polycarboxylic acid is in the range of 1.02:1 to 2:0.1.
[0010] While these PAE adhesive formulations are adequate for many
creping applications, there is a continuing need for an adhesive
with improved properties, including film rewettability, film
insolubility, and adhesion.
BRIEF SUMMARY
[0011] Disclosed herein are compositions, methods of manufacture,
processes of use. In one embodiment, the process for preparing the
polyamine-polyamidoamine-epihalohydrin (PPAE) resin comprises
reacting a polyamidoamine, a first polyamine, and an epihalohydrin
to form the polyamine-polyamidoamine-epihalohydrin resin, wherein
the polyamidoamine is prepared by a process comprising reacting a
polycarboxylic acid and/or a polycarboxylic acid derivative with a
second polyamine to form the polyamidoamine, wherein a molar ratio
of the second polyamine to the polycarboxylic acid and/or
polycarboxylic acid derivative is 1.05 to 2.0.
[0012] A process for forming a creped paper product comprising
applying an adhesive formulation comprising a
polyamine-polyamidoamine-epihalohydrin resin to a drying surface,
wherein the polyamine-polyamidoamine-epihalohydrin resin has a
rewettability ratio of 5 to 100, and an insolubility percentage of
5 to 100%, and wherein the polyamidoamine is prepared by a process
comprising reacting a polycarboxylic acid and/or a polycarboxylic
acid derivative with a second polyamine to form the polyamidoamine,
wherein a molar ratio of the second polyamine to the polycarboxylic
acid and/or polycarboxylic acid derivative is 1.05 to 2.0; pressing
a paper web against the drying surface to effect adhesion of the
paper web to the surface; and dislodging the paper web from the
drying surface by contact with a doctor blade to form the creped
paper product.
[0013] A composition comprises a
polyamine-polyamidoamine-epihalohydrin resin, wherein the
polyamidoamine is prepared by a process comprising reacting a
polycarboxylic acid and/or a polycarboxylic acid derivative with a
second polyamine to form the polyamidoamine, wherein a molar ratio
of the second polyamine to the polycarboxylic acid and/or
polycarboxylic acid derivative is 1.05 to 2.0.
[0014] The disclosure may be understood more readily by reference
to the following detailed description of the various features of
the disclosure and the examples included therein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The FIGURE graphically illustrates correlation between the
molar quantity of epichlorohydrin-reactive sites on polyamidoamine
and the molar quantity of charged epichlorohydrin.
DETAILED DESCRIPTION
[0016] Disclosed herein are
polyamine-polyamidoamine-epichlorohydrin (PPAE) resins for use in
adhesive compositions, methods of manufacture, and their use in
creping applications.
[0017] The PPAE resins are generally the reaction product of three
components: a polyamine, a polyamidoamine, and an epihalohydrin. In
contrast, the prior art PAE resins are generally formed from the
reaction product of two components: a polyamidoamine and a
difunctional crosslinker such as epichlorohydrin. In the present
invention, both the polyamidoamine and the polyamine can include
primary and secondary amines that can react with epihalohydrin.
Therefore, the epihalohydrin can cross-link the polyamidoamine and
the polyamine during the reaction to form the PPAE resins,
resulting in a branched polymeric structure. Applicants have
discovered that the addition of the polyamine component during the
reaction of the epihalohydrin and polyamidoamine components to form
the PPAE resin provides the resulting PPAE reaction product with
unexpectedly improved properties relative to the prior art PAE
resins especially as it relates to adhesive performance, and as
such, are suitable for use as creping adhesives in paper making
process, among other uses.
[0018] The PPAE resins can generally be formed by reacting
polyamine, polyamidoamine, and epihalohydrin in an aqueous medium.
The weight ratios of polyamine to polyamidoamine can be from 1:100
to 100:1; in other embodiments from 1:50 to 50:1; and in still
other embodiments from 1:20 to 20:1. The reaction temperature may
be from 25 to 100.degree. C.; in other embodiments from 40 to
90.degree. C.; and in still other embodiments from 50 to 80.degree.
