U.S. patent application number 10/117834 was filed with the patent office on 2002-10-31 for emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids.
This patent application is currently assigned to STEPAN COMPANY, A corporation of the State of Delaware. Invention is credited to Schultz, Alfred K., Siddiqui, Adnan.
Application Number | 20020161108 10/117834 |
Document ID | / |
Family ID | 24078294 |
Filed Date | 2002-10-31 |
United States Patent
Application |
20020161108 |
Kind Code |
A1 |
Schultz, Alfred K. ; et
al. |
October 31, 2002 |
Emulsion polymerization process utilizing ethylenically unsaturated
amine salts of sulfonic, phosphoric and carboxylic acids
Abstract
Disclosed is an improved method of making polymers. The method
utilizes at least one ethylenically unsaturated monomer and at
least one polymerizable surface active agent. The polymerizable
surface active agent is capable of co-polymerization with
traditional monomers and/or polymerization with itself (i.e.
homopolymerization) and is preferably substantially completely
consumed during the course of the polymerization. Polymers produced
by the method of the present invention are well suited for use in
coatings, adhesives, sealants, elastomers and the like, as they
form stable films, possess excellent adhesion properties and have
improved hydrolytic stability characteristics. The present
invention also encompasses homopolymeric surface active agents and
their use in polymerization reactions.
Inventors: |
Schultz, Alfred K.; (Lake
Villa, IL) ; Siddiqui, Adnan; (Arlington Heights,
IL) |
Correspondence
Address: |
McDonnell Boehnen Hulbert & Berghoff
32nd Floor
300 S. Wacker Drive
Chicago
IL
60606
US
|
Assignee: |
STEPAN COMPANY, A corporation of
the State of Delaware
|
Family ID: |
24078294 |
Appl. No.: |
10/117834 |
Filed: |
April 8, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10117834 |
Apr 8, 2002 |
|
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09521819 |
Mar 9, 2000 |
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6407162 |
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Current U.S.
Class: |
524/815 |
Current CPC
Class: |
C08F 220/14 20130101;
Y10S 526/932 20130101; C08F 220/06 20130101; C08F 220/1804
20200201; C08F 220/1804 20200201; C08F 226/02 20130101; C08F 220/06
20130101; C08F 220/14 20130101; C08F 226/02 20130101; Y10S 526/91
20130101; C08F 2/24 20130101; C08F 220/14 20130101; C08F 226/02
20130101; Y10S 526/911 20130101 |
Class at
Publication: |
524/815 |
International
Class: |
C08K 003/00 |
Claims
What is claimed:
1. A method for forming polymers comprising: a) preparing a mixture
comprising: i) at least one ethylenically unsaturated monomer; ii)
at least one polymerizable, surface active agent; wherein the
polymerizable, surface active agent is a salt or quatemary nitrogen
compound comprising: a) at least one acid, wherein the acid is a
sulfonic acid, a carboxylic acid, or a phosphoric acid, or a
mixture thereof; and b) at least one nitrogenous base, wherein the
nitrogenous base contains at least one nitrogen atom and at least
one ethylenically unsaturated moiety; and b) polymerizing the
mixture; wherein the polymerizable, surface active agent is capable
of polymerization with itself, copolymerization with the
ethylenically unsaturated monomer or co-polymerization with a
partially polymerized polymer particle.
2. A method according to claim 1, wherein a portion of the
polymerizable, surface active agent is partially consumed by
polymerization with itself, co-polymerization with the monomer
and/or co-polymerization with a partially polymerized polymer
particle.
3. A method according to claim 1, wherein the polymerizable,
surface active agent is substantially consumed by polymerization
with itself, co-polymerization with the monomer and/or
co-polymerization with a partially polymerized polymer
particle.
4. A method according to claim 1, wherein the polymerizable,
surface active agent is substantially completely consumed by
polymerization with itself, co-polymerization with the monomer
and/or co-polymerization with a partially polymerized polymer
particle.
5. A method according to claim 1, wherein the nitrogenous base is a
compound of the formula 35wherein R.sub.1, R.sub.2 and R.sub.3 are
independently hydrogen or organic groups containing an ethenylene
group, provided that at least one of R.sub.1-R.sub.3 is a straight
or branched chain alkyl group containing 1-8 carbon atoms and an
ethenylene functionality.
6. A method according to claim 1, wherein the nitrogenous base is
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, allyldimethyl amine, methyl 3-amino
crotonate, 3-amino crotononitrile, 3-amino-1-propanol vinyl ether,
2-(dimethylamino)ethyl acrylate, or 1,4-diamino-2-butene or a
mixture thereof.
7. A method according to claim 6, wherein the nitrogenous base is
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, or a
mixture thereof.
8. A method according to claim 1, wherein the acid is a sulfonic
acid, a sulfonic acid ester, a polysulfonic acid, a sulfonic acid
of an oil, a paraffin sulfonic acid, a lignin sulfonic acid, a
petroleum sulfonic acid, an olefin sulfonic acid, a polyolefin
sulfonic acid, a polyolefin polysulfonic acid, a carboxylic acid, a
polycarboxylic acid, a phosphoric acid, a polyphosphoric acid, a
phosphinic acid, or a polyphosphinic acid, or a mixture
thereof.
9. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:(R.sub.1).sub.n--Ar(SO.sub.3.sup.-M.sup.+)- .sub.mwherein
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl,
napthyl, polynapthyl, styryl, or polystyryl group, or a mixture
thereof; wherein M.sup.+ is a conjugate acid of the nitrogenous
base; wherein n=1-5 and m=1-8; and wherein the total number of
carbon atoms represented by (R.sub.1).sub.n is at least 5.
10. A method according to claim 9, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein Ar is a phenyl; wherein M.sup.+ is a conjugate acid
of the nitrogenous base, selected from the group consisting of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof; and wherein n=1 and m=1.
11. A method according to claim 10, wherein the polymerizable,
surface active agent is of the formula: 36wherein n1=4-18; and
wherein R' is hydrogen or saturated or unsaturated hydrocarbon
group having from about 1-8 carbon atoms.
12. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:(R.sub.1).sub.n1--{Ar(SO.sub.3.sup.-M.sup.-
+).sub.m1}--O--{Ar(So.sub.3.sup.-M.sup.+).sub.m2}--(R.sub.2).sub.n2wherein
R.sub.1 and R.sub.2 are independently hydrogen, or saturated or
unsaturated hydrocarbon groups having from about 1-24 carbon atoms;
wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl,
or polystyryl group, or a mixture thereof; wherein M.sup.+ is a
conjugate acid of the nitrogenous base; wherein n1 and n2 are
independently 0-5, provided that n1 and n2 are not both equal to
zero; and wherein m1 and m2 are independently 0-8, provided that m1
and m2 are not both equal to zero.
