U.S. patent application number 09/804377 was filed with the patent office on 2002-03-07 for color-stable polyalkyleneimine derivatives, fiberglass lubricants containing the same and processes for producing the same.
Invention is credited to Fry, Douglas F., Tuller, Frank Norman.
Application Number | 20020028910 09/804377 |
Document ID | / |
Family ID | 22695010 |
Filed Date | 2002-03-07 |
United States Patent
Application |
20020028910 |
Kind Code |
A1 |
Fry, Douglas F. ; et
al. |
March 7, 2002 |
Color-stable polyalkyleneimine derivatives, fiberglass lubricants
containing the same and processes for producing the same
Abstract
Polymer derivatives based upon polyalkyleneimine backbones
having a color stabilizing-effective amount of their reactive amino
functionalities substituted by either a carboxylic acid or an
amino-protecting group such as urea, are disclosed. Methods for
preparing said derivatives are also disclosed. Fiber lubricant
compositions comprising said polymer derivatives, and the
resistance to yellowing associated with such lubricants are
disclosed. Also disclosed are methods for treating fibers using the
polymer derivatives.
Inventors: |
Fry, Douglas F.; (Charlotte,
NC) ; Tuller, Frank Norman; (Simpsonville,
SC) |
Correspondence
Address: |
COGNIS CORPORATION
2500 RENAISSANCE BLVD., SUITE 200
GULPH MILLS
PA
19406
|
Family ID: |
22695010 |
Appl. No.: |
09/804377 |
Filed: |
March 12, 2001 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60188896 |
Mar 13, 2000 |
|
|
|
Current U.S.
Class: |
528/288 |
Current CPC
Class: |
C10N 2040/34 20130101;
Y10T 428/2967 20150115; Y10T 428/2969 20150115; C08G 73/028
20130101; C10N 2040/44 20200501; C03C 25/32 20130101; Y10T 428/2913
20150115; C10N 2040/32 20130101; C10N 2040/36 20130101; C10N
2040/50 20200501; C10M 2217/044 20130101; C10N 2040/38 20200501;
C10N 2040/42 20200501; C08G 73/0206 20130101; C10M 107/44 20130101;
C10M 2217/045 20130101; C10N 2040/30 20130101; C08G 18/71 20130101;
C10N 2040/40 20200501; Y10T 428/29 20150115; C08G 18/60 20130101;
Y10T 428/2938 20150115; C10N 2040/00 20130101 |
Class at
Publication: |
528/288 |
International
Class: |
C08G 069/00 |
Claims
What is claimed is:
1. A polymer derivative comprising a polyalkyleneimine backbone
having a number of reactive amino functionalities, each reactive
amino functionality having at least one reactive hydrogen atom,
wherein a color stabilizing-effective amount of the number of
reactive amino functionalities have a substituent-compound
independently selected from the group consisting of carboxylic
acids and amine-protecting compounds substituted in place of the at
least one reactive hydrogen atom, and wherein at least about 20% of
the reactive amino functionalities have a carboxylic acid
substituted in place of the at least one reactive hydrogen
atom.
2. The polymer derivative according to claim 1, wherein the
polyalkyleneimine backbone comprises a polyethyleneimine having a
molecular weight of from about 400 to about 2500.
3. The polymer derivative according to claim 1, wherein the
polyalkyleneimine backbone comprises a polyethyleneimine having a
molecular weight of from about 1000 to about 1800.
4. The polymer derivative according to claim 1, wherein the
carboxylic acids have from about 2 to about 18 carbon atoms.
5. The polymer derivative according to claim 1, wherein the
carboxylic acids have from about 2 to about 9 carbon atoms.
6. The polymer derivative according to claim 1, wherein the
substituent-compounds selected from the group consisting of
carboxylic acids comprise two or more C.sub.2-C.sub.18 carboxylic
acids.
7. The polymer derivative according to claim 6, wherein the
substituent-compounds selected from the group consisting of
carboxylic acids comprise acetic acid and pelargonic acid.
8. The polymer derivative according to claim 1, wherein the
amine-protecting compounds are selected from the group consisting
of urea, substituted ureas, isocyanates, cyanamides, haloformates,
azidoformates, carbonates, dicarbonates, sulfonyl halides, and
methylating agents.
9. The polymer derivative according to claim 1, wherein the
amine-protecting compounds are selected from the group consisting
of urea, substituted ureas, isocyanates, and cyanamides.
10. The polymer derivative according to claim 1, wherein the
amine-protecting compounds comprise urea.
11. The polymer derivative according to claim 1, wherein at least
about 75% of the number of reactive amino functionalities have a
substituent-compound substituted in place of the at least one
reactive hydrogen atom.
12. The polymer derivative according to claim 1, wherein at least
about 80% of the number of reactive amino functionalities have a
substituent-compound substituted in place of the at least one
reactive hydrogen atom.