C. The total solids of the PPAE resins can be from 5 to 80%; in
other embodiments from 10 to 50%; and in still other embodiments
from 15 to 30%. The pH values of the PPAE resins can be from 2 to
10; in other embodiments from 3 to 9; and in still other
embodiments from 3 to 8. The weight average molecular weight of the
PPAE resins can be from 350 Daltons (Da) to 10 million Da; in other
embodiments from 1000 Da to 5 million Da; and in still other
embodiments from 5000 Da to 3 million Da.
[0019] The rewettability ratios of the PPAE resins can be from 5 to
100, more preferably from 7 to 50, and most preferably from 10 to
40. The insolubility percentages of the PPAE resins can be from 5
to 100%, more preferably from 10 to 85%, and most preferably from
15% to 70%. The rewettability ratio and the insolubility percentage
are defined in the following sections.
[0020] The rewettability ratio and insolubility percentage are
generally determined after immersion of the PPAE resin in water.
The rewettability ratio is the weight ratio of a PPAE hydrogel
formed after water immersion to the dry PPEA resin, wherein the
hydrogel is the remaining PPAE resin plus any absorbed water after
immersion. In the rewettability test, 4 g of adhesive product is
added to a 200 mL beaker and dried at 90.degree. C. for one hour
and 110.degree. C. for four hours to obtain the adhesive product in
dry form. Afterwards, 50 g of water is added to the beaker. After
30 minutes of soaking at room temperature, excess water was removed
from the beaker by decantation and the weight of the hydrogel was
determined. The water used for rewetting was obtained by adding
NaCl to de-ionized water to adjust the conductivity to 90
.mu.s.
[0021] The insolubility percentage is calculated as the weight
percentage of the remaining PPAE resin after water immersion and
subsequent drying to the original adhesive dry solid content prior
to water immersion. In the insolubility test, 4 g of adhesive
product is added to a 200 mL beaker and dried at 90.degree. C. for
one hour and 110.degree. C. for four hours to determine weight of
the dry solid. Afterwards, 50 g of deionized or tap water is added
to the beaker, which is then placed on an incubating shaker (e.g.,
Thermo Scientific MAXQ 4450) at 60.degree. C. and 200 rpm. After 60
minutes of shaking, the adhesive suspension was poured onto a Nylon
membrane with a pore size of 5 micron (e.g., OSMONICS, model number
R50SP09025) and drained under vacuum. The remaining adhesive gel on
the membrane was then dried in a convection oven and the weight of
the remaining dried PPAE solid was determined. The insolubility
percentage of the adhesive product was calculated as the weight
percentage of the remaining dry solid content after immersion and
drying over the original adhesive dry solid content.
[0022] The polyamines utilized to form the PPAE resin are not
intended to be limited. Suitable polyamines generally include
ammonium, aliphatic amines, aromatic amines, and any
polyalkylenepolyamine, which includes polyethylene polyamines,
polypropylene polyamines, polybutylene polyamines, polypentylene
polyamines, polyhexylene polyamines, and mixtures thereof.
Exemplary polyamines include, without limitation, ethylene diamine
(EDA), diethylenetriamine (DETA), triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA),
bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine
(MBAPA), aminoethyl-piperazine (AEP), pentaetehylenehexamine (PEHA)
and mixtures thereof.
[0023] Likewise, the polyamidoamines employed for forming the PPAE
resins are not intended to be limited. Suitable polyamidoamines can
generally be prepared by heating a polycarboxylic acid and/or a
polycarboxylic acid derivative with one or more of the polyamines
as noted above at a temperature of 125 to 200.degree. C. for 1 to
10 hours while collecting the water of condensation produced in the
reaction at atmospheric pressure. The reaction is usually allowed
to proceed until the theoretical amount of water distillate is
collected from the reaction. Where a reduced pressure is employed,
lower temperatures such as 75.degree. C. to 180.degree. C. may be
utilized. At the end of this reaction, the resulting product is
dissolved in water at a concentration of about 20 to 90% by weight
total polymer solids, more typically at a concentration of about 30
to 80%, and most typically at a concentration of about 40 to
70%.