13. A method according to claim 12, wherein R.sub.1 is hydrogen and
R.sub.2 is a saturated or unsaturated hydrocarbon group having from
about 6-24 carbon atoms; wherein Ar is phenyl; wherein M.sup.+ is a
conjugate acid of the nitrogenous base, selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof; wherein n1-4 and n2-1; and wherein m1 and m2
both equal one.
14. A method according to claim 12, wherein R.sub.1 and R.sub.2 are
independently saturated or unsaturated hydrocarbon groups having
from about 6-24 carbon atoms; wherein Ar is phenyl, wherein M.sup.+
is a conjugate acid of the nitrogenous base, selected from the
group consisting of allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl
acrylate, and mixtures thereof; wherein n1 and n2 both equal one;
and wherein m1 and m2 both equal one.
15. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1--CH(SO.sub.3.sup.-M.sup.+)CO.sub.2- R.sub.2wherein
R.sub.1 and R.sub.2 are independently saturated or unsaturated
hydrocarbon groups having from about 1-24 carbon atoms; and wherein
M.sup.+ is a conjugate acid of the nitrogenous base.
16. A method according to claim 15, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein R.sub.2 is methyl, ethyl, or propyl, or a mixture
thereof; and wherein M.sup.+ is a conjugate acid of the nitrogenous
base, selected from the group consisting of allyl amine, diallyl
amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof.
17. A method according to claim 16, wherein the polymerizable,
surface active agent is of the formula: 37wherein n=3-18.
18. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1--CH(SO.sub.3.sup.-M.sup.+)CO.sub.2- M.sup.+wherein
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 3-24 carbon atoms; and wherein M.sup.+ is a conjugate acid of
the nitrogenous base.
19. A method according to claim 18, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; and wherein M.sup.+ is a conjugate acid of the nitrogenous
base, selected from the group consisting of allyl amine, diallyl
amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof.
20. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1--CH(SO.sub.3.sup.-M.sup.+)C(O)O(CH-
.sub.2CH(R')O).sub.nR.sub.2wherein R.sub.1 and R.sub.2 are
independently saturated or unsaturated hydrocarbon groups having
from about 1-24 carbon atoms; wherein R' is methyl or hydrogen;
wherein n=1-100; and wherein M.sup.+ is a conjugate acid of the
nitrogenous base.
21. A method according to claim 20, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 4-24 carbon
atoms; R' is methyl or hydrogen; R.sub.2 is methyl, ethyl, or
propyl, and mixtures thereof; M.sup.+ is the nitrogenous base,
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof; and wherein
n=1-100.
22. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1--(SO.sub.3.sup.-M.sup.+)wherein R.sub.1 is a
saturated or unsaturated hydrocarbon group having from about 6-24
carbon atoms; and wherein M.sup.+ is a conjugate acid of the
nitrogenous base.
23. A method according to claim 22, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; and wherein M.sup.+ is a conjugate acid of the nitrogenous
base, selected from the group consisting of allyl amine, diallyl
amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof.
24. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1CO.sub.2(CH.sub.2).sub.nCH(SO.sub.3-
.sup.+M.sup.+)CO.sub.2R.sub.2wherein R.sub.1 and R.sub.2 are
independently saturated or unsaturated hydrocarbon groups having
from about 1-24 carbon atoms; wherein n=0-10; and wherein M.sup.+
is a conjugate acid of the nitrogenous base.
25. A method according to claim 24, wherein R.sub.1 and R.sub.2 are
independently saturated or unsaturated hydrocarbon groups having
from about 1-24 carbon atoms; wherein n=1-6; and wherein M.sup.+ is
a conjugate acid of the nitrogenous base, selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof.
26. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1CO.sub.2(CH.sub.2).sub.nSO.sub.3.su-
p.-M.sup.+wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein n=1-10; and
wherein M.sup.+ is a conjugate acid of the nitrogenous base.
27. A method according to claim 26, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein n=1-5; and wherein M.sup.+ is a conjugate acid of
the nitrogenous base, selected from the group consisting
essentially of allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl
acrylate, or a mixture thereof.
28. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:(R.sub.1).sub.n--Ar--O(CH.sub.2CH(R')O).su-
b.m(SO.sub.3.sup.-M.sup.+)wherein R.sub.1 is a saturated or
unsaturated hydrocarbon group having from about 1-24 carbon atoms;
wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl,
or polystyryl group, and mixtures thereof; wherein R' is methyl or
hydrogen; wherein M.sup.+ is a conjugate acid of the nitrogenous
base; wherein n 1-4; wherein the total number of carbon atoms
represented by (R.sub.1).sub.n is at least 5; and wherein
m=0-100.
29. A method according to claim 28, wherein, R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein Ar is phenyl; wherein M.sup.+ is a conjugate acid of
the nitrogenous base, selected from the group consisting of allyl
amine, diallyl amine, triallyl amine, methallyl amine, N-methyl
N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures
thereof; wherein n=1; and wherein m=0-100.
30. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1O(CH.sub.2CH(R')O).sub.n(SO.sub.3.s-
up.-M.sup.+)wherein R.sub.1 is a saturated or unsaturated
hydrocarbon group having from about 1-24 carbon atoms; wherein R'
is methyl or hydrogen; wherein n=0-100; and wherein M.sup.+ is a
conjugate acid of the nitrogenous base.
31. A method according to claim 30, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein R' is methyl or hydrogen; wherein n=0-100; and
wherein M.sup.+ is a conjugate acid of the nitrogenous base,
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof.
32. A method according to claim 31, wherein the polymerizable,
surface active agent is of the formula: 38wherein n1=5-18.
33. A method according to claim 31, wherein the polymerizable,
surface active agent is of the formula: 39wherein n1=5-18; and
wherein n=1-20.
34. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1CO.sub.2.sup.-M.sup.+wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 4-24 carbon
atoms; and wherein M.sup.+ is a conjugate acid of the nitrogenous
base.
35. A method according to claim 34, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; and wherein M.sup.+ is a conjugate acid of the nitrogenous
base, selected from the group consisting of allyl amine, diallyl
amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof.
36. A method according to claim 35, wherein the polymerizable,
surface active agent is of the formula: 40wherein n=5-18.
37. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1CON(R')(CH.sub.2).sub.nCO.sub.2M.su- p.+wherein
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 1-24 carbon atoms; wherein R' is methyl, ethyl, propyl or
hydrogen; wherein M.sup.+ is a conjugate acid of the nitrogenous
base; and wherein n1-10.
38. A method according to claim 37, wherein M.sup.+ is a conjugate
acid of the nitrogenous base, selected from the group consisting of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof; wherein R' is methyl, ethyl, propyl or hydrogen;
and wherein n=2-5.
39. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1CON(R')(CH.sub.2).sub.nSO.sub.3M.su- p.+wherein
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 1-24 carbon atoms; wherein R' is methyl, ethyl, propyl or
hydrogen; wherein M.sup.+ is a conjugate acid of the nitrogenous
base; and wherein n=1-10.
40. A method according to claim 39, wherein M.sup.+ is a conjugate
acid of the nitrogenous base, selected from the group consisting of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof; wherein R' is methyl, ethyl, propyl or hydrogen;
and wherein n=2-5.
41. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1O(CH.sub.2CH(R')O).sub.nCOCH.sub.2S-
O.sub.3.sup.-M.sup.+wherein R.sub.1 is a saturated or unsaturated
hydrocarbon group having from about 1-24 carbon atoms; wherein R'
is methyl or hydrogen; wherein n=0-100; wherein M.sup.+ is a
conjugate acid of the nitrogenous base.
42. A method according to claim 41, wherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 6-24 carbon
atoms; wherein R' is methyl or hydrogen; wherein M.sup.+is a
conjugate acid of the nitrogenous base, selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof; and wherein n=0-100.
43. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:R.sub.1O(PO.sub.3).sup.x-M.sup.+.sub.ywher- ein R.sub.1 is
a saturated or unsaturated hydrocarbon group having from about 1-24
carbon atoms, phenyl, polyphenyl, napthyl, polynapthyl, styryl, or
polystyryl group, an alkyl/alkoxylate substituted phenyl, an
alkyl/alkoxylate substituted or poly-substituted polyphenyl, an
alkyl/alkoxylate substituted or poly-substituted napthyl, an
alkyl/alkoxylate substituted or poly-substituted polynapthyl, an
alkyl/alkoxylate substituted or poly-substituted styryl, or an
alkyl/alkoxylate substituted or poly-substituted polystyryl group,
and mixtures thereof; wherein M.sup.+ is a conjugate acid of the
nitrogenous base; wherein x=1 or 2; and wherein y=1 or 2.
44. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:[R.sub.1O(CH.sub.2CH(R')O).sub.m].sub.nP(O-
).sub.p.sup.x-M.sup.+.sub.ywherein R.sub.1 is a saturated or
unsaturated hydrocarbon group having from about 1-24 carbon atoms;
wherein R' is methyl or hydrogen; wherein M.sup.+ is a conjugate
acid of the nitrogenous base, selected from the group consisting of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof; m=0-100; wherein n=1 or 2; wherein p=2 or 3;
wherein x=1 or 2; and wherein y=1 or 2.
45. A method according to claim 1, wherein the polymerizable,
surface active agent is of the
formula:[(R.sub.1).sub.nArO(CH.sub.2CH(R')O).sub.m-
].sub.qP(O).sub.p.sup.x-M.sup.+.sub.ywherein R.sub.1 is a saturated
or unsaturated hydrocarbon group having from about 1-24 carbon
atoms; wherein Ar is phenyl; wherein R' is methyl or hydrogen;
wherein M.sup.+ is a conjugate acid of the nitrogenous base,
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein
n=1-4; wherein m=0-100; wherein q=1 or 2; wherein p=2 or 3; wherein
x=1 or 2; and wherein y=1 or 2.
46. A method according to claim 1, wherein at least one of the
ethylenically unsaturated monomers is styrene and is reacted with
at least one acrylic monomer.
47. A method according to claim 1, wherein at least one of the
ethylenically unsaturated monomers is at least one non-aromatic
vinyl compound.
48. A method according to claim 1, wherein at least one of the
ethylenically unsaturated monomers is vinyl acetate and is reacted
with at least one acrylic monomer.
48. A method according to claim 1, wherein at least one of the
ethylenically unsaturated monomers is at least one acrylic
monomer.
49. A method according to claim 1, wherein the polymerizable,
surface active agent and the monomer are combined in a ratio of
about 0.01:1 to about 3:1 on a weight basis.
50. A method according to claim 49, wherein the polymerizable,
surface active agent is present in the mixture in a concentration
of about 1-10 weight percent, based on the total weight of the
ethylenically unsaturated monomer present in the mixture.
51. A method according to claim 50, wherein the polymerizable,
surface active agent is present in the mixture in a concentration
of about 1-3 weight percent, based on the total weight of the
ethylenically unsaturated monomer present in the mixture.
52. A method according to claim 1, wherein the polymerizable
surface active agent is formed by contacting the acid with the
nitrogenous base.
53. A method according to claim 1, wherein the polymerizable
surface active agent is formed by contacting the nitrogenous base
with the acid.
54. A method according to claim 1, wherein steps (a) and (b) occur
simultaneously.
55. A method according to claim 1, wherein steps (a) and (b) occur
simultaneously and wherein the method is self-initiating.
56. A method according to claim 1, wherein the mixture is
substantially free of non-polymerizable, surface active agents.
57. A method according to claim 1, wherein the mixture further
comprises a supplemental surface active agent (iii); wherein the
supplemental surface active agent is a sodium, potassium, calcium,
magnesium, or ammonium salt of a substantially saturated anionic
surfactant, or a nonionic, cationic, or amphoteric surfactant, or a
mixture thereof; and wherein the supplemental surface active agent
is provided in a concentration of about 0.01 to about 20.0 percent
by weight, based on the total weight of polymerizable surface
active agent and supplemental surface active agent.
58. A method according to claim 5, wherein R.sub.1 is a hydrocarbon
group containing from about 2-20 carbon atoms and at least one
double bond, and wherein R.sub.2 and R.sub.3 are hydrogen.
59. A method according to claim 1 or claim 57, wherein the mixture
further comprises an initiator.
60. A method according to claim 1 or claim 57, wherein the mixture
is an emulsion, suspension or dispersion.
61. An emulsion, suspension or dispersion of polymers, suitable for
use in coating, adhesive, sealant and/or elastomer applications,
prepared by the method of claim 1 or claim 57.
62. A method according to claim 1, wherein the polymerizable
surface active agent is provided as a solution.
63. Polymers suitable for use in coating, adhesive, sealant and/or
elastomer applications, prepared by the method of claim 1 or claim
57.
64. A pre-polymerization mixture comprising: a) at least one
ethylenically unsaturated monomer; and b) at least one
polymerizable surface active agent; wherein the polymerizable,
surface active agent is a salt or quaternary nitrogen compound
comprising: a) at least one acid, wherein the acid is a sulfonic
acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof; and b) at least one nitrogenous base, wherein the
nitrogenous base contains at least one nitrogen atom and at least
one ethylenically unsaturated moiety; and
65. A polymer comprising: a) at least one monomer unit; and b) at
least one surface active agent unit; wherein the monomer unit is
derived from an ethylenically unsaturated monomer; wherein the
surface active agent is derived from a polymerizable surface active
agent; and wherein the ethylenically unsaturated monomer and the
polymerizable surface active agent have co-polymerized to form the
polymer.