13. The polymer derivative according to claim 1, wherein at least
about 90% of the number of reactive amino functionalities have a
substituent-compound substituted in place of the at least one
reactive hydrogen atom.
14. A polymer derivative comprising a polyethyleneimine backbone
having a molecular weight of about 1200 and a number of reactive
amino functionalities, each reactive amino functionality having at
least one reactive hydrogen atom, wherein at least about 90% of the
number of reactive amino functionalities have a
substituent-compound independently selected from the group
consisting of acetic acid, pelargonic acid and urea substituted in
place of the at least one reactive hydrogen atom, and wherein about
30% of the substituent-compounds comprise acetic acid and about 20%
of the substituent-compounds comprise pelargonic acid.
15. A polymer derivative prepared by a process comprising reacting
a polyalkyleneimine having a number of reactive amino
functionalities with a carboxylic acid and an amine-protecting
compound, under conditions sufficient to derivatize a color
stabilizing-effective amount of the reactive amino functionalities
with either the carboxylic acid or the amine-protecting compound,
wherein at least about 20% of the reactive amino functionalities
are derivatized with the carboxylic acid.
16. A process for preparing a polymer derivative, the process
comprising (a) providing a polyalkyleneimine having a number of
reactive amino functionalities per mole, (b) reacting the
polyalkyleneimine with at least one carboxylic acid and an
amine-protecting compound, wherein a total molar amount of the at
least one carboxylic acid and the amine-protecting compound is used
which is sufficient to derivatize a color stabilizing-effective
amount of the number of reactive amino functionalities per
mole.
17. The process according to claim 16, wherein the at least one
carboxylic acid and the amine-protecting compound are reacted in a
molar ratio of from about 2:3 to about 3:2.
18. The process according to claim 16, wherein the at least one
carboxylic acid and the amine-protecting compound are reacted with
the polyalkyleneimine sequentially.
19. The process according to claim 16, wherein the
polyalkyleneimine comprises a polyethyleneimine having a molecular
weight of from about 400 to about 2500.
20. The process according to claim 16, wherein the
polyalkyleneimine comprises a polyethyleneimine having a molecular
weight of from about 1000 to about 1800.
21. The process according to claim 16, wherein the at least one
carboxylic acid comprises a carboxylic acid have from about 2 to
about 18 carbon atoms.
22. The process according to claim 16, wherein the at least one
carboxylic acid comprises a carboxylic acid have from about 2 to
about 9 carbon atoms.
23. The process according to claim 16, wherein the at least one
carboxylic acid comprises a mixture of two or more carboxylic acids
having from about 2 to about 18 carbon atoms.
24. The process according to claim 16, wherein the at least one
carboxylic acid comprises a mixture of acetic acid and pelargonic
acid.
25. The process according to claim 17, wherein the at least one
carboxylic acid comprises a mixture of acetic acid and pelargonic
acid.
26. The process according to claim 25, wherein the pelargonic acid
and the acetic acid are reacted in a molar ratio of about 2:3.
27. The process according to claim 16, wherein the at least one
amine-protecting compound is selected from the group consisting of
urea, substituted ureas, isocyanates, cyanamides, haloformates,
azidoformates, carbonates, dicarbonates, sulfonyl halides, and
methylating agents.
28. The process according to claim 16, wherein the at least one
amine-protecting compound is selected from the group consisting of
urea, substituted ureas, isocyanates, and cyanamides.
29. The process according to claim 16, wherein the at least one
amine-protecting compound comprises urea.
30. The process according to claim 16, wherein a total molar amount
of the at least one carboxylic acid and the amine-protecting
compound is used which is sufficient to derivative at least about
75% of the number of reactive amino functionalities per mole.
31. The process according to claim 16, wherein a total molar amount
of the at least one carboxylic acid and the amine-protecting
compound is used which is sufficient to derivatize at least about
80% of the number of reactive amino functionalities per mole.
32. The process according to claim 16, wherein a total molar amount
of the at least one carboxylic acid and the amine-protecting
compound is used which is sufficient to derivatize at least about
90% of the number of reactive amino functionalities per mole.
33. A process for preparing a polymer derivative, the process
comprising (a) providing a polyethyleneimine having a molecular
weight of about 1200 and a number of reactive amino functionalities
per mole, (b) reacting the polyethyleneimine with acetic acid,
pelargonic acid and urea, wherein a total molar amount of the
acetic acid, pelargonic acid and urea is used which is sufficient
to derivative at least about 90% of the number of reactive amino
functionalities per mole.
34. A polymer derivative prepared by the process according to claim
16.
35. A polymer derivative prepared by the process according to claim
33.
36. A fiber lubricant composition comprising a polymer derivative
according to claim 1.
37. A fiber lubricant composition comprising a polymer derivative
according to claim 14.
38. A fiber lubricant composition comprising a polymer derivative
according to claim 15.
39. A fiber lubricant composition comprising a polymer derivative
according to claim 34.