[0024] In the preparation of the polyamidoamines, the molar ratio
of the polyamine to the polycarboxylic acid and/or polycarboxylic
acid derivative is at about from 1.05 to 2.0.
[0025] The polycarboxylic acid and/or polycarboxylic acid
derivatives thereof that may be used to prepare the polyamidoamines
are not intended to be limited. Suitable polycarboxylic acids
and/or derivatives thereof include but are not limited to malonic
acid, glutaric acid, adipic acid, azelaic acid, citric acid,
tricarballylic acid (1,2,3-propanetricarboxylic acid),
1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid,
N,N,N',N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, phthalic acid, isophthalic acid, terephthalic acid,
1,2,4-benzenetricarboxylic acid (trimellitic acid),
1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid),
carboxylate esters, acid halides, acid anhydrides, and mixtures
thereof.
[0026] Exemplary esters of polycarboxylic acids include, but are
not limited to, dimethyl adipate, dimethyl malonate, diethyl
malonate, dimethyl succinate, dimethyl glutarate and diethyl
glutarate. Exemplary acid anhydrides include, but are not limited
to, succinic anhydride, maleic anhydride,
N,N,N',N'-ethylenediaminetetraacetate dianhydride, phthalic
anhydride, mellitic anhydride, pyromellitic anhydride, and mixtures
thereof. Exemplary acid halides include, but are not limited to,
adipoyl chloride, glutaryl chloride, sebacoyl chloride, and
mixtures thereof.
[0027] The epihalohydrin is a difunctional crosslinker that is used
to prepare the PPAE resins. Exemplary epihalohydrins include
epichlorohydrin, epifluorohydrin, epibromohydrin, and epiiodohydrin
as well as alkyl-substituted epihalohydrins. In one embodiment, the
difunctional crosslinker for preparing the PPAE resins is
epichlorohydrin.
[0028] The PPAE resins can be used in creping adhesive formulations
for use in the creping process, which is commonly practiced in the
manufacture of tissue and towel grades of paper. The paper web used
in these applications can be comprised of various types of natural
and recycled fibers including wood pulps of chemical and mechanical
types. The fibers can comprise hardwood, softwood and cotton
fibers. The tissue web can also contain particulate fillers, fines,
ash, organic contaminates such as the cellophane from envelope
windows, adhesives such as PVA-styrene-butadiene and inks as well
as process chemicals used in the paper-making process such as
strength additives, softeners, surfactants and organic
polymers.
[0029] The PPAE creping adhesive formulation generally includes at
least the PPAE resin, which may be in the form of an aqueous
solution or a dispersion of about 20 to 95% water and 80 to 5%
PPAE. The formulation may further include one or more additional
components such as water-soluble polymers for use as co-adhesives,
such as additional polyamine epichlorohydrin resins,
polyacrylamide, poly(vinyl alcohol), polyvinylamine,
polyethyleneimine, polymethacrylamide, poly(acrylic acid),
poly(methacrylic acid), poly(hydroxyethyl acrylate),
poly(hydroxyethyl methacrylate), poly(n-vinyl pyrrolidinone),
poly(ethylene oxide), hydroxyethyl cellulose, hydroxypropyl
cellulose, guar gum, starch, agar, chitosan, alginic acid,
carboxymethyl cellulose, highly branched polyamidoamines, silylated
polyamidoamines, mixtures thereof, and the like. When combined with
other water-soluble polymers in the formulation, the weight ratio
of PPAE resins prepared according to the processes of the present
invention to the other water soluble polymers can be in the range
of from 0.01 to 0.99 up to from 0.99 to 0.01.