66. A method for forming polymers comprising: a) preparing a
mixture comprising: i) at least one ethylenically unsaturated
monomer; ii) at least one acid, wherein the acid is a sulfonic
acid, a carboxylic acid, or a phosphoric acid, or a mixture
thereof; and iii) at least one nitrogenous base, wherein the
nitrogenous base contains at least one nitrogen atom and at least
one ethylenically unsaturated moiety; b) polymerizing the
mixture.
67. A method according to claim 66, wherein the acid and the
nitrogenous base form a polymerizable, surface active agent;
wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound; wherein the polymerizable surface
active agent is capable of polymerization with itself,
copolymerization with the ethylenically unsaturated monomer and/or
co-polymerizing with a partially polymerized polymer particle; and
wherein the polymerizable, surface active agent is substantially
completely consumed by polymerization with itself,
co-polymerization with the monomer and/or co-polymerization with a
partially polymerized polymer particle.
68. A method according to claim 67, wherein a portion of the
nitrogenous base polymerizes with itself, co-polymerizes with the
monomer or co-polymerizes with a partially polymerized polymer.
69. A method for forming polymers comprising: a) preparing a
mixture comprising: i) at least one ethylenically unsaturated
monomer; ii) at least one homopolymeric surface active agent, the
homopolymeric surface active agent being a polymer formed by
polymerizing and/or co-polymerizing at least one polymerizable,
surface active agent; wherein the polymerizable, surface active
agent is a salt or quaternary nitrogen compound comprising: a) at
least one acid, wherein the acid is a sulfonic acid, a carboxylic
acid, or a phosphoric acid, or a mixture thereof; and b) at least
one nitrogenous base, wherein the nitrogenous base contains at
least one nitrogen atom and at least one ethylenically unsaturated
moiety; b) polymerizing the mixture.
70. A method according to claim 69, wherein the homopolymeric
surface active agent is capable of polymerization with itself,
co-polymerization with the monomer or co-polymerization with a
partially polymerized polymer particle.
71. A homopolymeric surface active agent formed by polymerizing at
least one polymerizable, surface active agent, wherein the
polymerizable, surface active agent is a salt comprising: a) at
least one acid, wherein the acid is a sulfonic acid, a carboxylic
acid, or a phosphoric acid, or a mixture thereof; and b) at least
one nitrogenous base, wherein the nitrogenous base contains at
least one nitrogen atom and at least one ethylenically unsaturated
moiety.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an improved emulsion
polymerization process utilizing ethylenically unsaturated amine
salts of sulfonic, phosphoric and carboxylic acids. More
specifically, the invention relates to emulsion polymerization
processes which utilize ethylenically unsaturated amine salts of
alkylbenzene sulfonic acids, alkyl olefin sulfonic acids, alkyl
alcohol sulfuric acid esters, or alkoxylated alkyl alcohol sulfuric
acid esters, fatty acids, and fatty phosphate acid esters, or
mixtures thereof, to form polymers, discrete solid polymeric
particles and latexes. Additionally, the present invention relates
to the use of the salts to impart improved adhesion,
hydrophobicity, resistance to film yellowing, scrubability,
anti-blooming, hydrolytic stability and shear stability
characteristics to polymer emulsions and latex formulations.
[0003] 2. Description of the Related Art
[0004] The emulsion polymerization of ethylenically unsaturated
monomers to form discrete solid polymeric particles for use in
coating, sealant, adhesive and/or elastomer (CASE) applications is
well known to the art. Conventional emulsion polymerization of
ethylenically unsaturated monomers employs one or more water
soluble surfactants to emulsify the monomers and the resulting
polymer products, i.e., latexes. The monomers used in emulsion
polymerization reactions are generally water-insoluble, but in some
cases may be water-soluble. During a typical emulsion
polymerization, a surfactant is used to suspend small portions of
monomer in a continuous or semi-continuous aqueous phase.
Typically, the monomer molecules are suspended as small spheres in
the aqueous phase, wherein the polymerization takes place within
the small spheres. The water soluble surface active agents, i.e.,
surfactants, typically utilized in emulsion polymerization
reactions are anionic, nonionic, and cationic surfactants or a
mixture thereof.
[0005] The polymeric particles formed by the emulsion
polymerization process are typically utilized in coating, sealant,
adhesive and/or elastomer (CASE) applications. In a traditional
emulsion polymerization reaction, the surfactant does not become
chemically bonded to the polymeric particles by carbon-carbon bond
formation but rather remains in the polymeric particle product
solution after the emulsion polymerization reaction is complete,
i.e., all of the monomer(s) is reacted. The unreacted surfactant
can have a detrimental effect on the polymer product solution, as
it can interfere with the performance of such polymerization
products in CASE applications; the suspension of polymeric
particles may become destabilized over time and undergo unwanted
coagulation. The unreacted surfactant may cause unwanted pealing of
a latex paint coating on a substrate, and decreased moisture and
scrubability resistance in other various CASE applications.
Additionally, residual surfactant can cause an undesirable
"blooming" that leads to surface irregularities in a resulting CASE
material that is applied to a substrate.
[0006] Several proposals have been made in the prior art to employ
a polymerizable surfactant as the surface active agent during an
emulsion polymerization reaction. U.S. Pat. No. 5,478,883
(incorporated herein by reference in its entirety) describes the
use of ethylenically unsaturated polymerizable water-soluble
nonionic surfactants formed by the reaction of a diallylamine
compound with ethylene oxide, propylene oxide or butylene oxide, in
emulsion polymerization reactions. Similarly, U.S. Pat. No.
5,162,475 (incorporated herein by reference) provides alpha-beta
ethylenically unsaturated poly(alkylenoxy) polymerizable surface
active compounds for use in emulsion polymerization. For additional
examples of polymerizable surfactants for use in emulsion
polymerization processes, see U.S. Pat. Nos. 4,377,185 and
4,049,608.
[0007] Non-polymerizable surfactant solutions to the traditional
problems encountered in performing an emulsion polymerization
process are numerous. U.S. Pat. No. 3,941,857 describes the use of
epoxy resins which react with the residual anionic, cationic or
nonionic surfactant. Polymerizable compounds such as allyl alcohol
(and esters thereof) have been found to be ineffective due to the
formation of undesirable high levels of coagulum in the final
emulsion polymerization product. Additionally, see U.S. Pat. No.
4,224,455.
[0008] Thus, there is a need for an emulsion polymerization process
for forming polymers and discrete polymeric particles that are well
suited for use in coatings (e.g., latex paints, electro-deposition,
container, paper and paperboard, can coatings, industrial coatings,
automotive coatings, textile coatings), adhesive (e.g., water- and
non-water borne adhesives, pressure sensitive adhesives, binders),
sealant (e.g. floor finishes, films, binders, non-woven binding
materials such as carpet backing, glass fibers) and elastomer
(CASE) applications.