40. A fiber lubricant composition comprising a polymer derivative
according to claim 35.
41. A method of lubricating a fiber material comprising providing a
fiber material and contacting the fiber material with a polymer
derivative according to claim 1.
42. A method of lubricating a fiber material comprising providing a
fiber material and contacting the fiber material with a polymer
derivative prepared by the process according to claim 16.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of priority, under 35 U.S.C.
.sctn.119(e), of U.S. Provisional Patent Application No.
60/188,896, filed Mar. 13, 2000, the entire contents of which are
herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] Fiber processing, including, for example, the manufacture of
continuous strands from numerous monofilaments or individual
fibers, usually involves the use of equipment which subjects the
monofilaments, individual fibers and/or continuous strands to high
speed, wherein the fiber materials are subjected to destructive
abrasive forces which can be the result of both mutual abrasion
between strands and/or between the strands and the equipment. At
any rate, it is usual to provide some lubrication for the fibers.
Fiber lubricants are commonly used during the production of many
different materials, including fiberglass and synthetic fibers such
as polyesters, polyolefins, polyacrylics, polyamides, etc. Fiber
lubricants are typically applied to fibers as a component of a
sizing composition, usually immediately after fiber formation, but
before fibers are gathered into a bundle, and may also added to
fiber materials to provide lubricity during subsequent usage.
[0003] One class of fiber lubricants is polyethyleneimine
polyamides. Polyethyleneimine polyamides are commonly used to
lubricate fiberglass. Polyethyleneimine polyamides generally
provide adequate lubricity in that filaments breaking, i.e., fuzz
formation is limited during processing and fiber tensile strength
is generally improved. However, in some processing applications
where the treated material is exposed to heat, air and the
combination thereof, the polyethyleneimine polyamides may become
discolored, evidenced by a yellowing of the material.
[0004] One method for combating the unattractive yellowing that
occurs during such processing of fibers such as fiberglass which
have been treated with sizing compositions including
polyethyleneimine polyamide lubricants, and/or other compounds
associated with yellowing, is to add a fluorescent whitening agent
to the sizing composition prior to use. Fluorescent whitening
agents can be expensive, and may be problematic in terms of
formulation, stability, solubility, etc.
[0005] Discoloration will not necessarily render the fiber material
unusable, but for aesthetic reasons, discoloration should be
avoided. Thus, there is a need in the art for a fiberglass
lubricant with the lubricating properties of polyethyleneimine
polyamides which possesses color stability when exposed to heat
and/or air.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention relates to a polymer derivative, and
more particularly, to a polyalkyleneimine polyamide-derivative
which can be used as a fiber lubricant. Polymer derivatives in
accordance with the present invention are particularly suitable as
lubricants for fiberglass processing. Polymer derivatives in
accordance with the present invention, and lubricant and sizing
compositions containing such polymer derivatives, exhibit excellent
color stability (i.e., reduced yellowing) when exposed to heat
and/or air during or subsequent to fiber processing, as compared to
commercially available polyalkyleneimine polyamide fiber
lubricants.
[0007] One aspect of the present invention includes a polymer
derivative which comprises a polyalkyleneimine backbone which has a
number of reactive amino functionalities, each reactive amino
functionality having at least one reactive hydrogen atom, wherein a
color stabilizing-effective amount of the number of reactive amino
functionalities have a substituent-compound independently selected
from carboxylic acids and amine-protecting compounds substituted in
place of a reactive hydrogen atom, and wherein at least about 20%
of the substituent-compounds are selected from the group consisting
of carboxylic acids. In preferred embodiments of this and other
aspects of the present invention, the polyalkyleneimine backbone is
a polyethyleneimine having a molecular weight of from about 1000 to
about 1800 and the amine-protecting compound comprises urea.
[0008] Another aspect of the present invention includes a polymer
derivative prepared by a process which comprises reacting a
polyalkyleneimine having a number of reactive amino functionalities
with a carboxylic acid and an amine-protecting compound, under
conditions which are sufficient to derivatize a color
stabilizing-effective amount of the reactive amino functionalities
with either the carboxylic acid or the amine-protecting compound,
wherein at least about 20% of the reactive amino functionalities
are derivatized with the carboxylic acid.
[0009] Yet another aspect of the present invention includes a
process for preparing a polymer derivative wherein the process
comprises: (a) providing a polyalkyleneimine having a number of
reactive amino functionalities per mole; (b) reacting the
polyalkyleneimine with at least one carboxylic acid and an
amine-protecting compound, wherein a total molar amount of the at
least one carboxylic acid and the amine-protecting compound is used
which is sufficient to derivatize a color stabilizing-effective
amount of the number of reactive amino functionalities per mole of
polyalkyleneimine. In some preferred embodiments of this and other
aspects of the present invention, a polyethyleneimine having a
molecular weight of about 1200 is reacted with acetic acid,
pelargonic acid and urea, wherein a total molar amount of the
acetic acid, pelargonic acid and urea is substantially equal to the
number of reactive amino functionalities per mole of
polyethyleneimine. The present invention also includes polymer
derivatives prepared by processes in accordance with this aspect of
the invention.