[0030] Creping adhesive formulations comprising the PPAE resin may
also comprise one or more release aids, as well as other additives
that may affect the creping process. This is known as the creping
adhesive package. Suitable creping release agents are, for example,
disclosed in U.S. Pat. Nos. 5,660,687; and 5,833,806, the
disclosures of which are incorporated herein by reference in their
entireties. Exemplary release aids include, without limitation,
mineral oil, vegetable oil, polyethylene glycol monoester,
polyethylene glycol diester, ethoxylated polyethylene glycol, fatty
acid imidazolinium surfactant, ethylene glycol, propylene glycol,
diethylene glycol, glycerol, sorbitol, dipropylene glycol,
pyrrolidone, aromatic sulfonamides, triethanolamine,
diethanolamine, and mixtures thereof. In addition to adhesive
components and release agent additives, creping adhesive
formulations can further comprise surfactants, dispersants, salts
to adjust the water hardness, acids or bases to adjust the pH of
the creping adhesive composition, modifiers, or other useful
additives. Suitable modifiers include, but are not limited to, the
tackifier resins of U.S. Pat. No. 6,133,405, or the stabilizers of
U.S. Pat. No. 6,280,571, the disclosures of which are incorporated
herein by reference in their entireties. By way of example, the
creping adhesive formulation may include phosphate such as
monoammonium phosphate and diammonium phosphate as well as
plasticizers such as glycerol, and polyethylene glycol.
[0031] The PPAE resins can be applied either by themselves or in
combination with other components in the creping adhesive package
as a means for creping a fibrous web, and employing this means to
crepe the web. Further in this regard, the creping process of the
invention can include the steps of applying the PPAE resin either
by itself or in combination with the creping adhesive package to a
drying surface for the fibrous web, providing a fibrous web,
pressing the fibrous web against the drying surface to adhere this
web to the surface, and dislodging the fibrous web from the drying
surface with a creping device to crepe the fibrous web.
[0032] Application of the creping adhesives can be done in any
manner known in the art and in forms comprising aqueous, solid,
dispersion, or aerosol. One preferred mode of application is via a
spray boom directed at the surface of the drying surface prior to
transfer of the paper web. The creping adhesives can also be added
at the wet end of the paper machine or can be applied to the wet
web prior to its contact with the surface. Spray application of the
creping adhesive can be done according to any of the conventional
methods known in the art or any desired combination of application
procedures.
[0033] An exemplary process includes applying an adhesive
formulation comprising a polyamine-polyamidoamine-epihalohydrin
resin to a drying cylinder; pressing a paper web against the drying
cylinder to effect adhesion of the paper web to a surface of the
drying cylinder to effect adhesion of the paper web to the drying
cylinder; and dislodging the paper web from the drying cylinder by
contact with a doctor blade to form the creped paper.
[0034] The total amount of the PPAE resin that is applied from
about 0.01 g/kg to 5g/kg (0.02 lb/ton to 10 lb/ton) based on the
dry weight of the creping adhesive and dry weight of the paper web.
The unit lb/ton, as used herein, refers to the dry amount of the
creping adhesive measured in lbsiton relative to the dry amount of
paper measured in tons.
[0035] The following examples fall within the scope of, and serve
to exemplify, the more generally described methods set forth above.
The examples are presented for illustrative purposes only, and are
not intended to limit the scope of the disclosure.
Examples 1-3
Preparation of Polyamidoamines
[0036] Polyamidoamine was first prepared by a condensation reaction
of an excess amount of diethylenetriamine with adipic acid. In
particular, diethylenetriamine was added to a three neck flask.
Adipic acid was then slowly added to the flask and the reaction
mixture heated to 165-170.degree. C. and maintained for a period of
5 hours. At the end of the reaction, the product was diluted with
water to adjust the concentration to 60% and the temperature was
lowered to room temperature. Table 1 shows the charge ratios of
diethylenetriamine and adipic acid.