SUMMARY OF THE INVENTION
[0009] The present invention utilizes a novel group of compounds in
the form of ethylenically unsaturated amine salts of sulfonic,
phosphoric and carboxylic acids, which display surface activity,
i.e. they are surfactants. It has been discovered that these
compounds function as reactive surfactants, i.e. surface active
agents in polymerization processes, particularly emulsion
polymerization processes. The surface active agents of the present
invention are capable of polymerizing with themselves (to form
homopolymeric surface active agents) and/or are capable of
co-polymerizing with other ethylenically unsaturated monomers of
the type which are commonly employed in polymerization processes.
The polymerizable surface active agents utilized in the present
invention are prepared from readily available, economical raw
materials, and generally, their preparation does not require any
special handling or equipment.
[0010] Accordingly, an improved method is provided for forming
polymers utilizing polymerizable surface active agents detailed
herein. Generally, the improved method comprises:
[0011] a) preparing a mixture comprising:
[0012] i) at least one ethylenically unsaturated monomer;
[0013] ii) at least one polymerizable, surface active agent;
[0014] wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound comprising:
[0015] a) at least one acid, wherein the acid is a sulfonic acid, a
carboxylic acid, or a phosphoric acid, or a mixture thereof;
and
[0016] b) at least one nitrogenous base, wherein the nitrogenous
base contains at least one nitrogen atom and at least one
ethylenically unsaturated moiety; and
[0017] b) polymerizing the mixture;
[0018] wherein the polymerizable, surface active agent is capable
of polymerization with itself, co-polymerization with the
ethylenically unsaturated monomer or co-polymerization with a
partially polymerized polymer particle. Somewhat preferably, the
nitrogen atom is linked covalently, directly or indirectly, to the
ethylenically unsaturated moiety of the nitrogenous base.
[0019] The polymers prepared utilizing the polymerizable surface
active agents of the present invention may be used as the primary
resin component or a minor resin component of a resin mixture which
is used to prepare latexes, coatings, adhesives, sealants,
elastomers, binders, inks, floor finishes and the like. A polymer
is defined herein as a product produced by polymerizing two or more
monomers, which may be the same or different. Additionally, the
polymer may have incorporated into it, surface active agent
monomers and/or homopolymeric surface active agents. The various
final compositions, application and polymer products described
herein may contain various optional ingredients such as fillers,
pigments, colorants, solvents, plasticizers, antioxidants, curing
agents, thickeners, non-polymerizable surface active agents
(surfactants), preservatives, wet strength additives, and the
like.
[0020] The present invention provides an improved polymerization
process for forming polymers, wherein the polymerizable surface
active agent used in the polymerization reaction does not interfere
with the quality of the CASE applications. Various classes of
polymers formed in the present invention, upon application to
textiles, fabrics, and other substrates, may reduce the shrinkage
of cotton fabrics, cotton/polyester blend fabrics, cotton/rayon
blend fabrics, rayon fabrics, and cellulosic or
cellulosic/synthetic blend fabrics.
[0021] The present invention provides an improved polymerization
process, for making suspension or dispersions of polymers which
exhibit enhanced mechanical stability and the ability to withstand
freezing and thawing while at the same time retaining good
dispersion or suspension.
[0022] The present invention provides an improved polymerization
process, wherein the resulting polymers exhibit/impart improved
adhesion of a CASE to a substrate, e.g. they are substantially
resistant to pealing and cracking.
[0023] The present invention provides an improved polymerization
process, wherein the resulting polymers exhibit/impart improved
anti-yellowing properties when employed in a CASE application.
[0024] The present invention provides an improved polymerization
process, wherein the resulting polymers exhibit/impart improved
scrubability properties of a CASE application.
[0025] The present invention provides an improved polymerization
process, wherein the resulting polymers exhibit/impart improved
solvent resistance properties when employed in a CASE
application.
[0026] The present invention provides an improved polymerization
process, wherein the resulting polymers exhibit/impart improved
film rewet properties when employed in a CASE application.
[0027] The present invention provides an improved polymerization
process, wherein coatings formed, using the polymers of the present
invention, remain uniform and stable upon the passage of time
and/or exposure to moisture at ambient or elevated temperature.
[0028] The present invention provides polymers suitable for use in
coating, adhesive, sealant and/or elastomer (CASE) applications.
The polymers may be in a variety of forms, such as, for example,
solids, flakes, powders, semi-solids, thick pastes,
flowable/pumpable pastes (i.e. G-phase pastes), liquids, gels,
"ringing" gels, dilute or concentrated solutions and the like. The
polymers may be spray dried, flaked, extruded, or the like.
[0029] The present invention additionally provides homopolymeric
surface active agents comprised of polymerized, polymerizable
surface active agents or blends of polymerizable surface active
agents. These homopolymeric surface active agents are useful in the
polymerization processes detailed herein. The present invention
further provides homopolymeric surface active agent/polymerizable
surface active agent blends comprised of partially polymerized,
polymerizable surface active agents and non-polymerized,
polymerizable surface active agents. These
homopolymeric/polymerizable surface active agent blends are also
useful in the polymerization processes detailed herein.
[0030] The improved polymerization process of the present invention
preferably does not require the use of a surfactant which contains
residual formaldehyde or other low molecular weight volatile
organic compounds. However, while not usually desirable, low
molecular weight volatile organic compounds and/or residual
formaldehyde may be present in the polymerization products of the
present invention. Further, the polymerization process of the
present invention provides latexes with improved shear stability,
improved pH stability, improved shelf storage stability and
improved ease of viscosity modification.
[0031] The polymerizable surface active agent may be added to the
mixture in a batch mode (i.e. all at once), a continuous mode (i.e.
by addition of an amount of the polymerizable surface active agent
throughout the polymerization) or in a semi-continuous mode (i.e.
addition of portions of the polymerizable surface active agent at
various times during the polymerization).
[0032] The polymerizable surface active agents utilized in the
present invention are generally formed by combining at least one
acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a
phosphoric acid, or a mixture thereof, with a nitrogenous base,
wherein the nitrogenous base contains at least one nitrogen atom
and at least one ethylenically unsaturated moiety. The
polymerizable surface active agents of the present invention
generally contain a quaternary nitrogen atom and are in the form of
salts or quaternary nitrogen compounds.
[0033] Various functional groups may be incorporated in the
polymerizable surfactants of the present invention, in either the
acid or the nitrogenous base, to form specialty polymerizable
surface active agents. These specialty polymerizable surface active
agents may posses various properties such as, for example, biocidal
activity, herbicidal activity, pesticidal activity, anti-static
activity and the like, either before or after polymerization with
known monomers or polymerization with themselves. Additionally, the
polymerizable surface active agents of the present invention may be
utilized in forming biodegradable polymers, photoreactive polymers,
sunscreen enhancing polymers, fabric softening polymers, polyol
polymers, ophthalmic polymers, lubricants and the like.