[0010] Other aspects of the present invention include fiber
lubricant compositions and sizing compositions comprising one or
more polymer derivatives according to any one of the aspects or
embodiments of the present invention.
[0011] The present invention also includes a method of lubricating
a fiber material comprising providing a fiber material and
contacting the fiber material with a polymer derivative according
to any one of the aspects or embodiments of the present
invention.
[0012] As used herein, the terms "react", "substitute", and
"derivatize", and their various tenses, all synonymously refer to a
chemical reaction between a substituent-compound (i.e., a
carboxylic acid or an amine-protecting compound) and a reactive
amino functionality of a polyalkyleneimine.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Polyalkyleneimines useful in accordance with the present
invention include any polyalkyleneimines having reactive amino
functionalities suitable for reaction with, for example, a
carboxylic acid, such as, for example, the polyalkyleneimines
described in U.S. Pat. No. 3,597,265, the entire contents of which
are incorporated herein by reference, including mixtures of two or
more different polyalkyleneimines. As used herein, the phrase
"reactive amino functionality" shall refer to any primary or
secondary nitrogen atom in a polyalkyleneimine. Also, as used
herein, the terms "polyalkyleneimine backbone" and
"polyethyleneimine backbone" refer to that portion of the resulting
polymer derivative in accordance with the present invention which
is derived from the original polyalkyleneimine or polyethyleneimine
starting material, respectively.
[0014] The polyalkyleneimine, or the polyalkyleneimine backbone
(which terms when referring to molecular weight are used
synonymously), will preferably have a molecular weight of from
about 300 to about 70000, and more preferably from about 400 to
about 2500. Thus, when referring to the molecular weight of the
polyalkyleneimine backbone of a polymer derivative in accordance
with the present invention, such weights include reactive hydrogen
atoms removed from the original polyalkyleneimine starting material
upon substitution with a carboxylic acid or amine-protecting
compound. Particularly preferred polyalkyleneimines are
polyethyleneimines. Preferred polyethyleneimines will have a
molecular weight of from about 1000 to about 1800, with molecular
weights of about 1200 being most preferred at least in part due to
commercial availability and economics.
[0015] Polyalkyleneimines, and particularly polyethyleneimines, can
be commercially obtained from a wide range of sources including,
for example, Aceto Corp. (Nippon Shokubai, Japan) and BASF.
However, synthetic production of such polyalkyleneimines can be
accomplished by known polymerization methods such as, for example,
acid catalyzed polymerization of applicable monomers, including but
not limited to, ethyleneimine (aziridine) and substituted
aziridines.
[0016] The number of reactive amino functionalities per mole that
any particular polyalkyleneimine will have is a function of its
molecular weight, and may further vary slightly at any one
particular molecular weight. For example, a polyethyleneimine with
a molecular weight of about 1200 will have about 28 or 29 total
amino functionalities per mole of that polyethyleneimine. However,
from about 7 to about 9 of the total number of amino
functionalities are likely to be tertiary. Thus, the number of
reactive amino groups in a mole of a polyethyleneimine with a
molecular weight of about 1200 can vary from about 20 to 21, and
may vary more. Standard and well-known analytical methods, such as,
for example, C.sup.13NMR, can assist in a determination of the
number of reactive amino functionalities per mole of a particular
polyalkyleneimine, if unknown.
[0017] Carboxylic acids useful in accordance with the present
invention preferably have from about 2 to about 26 carbon atoms,
including fatty acids (i.e., C.sub.6-C.sub.22), preferably from
about 2 to about 18 carbon atoms, and most preferably from about 2
to about 9 carbon atoms. Carboxylic acids useful in accordance with
the present invention may be linear or branched, and saturated or
unsaturated. However, saturated acids are preferred as unsaturated
acids may be more likely to yellow upon oxidation.
[0018] In certain preferred embodiments of the present invention,
mixtures of two or more carboxylic acids are used. Accordingly, for
example, two or more carboxylic acids having from about 2 to about
26 carbon atoms, or preferably from about 2 to about 18 carbon
atoms, and most preferably from about 2 to about 9 carbon atoms,
along with an amine-protecting compound, could be reacted with a
polyalkyleneimine.
[0019] Mixtures of carboxylic acids include, but are not limited
to, naturally occurring mixtures of fatty acids such as those
obtained from palm or coconut oils, often referred to as technical
mixtures. Such technical mixtures may contain several different
chain length acids, such as a mixture having two or more acids of
from 5 to 10 carbons atoms in length, or two or more acids having
chain lengths of from 12 to 20 carbon atoms. A particularly
preferred mixture of two or more carboxylic acids comprises
pelargonic acid and acetic acid. The acids used in accordance with
the present invention can be obtained commercially or obtained from
natural sources by distillation. Non-naturally occurring fatty
acids having an odd number of carbon atoms can also be obtained
commercially or by known synthetic processes, such as via the
oxidation of nonyl alcohol in the case of pelargonic acid. Acetic
acid, or other short chain acids, may be used in conjunction with a
longer fatty acid to impart water-solubility to the resulting
polymer derivative.