TABLE-US-00001 TABLE 1 Charge ratios of polyamidoamine
Diethylenetriamine/adipic acid molar Example ratio 1 1.4 2 1.6 3
1.8 4 1.0
Examples 4-16
Preparation of PPAE Resins
[0037] Polyamidoamine, polyamine, and water were first added to a
one liter reactor with reflux. The reactor was heated to 70.degree.
C. and maintained at this temperature throughout the reaction.
Epichlorohydrin was then added to the reactor slowly to increase
product viscosity. Water was added stepwise during the reaction to
reduce viscosity buildup rate to avoid product gelation. Once the
product reached the desired viscosity range, final charge of water
was added to the reactor and pH was adjusted to around 5.0 using
concentrated sulfuric acid (95%). The total solids of the products
were around 15%. Table 2 shows the charge ratios and properties of
the PPAE products.
TABLE-US-00002 TABLE 2 Charge ratios and properties of PPAE resins
Brookfield Polyamine/ viscosity Ex. polyamidoamine at 23.degree. C.
No. Polyamidoamine Polyamine weight ratio pH (cP) 4 Example 1 TETA
0.22 5.0 24 5 Example 1 TETA 0.22 5.0 55 6 Example 1 TETA 0.22 5.0
95 7 Example 2 DETA 0.07 4.9 24 8 Example 2 DETA 0.07 4.9 52 9
Example 2 DETA 0.07 4.9 69 10 Example 2 DETA 0.07 5.0 96 11 Example
3 DETA 0.07 5.0 26 12 Example 3 DETA 0.07 5.0 82 13 Example 3 DETA
0.07 5.0 96 14 Example 3 TETA 0.24 5.0 5 15 Example 3 TETA 0.24 5.0
26 16 Example 3 TETA 0.24 5.0 92
Comparative Examples 1-5
[0038] Polyamidoamine and water were added to a one liter reactor
with reflux. The reactor was heated to 70.degree. C. and maintained
at this temperature throughout the reaction. Epichlorohydrin was
then added to the reactor slowly to increase product viscosity.
Water was added stepwise during the reaction to reduce viscosity
buildup rate to avoid product gelation. Once the product reached
the desired viscosity range, final charge of water was added to the
reactor and pH was adjusted to around 5.0 using concentrated
sulfuric acid (95%). The total solids of the products were around
15%. Table 3 shows the charge ratios and properties of the
Comparative Examples. The Omnicrepe 681 AX adhesive referenced in
Table 3 below was a commercial creping adhesive product available
from Kemira Chemicals.
TABLE-US-00003 TABLE 3 Charge ratios and properties of comparative
examples Polyamine/ Brookfield Comparative polyamidoamine viscosity
at Examples Polyamidoamine weight ratio pH 23.degree. C. (cP) 1
Example 1 1.4 5.0 23 2 Example 1 1.4 5.0 64 3 Example 3 1.8 5.0 7 4
Example 3 1.8 5.0 40 5 Example 3 1.8 5.0 93 6 Example 2 1.6 5.0 37
7 Example 2 1.6 5.0 97 8 Example 2 1.6 5.0 140 9 Example 4 1.0 4.0
90 Omnicrepe ~1.0 4.0 681 AX
Epichlorohydrin-Reactive Sites on Polyamidoamine
[0039] The polyamidoamine samples contain both primary amine groups
and secondary amine groups. It is commonly accepted that each
secondary amine group reacts with one epichlorohydrin molecule,
whereas each primary amine group reacts with two epichlorohydrin
molecules. Therefore, the total number of epichlorohydrin-reactive
sites in a polyamidoamine sample is defined as
N=a1+2.times.a2 (1)
N is the molar quantity of epichlorohydrin-reactive sites, a1 is
the molar quantity of secondary amine groups, and a2 is the molar
quantity of primary amine groups. a1 and a2 are defined as
a 1 = n m 1 M W 2 ( 2 ) a 2 = ( m 1 M W 1 - m 2 M W 2 ) .times. 2 (
3 ) ##EQU00001##
where m1 is the mass of polyamine used to prepare the
polyamidoamine sample, m2 is the mass of dicarboxylic acid and/or
its derivative used to prepare the polyamidoamine sample, MW1 is
the formula weight of polyamine, MW2 is the formula weight of
dicarboxylic acid or its derivative and n is the number of
secondary amines in the polyamine
[0040] Reduced specific viscosity (RSV) was measured using a glass
capillary viscometer at 30.degree. C. The efflux time of each
sample was determined three times and the average efflux time was
calculated. The RSV was calculated as following
RSV=(t-t.sub.0)/(t.sub.0c) (4),
wherein t is the average efflux time of the polyamidoamine sample
diluted with 1 M NaCl solution, t.sub.0 is the average efflux time
of 1 M NaCl solution, c is the concentration of the diluted
polyamidoamine sample which was 5 wt %.