[0034] These and other objects and advantages, as well as the
scope, nature, and utilization of the claimed invention will become
apparent to those skilled in the art from the following detailed
description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS formulation prepared according to
Example #1.
DETAILED DESCRIPTION OF THE INVENTION
[0035] A method is provided for forming polymers utilizing
polymerizable surface active agents, wherein the method comprises:
(1) preparing a mixture comprising at least one ethylenically
unsaturated monomer and at least one polymerizable surface active
agent; and (2) polymerizing the mixture. Generally, any
ethylenically unsaturated monomer that is capable of undergoing
polymerization may be utilized in the present invention. The method
of the present invention is particularly well suited to emulsion
polymerization but may also be conducted as a solution
polymerization, suspension polymerization, micro emulsion
polymerization or inverse emulsion polymerization. The
polymerization may be conducted in any manner known to the art,
including but not limited to, free-radical initiated
polymerization, thermal initiated polymerization and redox
initiated polymerization using, for example, batch, continuous, or
controlled monomer feed processes, known conditions of stirring
time and temperature, and known kinds of additives such as
initiators, surfactants, electrolytes, pH adjusting agents,
buffering agents, protective colloids and the like. In general, the
polymerization process of the present invention will be carried out
from about 20.degree. C. to about 120.degree. C. (e.g., between
about 50.degree. C. and about 110.degree. C.). These polymerization
temperatures will vary with respect to the reactivity and
concentration of the polymerization initiator being used. Batch
polymerization times may vary depending on the method of
polymerization and the monomers being polymerized. Such times may
vary from about 2 to about 10 hours. In general, the mixture may be
a solution, emulsion, suspension or dispersion of the ethylenically
unsaturated monomer and the polymerizable surface active agent.
Further, the polymerizable surface active agent may be provided to
the mixture as an aqueous solution.
[0036] In accordance with the present invention, polymerization may
occur simultaneously as the mixture is being formed (i.e. as the
monomer and the polymerizable surface active agent come in contact,
a self-initiating polymerization occurs). Accordingly, the present
invention also encompasses a method for continuous polymerization,
utilizing at least one ethylenically unsaturated monomer and at
least one polymerizable surface active agent.
[0037] The polymerizable, surface active agents utilized in the
present invention are salts or quaternary nitrogen compounds
comprising:
[0038] a) at least one acid, wherein the acid is a sulfonic acid, a
carboxylic acid, or a phosphoric acid, or a mixture thereof;
and
[0039] b) at least one nitrogenous base, wherein the nitrogenous
base contains at least one nitrogen atom and at least one
ethylenically unsaturated moiety.
[0040] The polymerizable surface active agents are generally
capable of polymerization with themselves, co-polymerization with
the ethylenically unsaturated monomer or co-polymerization with a
partially polymerized polymer particle. In a somewhat preferred
embodiment, the polymerizable surface active agent is partially
(i.e. 150 percent by weight of the polymerizable surface active
agent) consumed by polymerization with itself, co-polymerization
with the monomer and/or co-polymerization with a partially
polymerized polymer particle. In a more preferred embodiment, the
polymerizable, surface active agent is substantially (i.e. 50-90
percent by weight of the polymerizable surface active agent)
consumed by polymerization with itself, co-polymerization with the
monomer and/or co-polymerization with a partially polymerized
polymer particle. In a most preferred embodiment, the
polymerizable, surface active agent is substantially completely
(i.e. greater than 90 percent by weight of the polymerizable
surface active agent) consumed by polymerization with itself,
co-polymerization with the monomer and/or co-polymerization with a
partially polymerized polymer particle.
[0041] The polymerizable surface active agent and the monomer are
generally combined in a ratio of about 0.01:1 to about 3:1 on a
weight basis. In a preferred embodiment, the polymerizable surface
active agent is present in the mixture in a concentration of about
1-100 weight percent, based on the total weight of the
ethylenically unsaturated monomer present in the mixture. In a more
preferred embodiment, the polymerizable surface active agent is
present in the mixture in a concentration of about 1-20 weight
percent, based on the total weight of the ethylenically unsaturated
monomer present in the mixture.
[0042] In general, the method of preparing polymers in accordance
with the present invention does not require the use of a
non-polymerizable surfactant, i.e. the mixture is substantially
free of non-polymerizable, surface active agents. However, in a
somewhat less preferred embodiment, the mixture further comprises a
supplemental, non-polymerizable surfactant (iii); wherein the
supplemental surfactant is a sodium, potassium, calcium, magnesium,
or ammonium salt of a substantially saturated anionic surfactant,
or a nonionic, cationic, or amphoteric surfactant, or a mixture
thereof; and wherein the supplemental surfactant is provided in a
concentration of about 0.01 to about 20.0 percent by weight, based
on the total weight of polymerizable surface active agent and
supplemental surfactant provided in the reaction zone.
[0043] The present invention provides pre-polymerization mixtures
comprising (1) at least one ethylenically unsaturated monomer; and
(2) at least one polymerizable surface active agent; wherein the
ethylenically unsaturated monomer and the polymerizable surface
active agent are defined as above or below. This pre-polymerization
mixture may be polymerized by a variety of initiation methods known
to the art.
[0044] The present invention provides polymers comprising: (1) at
least one monomer unit; and (2) at least one surface active agent
unit; wherein the monomer unit is derived from an ethylenically
unsaturated monomer; wherein the surface active agent is derived
from a polymerizable surface active agent; and wherein the
ethylenically unsaturated monomer and the polymerizable surface
active agent have co-polymerized to form the polymer.
[0045] In another embodiment, the present invention provides a
method for forming polymers, wherein the method comprises (1)
preparing a mixture comprising at least one ethylenically
unsaturated monomer, at least one acid, wherein the acid is a
sulfonic acid, a carboxylic acid, or a phosphoric acid, or a
mixture thereof, and at least one nitrogenous base, wherein the
nitrogenous base contains at least one nitrogen atom and at least
one ethylenically unsaturated moiety; and (2) polymerizing the
mixture. In accordance with this embodiment, the acid and the
nitrogenous base may form a polymerizable, surface active agent in
situ; wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound; wherein the polymerizable surface
active agent is capable of polymerization with itself,
co-polymerization with the ethylenically unsaturated monomer and/or
co-polymerizing with a partially polymerized polymer particle; and
wherein the polymerizable, surface active agent is substantially
completely consumed by polymerization with itself,
co-polymerization with the monomer and/or co-polymerization with a
partially polymerized polymer particle. In one alternative, the
nitrogenous base may partially or completely co-polymerize with the
ethylenically unsaturated monomer, followed by formation of a
surface active agent (i.e. complexation/salt formation with the
acid). Without being bound by any particular theory, it is believed
that the nitrogenous base is incorporated into the polymer
back-bone and the acid forms an ion pair, i.e. a salt, with the
nitrogen atom of the nitrogenous base, thereby adhering to the
polymer and forming a positively charged nitrogen atom. In another
alternative within the purview of this embodiment, a portion of the
nitrogenous base may polymerize with itself, co-polymerizes with
the ethylenically unsaturated monomer or co-polymerize with a
partially polymerized polymer, followed by complexation/salt
formation with the acid. In another alternative, the nitrogenous
base may partially or completely co-polymerize with a homopolymeric
surfactant, followed by complexation/salt formation with the
acid.