[0020] Amine-protecting compounds useful in accordance with the
present invention are capable of reacting with primary and
secondary amine functionalities with sufficient favorability
(thermodynamic, kinetic or otherwise) to substitute reactive amino
functionalities present in a polyalkyleneimine, that are not
otherwise substituted by the carboxylic acid(s) used in accordance
with the present invention, such that a color stabilizing-effective
amount of the number of reactive amino functionalities in the
polyalkyleneimine backbone are substituted (i.e., reacted with or
derivatized by, either a carboxylic acid or an amine-protecting
compound). In general, in accordance with the present invention, a
"color stabilizing-effective amount", means an amount which is at
least about 60-65% of the total number of reactive amino
functionalities present in a given polyalkyleneimine backbone. In
preferred embodiments of the present invention, at least about 75%
of the number of reactive amino functionalities in the
polyalkyleneimine backbone are substituted. In increasingly more
preferred embodiments of the present invention, at least about 80%,
and at least about 90% of the number of reactive amino
functionalities in the polyalkyleneimine backbone are substituted.
Even more preferably, an amine-protecting compound used in
accordance with the present invention will react with the reactive
amino functionalities of the polyalkyleneimine with sufficient
favorability, such that at least about 92% of the number of
reactive amino functionalities in the polyalkyleneimine backbone
are substituted, and in the most preferred embodiments of the
present invention, at least about 94% of the number of reactive
amino functionalities will be substituted.
[0021] Amine-protecting compounds useful in accordance with
preferred embodiments of the present invention include, but are not
limited to, urea and substituted ureas according to the general
formula (I), isocyanates, cyanamides and substituted cyanamides,
haloformates, azidoformates, sulfonyl halides, carbonates,
dicarbonates, and methylating agents: 1
[0022] wherein each R independently represents a hydrogen atom, or
an alkyl or aryl group having up to 30 carbon atoms. Urea compounds
useful in accordance with the present invention include
unsubstituted urea (CO(NH.sub.2).sub.2), N-substituted,
N,N'-substituted, N,N-substituted, N',N'-substituted, and
N,N,N',N'-substituted ureas. Any substituent which does not
interfere with the reaction between the urea carbonyl group and the
remaining reactive amino functionalities in a polyalkyleneimine can
be present, including, for example, alkyl substituents having from
1 to 30 carbon atoms, which may be linear or branched, and cyclic
or acyclic.
[0023] Some compounds within the broad classes of compounds set
forth above may not react with sufficient favorability to be
considered a preferred amine-protecting compound, or even adequate.
For example, dimethyl carbonate fails to provide a polymer
derivative having at least about 90% of its reactive amino
functionalities substituted in accordance with the present
invention. However, other more reactive amine-protecting compounds
may be effective, but could be considered too costly, such as in
the case of some more reactive carbonates, or too toxic, such as
with dimethyl sulfate. Preferred amine-protecting compounds
include, but are not limited to, urea and substituted ureas
according to the general formula (I), isocyanates, cyanamides and
substituted cyanamides. More preferred amine-protecting compounds
include, but are not limited to, urea and substituted ureas
according to the general formula (I), wherein each R independently
represents a hydrogen atom, or an aliphatic hydrocarbon group
having up to 9 carbon atoms, and even more preferably no more than
3 carbon atoms. The most preferred amine-protecting compound is
unsubstituted urea ("urea"), in part due to its low price.
[0024] Isocyanates useful as amine-protecting compounds include
monofunctional isocyanates, such as, for example, ethyl isocyanate,
octyl isocyanate and phenyl isocyanate to name a few. Cyanamide and
substituted cyanamides, including mono- and di-substituted
cyanamides wherein the substituents are selected from alkyl or aryl
groups having up to 30 carbon atoms can be used as well.
[0025] As discussed above, polymer derivatives in accordance with
the present invention comprise polyalkyleneimine backbones with a
color stabilizing-effective amount of the number of reactive amino
functionalities in the backbone substituted by either a carboxylic
acid or an amine-protecting compound. Processes in accordance with
the present invention, aiming to provide polymer derivatives
satisfying such substituent criteria will preferably react a
polyalkyleneimine with one or more carboxylic acids and at least
one amine-protecting compound in accordance with the quantities
described below.