[0041] Table 4 lists the active polyamidoamine mass (PA mass), the
calculated molar quantities of epichlorohydrin-reactive sites on
polyamidoamine (EPI sites), the RSVs of the polyamidoamine samples
(RSV), and also the mass quantities of charged epichlorohydrin to
increase sample final viscosity above 50 cps at 23.degree. C. (EPI
mass). As shown in FIG. 1, the x-axis is the ratio of EPI sites
over the product of RSV and PA mass, the y-axis is the ratio of EPI
mass over PA mass. For four PAE resins, the correlation between
x-axis and y-axis is linear with a R.sup.2 of 0.999. In contrast,
the data points for the PPAE resins show a complex non-linear
correlation and do not fit the PAE linear correlation. Furthermore,
the data points of the PPAE resins are all above the fitted line
for the PAE resins, suggesting that a greater amount of
epichlorohydrin is required to achieve the desired viscosity range
compared to the PAE resins. Theoretically, the ratio of EPI mass
over PA mass (y-axis) of the PPAE resins will become infinitely
large when the ratio of PA mass over extra polyamine mass becomes
infinitely small. Overall, these differences demonstrate that the
molecular structure of the PPAE resins is fundamentally different
from that of the PAE resins.
TABLE-US-00004 TABLE 4 Polyamidoamine mass (PA mass),
epichlorohydrin-reactive sites on polyamidoamine (EPI sites),
reduced specific viscosity (RSV), and the mass quantities of
charged epichlorohydrin to increase sample final viscosity above 50
cps at 23.degree. C. (EPI mass) Backbone DETA/Adipic PA EPI EPI
Chem- acid molar mass sites RSV mass Name istry ratio (g) (mole)
(dL/g) (g) Comparative PAE 1.4 107.7 1.27 0.083 21.5 Example 2
Comparative PAE 1.8 77.0 1.30 0.066 29.3 Example 5 Comparative PAE
1.6 53.6 0.781 0.074 15.4 Example 7 Comparative PAE 1.0 129.6 0.608
0.156 5.3 Example 9 Example 6 PPAE 1.4 58.2 0.690 0.083 24.5
Example 10 PPAE 1.6 68.7 1.00 0.074 25.6 Example 13 PPAE 1.8 87.2
1.48 0.066 40.4 Example 16 PPAE 1.8 82.6 1.40 0.066 48.2
Adhesive Performance Tests
[0042] In this invention, a rewettability test and an insolubility
test were carried out to study adhesive properties. The
rewettability test provides the insight about adhesive
re-activation when in contact with the wet paper sheet. A more
rewettable adhesive deposit will become softer in contact with the
wet sheet since water plasticizes the adhesive deposit.