[0046] The present invention provides polymers comprising: (1) at
least one monomer unit; (2) at least one acid, wherein the acid is
a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a
mixture thereof; and at least one nitrogenous base, wherein the
nitrogenous base contains at least one nitrogen atom and at least
one ethylenically unsaturated moiety; wherein the monomer unit is
derived from an ethylenically unsaturated monomer; wherein the
nitrogenous base is homopolymerized, co-polymerized with the
monomer, and/or polymerized with a partially polymerized polymer,
wherein the acid complexes to the nitrogen atom(s), to form a salt-
or a quaternary nitrogen-containing polymer.
[0047] In another embodiment, the present invention provides a
method for forming polymers, wherein the method comprises: (1)
preparing a mixture comprising at least one ethylenically
unsaturated monomer and at least one homopolymeric surface active
agent, the homopolymeric surface active agent being a polymer
formed by polymerizing at least one polymerizable, surface active
agent; wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound comprising at least one acid, wherein
the acid is a sulfonic acid, a carboxylic acid, or a phosphoric
acid, or a mixture thereof, and at least one nitrogenous base,
wherein the nitrogenous base contains at least one nitrogen atom
and at least one ethylenically unsaturated moiety; and (2)
polymerizing the mixture.
[0048] The present invention provides homopolymeric surface active
agents. These homopolymeric surface active agents are formed by
polymerizing at least one polymerizable, surface active agent,
wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound comprising at least one acid, wherein
the acid is a sulfonic acid, a carboxylic acid, or a phosphoric
acid, or a mixture thereof; and at least one nitrogenous base,
wherein the nitrogenous base contains at least one nitrogen atom
and at least one ethylenically unsaturated moiety. Optionally, the
homopolymeric surface active agents may be formed by partially or
completely polymerizing the nitrogenous base, followed by
complexation of the resulting polymer with the acid, wherein the
acid complexes to the nitrogen atom(s), to form a salt- or a
quaternary nitrogen-containing homopolymeric surface active
agent.
[0049] The homopolymeric surface active agents of the invention are
generally capable of polymerization with themselves,
co-polymerization with the monomer or co-polymerization with a
partially polymerized polymer.
[0050] In another embodiment, the present invention provides a
method for forming polymers, wherein the method comprises: (1)
partially polymerizing at least one ethylenically unsaturated
monomer to form a partially polymerized polymer/monomer mixture;
(2) adding to the partially polymerized polymer/monomer mixture at
least one polymerizable surface active agent and/or at least one
homopolymeric surface active agent, to form a partially polymerized
polymer/monomer/surface active agent mixture; and (3) polymerizing
the partially polymerized polymer/monomer/surface active agent
mixture; wherein the homopolymeric surface active agent being a
polymer formed by polymerizing at least one polymerizable, surface
active agent; wherein the polymerizable, surface active agent is a
salt or quaternary nitrogen compound comprising at least one acid,
wherein the acid is a sulfonic acid, a carboxylic acid, or a
phosphoric acid, or a mixture thereof, and at least one nitrogenous
base, wherein the nitrogenous base contains at least one nitrogen
atom and at least one ethylenically unsaturated moiety.
[0051] In another embodiment, the present invention provides a
method for forming polymers, wherein the method comprises: (1)
preparing a mixture comprising at least one ethylenically
unsaturated monomer and at least one non-polymerizable,
supplemental surface active agent; (2) partially polymerizing the
mixture to form a partially polymerized
polymer/monomer/supplemental surface active agent mixture; (3)
adding to the partially polymerized polymer/monomer/supplemental
surface active mixture at least one polymerizable surface active
agent and/or at least one homopolymeric surface active agent, to
form a partially polymerized polymer/monomer/supplemental surface
active agent/polymerizable surface active agent mixture; and (4)
polymerizing the partially polymerized polymer/monomer/surface
active agent/polymerizable surface active agent mixture; wherein
the homopolymeric surface active agent being a polymer formed by
polymerizing at least one polymerizable, surface active agent;
wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound comprising at least one acid, wherein
the acid is a sulfonic acid, a carboxylic acid, or a phosphoric
acid, or a mixture thereof, and at least one nitrogenous base,
wherein the nitrogenous base contains at least one nitrogen atom
and at least one ethylenically unsaturated moiety; and wherein the
supplemental surface active agent is generally non-polymerizable
and is defined herein.
[0052] In another embodiment, the present invention provides a
method for forming polymers, and suspension or dispersions of
polymers, wherein the method comprises: (1) preparing a mixture
comprising at least one ethylenically unsaturated monomer and at
least one non-polymerizable, supplemental surface active agent; (2)
polymerizing the mixture to form a polymer mixture; and (3) adding
at least one polymerizable surface active agent and/or at least one
homopolymeric surface active agent to the polymer mixture; wherein
the homopolymeric surface active agent being a polymer formed by
polymerizing at least one polymerizable, surface active agent;
wherein the polymerizable, surface active agent is a salt or
quaternary nitrogen compound comprising at least one acid, wherein
the acid is a sulfonic acid, a carboxylic acid, or a phosphoric
acid, or a mixture thereof, and at least one nitrogenous base,
wherein the nitrogenous base contains at least one nitrogen atom
and at least one ethylenically unsaturated moiety.
[0053] The present invention encompasses polymers prepared by any
of the methods or processes described herein. Generally, the
methods of the present invention encompass, emulsions, suspensions
or dispersion of polymer obtained therefrom.
Ethylenically Unsaturated Monomers
[0054] The ethylenically unsaturated monomer or monomers that may
be polymerized or co-polymerized according to the present invention
are known to the art and are described below in a representative
manner. Examples of suitable ethylenically unsaturated monomers
are, for example, mono- and polyunsaturated hydrocarbon monomers,
vinyl esters (e.g., vinyl esters of C.sub.1 to C.sub.6 saturated
monocarboxylic acids), vinyl ethers, monoethylenically unsaturated
mono- and polycarboxylic acids and there alkyl esters (e.g.,
acrylic acid esters and methacrylic acid esters, particularly the
C.sub.1 to C.sub.12 alkyl, and more particularly the C.sub.1 to
C.sub.4 alkyl esters), the nitriles, vinyl and vinylidene halides,
and amides of unsaturated carboxylic acids and amino monomers.