[0026] Processes for preparing polymer derivatives in accordance
with the present invention generally react a polyalkyleneimine with
at least one carboxylic acid and an amine-protecting compound,
wherein a total molar amount of the at least one carboxylic acid
and the amine-protecting compound is used which is sufficient to
derivatize a color stabilizing-effective amount of the number of
reactive amino functionalities per mole. The total molar amount of
the at least one carboxylic acid and the amine-protecting compound
which is sufficient is generally equivalent to the number of
reactive amino functionalities to be substituted. For example,
approximately 22 to 23 moles of total carboxylic acid and
amine-protecting compound would be reacted with a polyalkyleneimine
backbone having 30 reactive amino functionalities per mole, to
produce a polymer derivative having at least about 75% of the
reactive amino functionalities substituted.
[0027] The carboxylic acid(s) and the amine-protecting compound(s)
are generally reacted with the polyalkyleneimine in an
acid:protectant molar ratio of from about 1:4 to about 4:1. A more
preferred acid:protectant molar ratio of from about 2:3 to about
3:2. Even more preferably, an acid:protectant molar ratio of from
about 1:1 to about 1.2:1 is employed.
[0028] When a mixture of carboxylic acids is used, the mole ratio
of acids may be adjusted in any necessary manner to provide for
increased lubrication, or increased water solubility, etc. For
example, when acetic acid and pelargonic acid are used together, a
preferred molar ratio of pelargonic acid to acetic acid is from
about 9:1 to 1:9, with about 2:3 being more preferred.
[0029] The polymer derivatives in accordance with the present
invention can be prepared by reacting a polyalkyleneimine with a
carboxylic acid(s) and an amine-protecting compound(s), either
sequentially or simultaneously. The polymer derivatives are
preferably prepared by heating a polyalkyleneimine to a temperature
of from about 30.degree. C. to about 100.degree. C., and more
preferably from about 50 to about 60.degree. C., and slowly adding
appropriate amounts of one or more carboxylic acids. The mixture of
the polyalkyleneimine and the one or more carboxylic acids is then
heated and held at a temperature of from about 160.degree. C. to
about 220.degree. C., preferably from about 180.degree. C. to about
200.degree. C., until no more substantial amounts of distillate are
produced. This reaction is preferably allowed to proceed as close
to completion as possible. The resulting partially amidated
polyalkyleneimine is then cooled to a temperature of from about
100.degree. C. to about 140.degree. C., preferably lower than about
120.degree. C., and most preferably to about 100.degree. C. When
using an amine-protecting compound such as a urea or a cyanamide,
processing can preferably be assisted by adding water to the
partially amidated polyalkyleneimine. An appropriate amount of an
amine-protecting compound is then added, and the temperature is
elevated, preferably slowly, up to about 140.degree. C., and
maintained at the slightly elevated temperature until the reaction
is essentially complete, for example, in the case of urea, when the
production of ammonia diminishes, and preferably for several hours.
For example, the reaction is preferably allowed to proceed for at
least about 3 to 4 hours. Water, preferably deionized water, may be
added to dilute the resulting polymer derivative. The derivative,
or optionally diluted derivative, is transferred to a suitable
container. Some degree of dilution is preferred where the neat
polymer derivative may be difficult to handle, such as in the case
of a glass composition.
[0030] Fiber lubricant and sizing compositions in accordance with
the present invention may be prepared by suitable dilution of a
polymer derivative in accordance with the present invention with a
solvent, preferably water. Such compositions may also include
additional optional ingredients, such as antioxidants. Antioxidants
which may be included can be of any variety, such as those
described in U.S. Pat. No. 5,646,207, the entire contents of which
are incorporated herein by reference, including sodium
hypophosphite which is preferred. An antioxidant, such as sodium
hypophosphite can be added to a fiber lubricant composition in
accordance with the present invention in an amount of up to about
20% by weight, based on the solids content, and preferably about
10% by weight.
[0031] Fiber lubricants in accordance with the present invention
provide excellent lubricity while maintaining excellent
color-stability at elevated temperatures. The tendency of
polyethyleneimine polyamides to yellow at elevated temperatures in
air (approximately 100.degree. C. or more) is significantly reduced
in lubricant compositions according to the present invention. Thus,
the present invention also provides a method of lubricating
fiberglass materials in which yellowing upon exposure of the
materials to heat is reduced.
[0032] The method of the present invention includes providing a
fiber material and a fiber lubricant composition or sizing
composition according to the present invention, and contacting the
material with the composition. Excess lubricant or sizing
composition may be drained, and the material dried. The material
may be brought into contact with a lubricant or sizing composition
by any known method, including for example, immersion, spraying,
kiss-roll and brushing. Drying can be accomplished by placing the
fiberglass material in an oven. Heating times and temperatures can
be adjusted depending on the oven or heat source used.
[0033] The present invention will now be illustrated in more detail
by reference to the following specific, non-limiting examples.