Consequently, the Yankee dryer and the sheet form a more intimate
contact, resulting in a higher adhesion. The insolubility test was
employed to determine the percentage of the adhesive remaining
un-dissolved in the presence of water. Therefore, the insolubility
is closely related to the "durability" of the adhesive on the
Yankee.
[0043] In the rewettability test, 4 g of adhesive product was added
to a 200 mL beaker and dried at 90.degree. C. for one hour and
110.degree. C. for four hours to obtain the adhesive product in dry
form. Afterwards, 50 g of water was added to the beaker. After 30
minutes of soaking at room temperature, excess water was removed
from the beaker by decantation and the weight of adhesive hydrogel
was determined. The water used for rewetting was obtained by adding
NaCl to de-ionized water to adjust the conductivity to 90 .mu.s.
The rewettability ratio was calculated as the weight ratio of the
adhesive hydrogel to the dry adhesive. Table 5 shows the
rewettability result. When comparing the PPAE samples and the PAE
samples prepared using the same polyamidoamine, the PPAE samples
provided higher rewettability ratios than the PAE samples.
TABLE-US-00005 TABLE 5 Rewettability results Backbone DETA/Adipic
Rewettability Example Chemistry acid molar ratio ratio Comparative
PAE 1.4 7.4 Example 2 Comparative PAE 1.8 13.8 Example 4
Comparative PAE 1.6 18.0 Example 7 Omnicrepe 681 PAE ~1.0 9.2 AX
Example 5 PPAE 1.4 20.0 Example 10 PPAE 1.6 21.1 Example 13 PPAE
1.8 17.0
[0044] In the insolubility test, 4 g of adhesive product was added
to a 200 mL beaker and dried at 90.degree. C. for one hour and
110.degree. C. for four hours to determine the dry solid content.
Afterwards, 50 g of water was added to the beaker which was then
placed on an incubating shaker (Thermo Scientific MAXQ 4450) at
60.degree. C. and 200 rpm. After 60 minutes of shaking, the
adhesive suspension was poured on a Nylon membrane with a pore size
of 5 micron (OSMONICS, model number R50SP09025) and drained under
vacuum. The remaining adhesive gel on the membrane was then dried
in a convection oven and the weight of the dry solid was
determined. The insolubility percentage of the adhesive product was
calculated as the weight percentage of the remaining dry solid
content over the original adhesive dry solid content. The results
are shown in Table 6.
[0045] Adhesive rewettability and insolubility are often inversely
related to each other. For example, increasing adhesive
hydrophobicity can increase adhesive insolubility but decrease
adhesive rewettability. In contrast, decreasing adhesive
cross-linking degree can increase adhesive rewettability but
decrease adhesive insolubility. However, the introduction of
polyamine in the polyamidoamine epichlorohydrin resin structure can
increase both properties at the same time relative to PAE. As shown
in Table 6, both Comparative Example 4 (PAE) and Example 15 (PPAE)
were prepared using the same polyamidoamine with a DETA/AA ratio of
1.8. Relative to the PAE resin, the incorporation of extra TETA in
Example 15 not only increased the rewettability ratio from 13.8 to
15.4 but also resulted in an increase in the insolubility
percentage from 46% to 58%.
TABLE-US-00006 TABLE 6 Rewettability and insolubility results
Backbone DETA/Adipic acid Rewettability Insolubility Example
Chemistry molar ratio ratio (%) Comparative PAE 1.8 13.8 46 Example
4 Example 15 PPAE 1.8 15.4 58
[0046] This written description uses examples to disclose the
invention, including the best mode, and also to enable any person
skilled in the art to make and use the invention. The patentable
scope of the invention is defined by the claims, and may include
other examples that occur to those skilled in the art. Such other
examples are intended to be within the scope of the claims if they
have structural elements that do not differ from the literal
language of the claims, or if they include equivalent structural
elements with insubstantial differences from the literal languages
of the claims.
* * * * *