EXAMPLE 1
[0034] Approximately 0.250 moles of Epomin.RTM. SP-012, a
polyethyleneimine with a molecular weight of about 1200 (Aceto
Corp., Lake Success, N.Y.; Nippon Shakabi, Japan) were reacted with
approximately 1.08 moles of Emery.RTM. 1203 pelargonic acid (Cognis
Corp., Cincinnati, Ohio) and approximately 1.48 moles of glacial
acetic acid. The mixture was heated to 190.degree. C. and held
there for about 2 hours. The resulting polyethyleneimine polyamide
was allowed to cool to about 100.degree. C.
[0035] About 60 grams of deionized water and approximately 2.36
moles of urea were combined with the cooled polyethyleneimine
polyamide, and the mixture was slowly heated to 130.degree. C. and
then held at that temperature for about 3.5 hours. The resulting
yellow foam was then cooled to 100.degree. C.
[0036] Deionized water, heated to about 50.degree. C. and in an
amount sufficient to make a 50% aqueous solution, was combined with
the polyethyleneimine polyamide derivative and stirred until
solution was complete.
[0037] A 5% (solids) solution of the product was prepared, and its
pH adjusted to 5-6 using glacial acetic acid. A square of unsized,
heat-cleaned fiberglass fabric was dipped into the solution and
removed. Excess solution was allowed to drain from the fabric and
the fabric was then placed in an air-draft oven at 130.degree. C.
for 1 hour to produce a fiberglass fabric square treated with a
lubricant in accordance with one embodiment of the present
invention.
[0038] The degree of yellowing of the treated fiberglass fabric
square was evaluated, both quantitatively and subjectively, as
follows. The whiteness, or absence of yellowing, of the fabric
square was measured quantitatively via two standard methods. The
first method of evaluation used was the standard method according
to ASTM E313-00 "Standard practice for Calculating Yellowness and
Whiteness Indices from Instrumentally Measured Color Coordinates",
using an X-Rite.RTM. Model 978 spectrophotometer. The results set
forth in Table 1 are identified as "We". ASTM E313 procedures and
guidelines can be obtained from the American Society for Testing
and Materials, (West Conshohocken, Pa., www.astm.org), and the
entire contents of ASTM E313-00 are hereby incorporated herein by
reference. The second method of evaluation used was the standard
method according to CIE Publication No. 15.2, using an X-Rite.RTM.
Model 978 spectrophotometer. The results set forth in Table 1 are
identified as "W". CIE Publication No. 15.2 procedures and
guidelines can be obtained from the International Commission on
Illumination, (Vienna, Austria, www..cie.co.at), and the entire
contents of CIE Publication No. 15.2 are hereby incorporated herein
by reference. Finally subjective evaluation was performed via
visual inspection and qualified as either white or yellow in
accordance with the noticeability of any significant yellowing. An
evaluation of "white" indicates that no significant visible
yellowing was observed.
EXAMPLE 2
[0039] A polyethyleneimine polyamide prepared in accordance with
Example 1 was derivatized with ethyl isocyanate (.about.2.36 moles)
at 100-120.degree. C. for 1 hour, and the resulting
polyethyleneimine polyamide derivative was diluted with deionized
water to make a 40% solution. A 5% (solids) solution of the product
was prepared and made acidic (pH 5-6) with glacial acetic acid. An
identical square of heat-cleaned, unsized fiberglass fabric, as was
used in Example 1, was immersed in the solution and subjected to
the identical drying treatment as in Example 1. Whiteness
measurements of the fabric square treated in accordance with this
example were conducted in accordance with the analytical procedures
set forth above in Example 1. The results are set forth below in
Table 1.
EXAMPLE 3
[0040] A polyethyleneimine polyamide prepared in accordance with
Example 1 was diluted with about 250 grams of deionized water, then
treated with glacial acetic acid (.about.2.64 moles) and a 23%
solution of cyanamide (.about.2.64 moles) at 100.degree. C. The
mixture was heated to reflux for about 4.5 hours, then cooled to
room temperature, to give a 54% solution of a polyethyleneimine
polyamide guanidinium acetate derivative. A 5% (solids) solution of
the product was prepared (pH 5-6). An identical square of
heat-cleaned, unsized fiberglass fabric, as was used in Example 1,
was immersed in the solution and subjected to the identical drying
treatment as in Example 1. Whiteness measurements of the fabric
square treated in accordance with this example were conducted in
accordance with the analytical procedures referenced above in
Example 1. The results are set forth below in Table 1.
Control Example
[0041] An identical square of heat-cleaned, unsized fiberglass
fabric, not subjected to any treatment with a lubricant was
evaluated in terms of whiteness, in accordance with the analytical
procedures referenced above in Example 1. The results are set forth
below in Table 1.
Comparative Example 1
[0042] A polyethyleneimine polyamide prepared in accordance with
Example 1 was derivatized with dimethyl carbonate (.about.3.26
moles), and the mixture refluxed for 1 hour. The volatiles were
removed by distillation, and the resulting polyethyleneimine
polyamide partial carbamate derivative was diluted with deionized
water to make a 44% solution. A 5% (solids) solution of the product
was prepared and made acidic (pH 5-6) with glacial acetic acid. An
identical square of heat-cleaned, unsized fiberglass fabric, as was
used in Example 1, was immersed in the solution and subjected to
the identical drying treatment as in Example 1. Whiteness
measurements of the fabric square treated in accordance with this
example were conducted in accordance with the analytical procedures
referenced above in Example 1. The results are set forth below in
Table 1.
Comparative Example 2
[0043] A polyethyleneimine polyamide prepared in accordance with
Example 1 was diluted with deionized water to approximately 50%
solids, cooled to 50.degree. C., and acrylonitrile (.about.2.40
moles) was added drop-wise. The mixture was held at
.about.50.degree. C. for about 3 hours, then was cooled to room
temperature. The resulting partially-cyanoethylated
polyethyleneimine polyamide was diluted with deionized water to
make a 5% solids solution which was made acidic (pH 5-6) with
glacial acetic acid. An identical square of heat-cleaned, unsized
fiberglass fabric, as was used in Example 1, was immersed in the
solution and subjected to the identical drying treatment as in
Example 1. Whiteness measurements of the fabric square treated in
accordance with this example were conducted in accordance with the
analytical procedures referenced above in Example 1. The results
are set forth below in Table 1.
Comparative Example 3
[0044] A polyethyleneimine polyamide prepared in accordance with
Example 1 was diluted with deionized water to approximately 50%
solids, cooled to 41.degree. C., and formic acid (.about.3.96
moles) was added, followed by paraformaldehyde (.about.1.26 moles).
The mixture was heated at 40-60.degree. C. for about 7 hours, then
cooled to room temperature. The resulting partially-N-methylated
polyethyleneimine polyamide was diluted with deionized water to
make a 5% (solids) solution which was acidic (pH 3-4). An identical
square of heat-cleaned, unsized fiberglass fabric, as was used in
Example 1, was immersed in the solution and subjected to the
identical drying treatment as in Example 1. Whiteness measurements
of the fabric square treated in accordance with this example were
conducted in accordance with the analytical procedures referenced
above in Example 1. The results are set forth below in Table 1.
Comparative Example 4
[0045] An identical square of heat-cleaned, unsized fiberglass
fabric, as was used in Example 1, was immersed in a 5% (solids)
solution (pH 5-6) of a commercially available polyethyleneimine
polyamide fiberglass lubricant (Emery.RTM. 6717L), and subjected to
the identical drying treatment as in Example 1. Whiteness
measurements of the fabric square treated in accordance with this
example were conducted in accordance with the analytical procedures
referenced above in Example 1. The results are set forth below in
Table 1.
Comparative Example 5
[0046] An identical square of untreated, unsized fiberglass fabric,
as was used in Example 1, was immersed in a commercially available
polyethyleneimine polyamide fiberglass lubricant (Alubraspin.RTM.
226), and subjected to the identical drying treatment as in Example
1. Whiteness measurements of the fabric square treated in
accordance with this example were conducted in accordance with the
qualitative analytical procedures referenced above in Example 1.
The results are set forth below in Table 1.
1TABLE 1 Example Lubricant/Derivative Whiteness [We] Whiteness [W]
Visual No. Type (if any) (ASTM E313) (CIE Pub. 15.2) Eval. Control
untreated FG fabric 60.69 60.35 white 1 urea-derivative 17.14 10.49
white 2 ethyl isocyanate- 27.02 29.65 white derivative 3
cyanamide-derivative 10.23 5.35 white Comp. 1 dimethyl carbonate-
-21.43 -47.84 yellow derivative Comp. 2 acrylonitrile-derivative
-21.8 -36.08 yellow Comp. 3 paraform/formic acid- -22.14 -47.02
yellow derivative Comp. 4 Emery .RTM. 6717L Lubricant -11.8 -28.95
yellow Comp. 5 Alubraspin .RTM. 226 n.q.e. n.q.e. yellow Lubricant
In Table 1, "n.q.e." means not quantitatively evaluated.
[0047] As evidenced by the results set forth above in Table 1,
fiber lubricants containing polyethyleneimine polyamide derivatives
in accordance with the present invention exhibit a significant and
unexpected resistance to yellowing. The reduced yellowing upon
drying as compared to commercially available lubricants containing
polyethyleneimine polyamides is significantly improved.
Qualitatively, it has been observed, that little or no significant,
visible yellowing occurs on fibers treated with lubricants
containing polyethyleneimine polyamide derivatives in accordance
with the present invention.
[0048] It will be appreciated by those skilled in the art that
changes could be made to the embodiments described above without
departing from the broad inventive concept thereof. It is
understood, therefore, that this invention is not limited to the
particular embodiments disclosed, but it is intended to cover
modifications within the spirit and scope of the present invention
as defined by the appended claims.
* * * * *
References