[0055] Examples of suitable hydrocarbon monomers for use in the
present invention include styrene compounds (e.g., styrene,
carboxylated styrene, and alpha-methyl styrene), ethylene,
propylene, butylene, and conjugated dienes (e.g., butadiene,
isoprene and co-polymers of butadiene and isoprene). Examples of
vinyl and vinylidene halides include vinyl chloride, vinylidene
chloride, vinyl fluoride and vinylidene fluoride.
[0056] Examples of acrylic esters and methacrylic esters suitable
for use in the present invention include C.sub.1-C.sub.12 (e.g.,
C.sub.1-C.sub.4) alkyl acrylates and methacrylates. Typical alkyl
esters and methacrylic esters include methyl acrylate, methyl
methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl
acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl
methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl
acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl
acrylate, t-butyl methacrylate, 3,3-dimethylbutyl acrylate,
3,3-dimethyl butyl methacrylate, and lauryl acrylate.
[0057] Suitable vinyl esters for use in the present invention
include aliphatic vinyl esters, such as vinyl formate, vinyl
acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl
valerate, and vinyl caproate, and allyl esters of saturated
monocarboxylic acids, such as allyl acetate, allyl propionate and
ally lactate.
[0058] Vinyl ethers suitable for use in the present invention
include methylvinyl ether, ethylvinyl ether and n-butylvinyl ether.
Typically vinyl ketones include methylvinyl ketone, ethylvinyl
ketone and isobutylvinyl ketone. Suitable dialkyl esters of
monoethylenically unsaturated dicarboxylic acids include dimethyl
maleate, diethyl maleate, dibutyl maleate, dioctyl maleate,
diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditridecyl
maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate,
dibutyl fumarate, dioctyl fumarate, diisooctyl fumarate, didecyl
fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate,
and dioctyl itaconate.
[0059] Monoethylenically unsaturated monocarboxylic acids suitable
for use in the present invention include acrylic acid, methacrylic
acid, ethacrylic acid, and crotonic acid. Suitable
monoethylenically unsaturated dicarboxylic acids include maleic
acid, fumaric acid, itaconic acid and citraconic acid. Suitable
monoethylenically unsaturated tricarboxylic acids include aconitic
acid and the halogen-substituted derivatives (e.g.,
alphachloracylic acid), and the anhydrides of these acids (e.g.,
maleic anhydride and citraconic anhydride).
[0060] Nitriles of the above ethylenically unsaturated mono-, di-
and tricarboxylic acids which are suitable monomers include
acrylonitrile, alpha-chloroacrylonitrile and methacrylonitrile.
Suitable amides of these carboxylic acids include unsubtituted
amides such as acrylamide, methacrylamide and other
alpha-substituted acrylamides and N-substituted amides obtained by
the reaction of the amides of the aforementioned mono- and
polycarboxylic acids with and aldehyde (e.g., formaldehyde).
Typical N-substituted amides include N-methylolacrylamide,
N-methylolmethacrylamide alkylated N-methylolacrylamides and
N-methylolmethacrylarnides (e.g., N-methyoxymethylacrylamide and
N-methoxymethylmethacrylamide).
[0061] Amino monomers useful in the present invention include
substituted and unsubstituted aminoalkyl acrylates, hydrochloride
salts of amino monomers and methacrylates, such as
beta-aminoethylacrylate, beta-amino-ethylmethacrylate,
dimethylaminomethylacrylate, beta-methylaminoethylacrylate, and
dimethylaminomethylmethacrylate.
[0062] Hydroxy-containing monomers useful in the present invention
include beta-hydroxyethylacrylate, beta-hydroxypropylacrylate,
gamma-hydroxypropylacrylate and beta-hydroxyethylmethacrylate.
[0063] Monomers useful in the present invention may be
homopolymerized or co-polymerized, i.e., one or more different
monomers capable of polymerization may be used.
Polymerizable Surface Active Agents
[0064] The polymerizable surface active agents utilized in the
present invention are salts or quaternary nitrogen compounds
comprising at least one acid, wherein the acid is a sulfonic acid,
a carboxylic acid, or a phosphoric acid, or a mixture thereof, and
at least one nitrogenous base, wherein the nitrogenous base
contains at least one nitrogen atom and at least on ethylenically
unsaturated moiety. The polymerizable surface active agents is
usually present in the mixture in a concentration from about
0.01-100.0 percent by weight based on the total weight of the
ethylenically unsaturated monomer. In general, although not
required, the polymerizable surface active agents have a
homophilic/lipophilic balance (HLB) of less than about 45. In a
somewhat more preferred embodiment, the polymerizable surface
active agents have an HLB of about 5-40. The polymerizable surface
active agents are generally capable of polymerization with
themselves, co-polymerization with the ethylenically unsaturated
monomer, or co-polymerization with a partially polymerized
polymer.
[0065] More specifically, while the nitrogenous base may be capable
of some degree of surface activity, in the present invention it is
the acid portion of the polymerizable surfactant that is
responsible for the surfactant character and the HLB of the
compound. In preferred embodiments, the nitrogenous base
contributes little or no surfactant character to these materials.
In other words, the acids are generally capable of acting as
surfactants when they are present as anions of the acid and the
associated counterion is any positively charged species. The most
common positively charged species are sodium, potassium, ammonium,
calcium and magnesium ions. In fact, the acid portion of the
polymerizable surfactant may be supplied as a sodium, potassium, or
other salt of the carboxylic, phosphoric or sulfonic acid and then
combined with the nitrogenous base to form the inventive
surfactant.
[0066] The polymerizable surface active agents of the present
invention are prepared from readily available, economical raw
materials, and generally, their preparation does not require any
special handling or equipment. The polymerizable surface active
agents may be prepared in a batch mode or a continuous mode; they
may be prepared by contacting nitrogenous base with the acid or
contacting the acid with the nitrogenous base. By contacting it is
meant that the acid(s) is added to the nitrogenous base and the
components are mixed, or the ethylenically unsaturated amine(s) is
added to the acid(s) and the components are mixed. The acid may be
present as an anion and the base may be present as a cation (i.e. a
quaternary nitrogen) in the mixture. The acid and nitrogenous base
are in the form of salts or quaternary nitrogen compounds. As known
by one skilled in the art, upon mixing the acid and nitrogenous
base together, the nitrogenous base becomes a conjugate acid and
the acid becomes a conjugate base.
[0067] The surface active agents and blends of surface active
agents may be prepared in a variety of forms such as, for example,
liquids, solutions, solids, powders, flakes, semi-solids, gels,
"ringing" gels, G-phase liquids, hexagonal phase solids, or thick
pastes. The surface active agents may be spray dried, flaked,
extruded, and the like. Although not critical to the present
invention, the polymerizable surface active agents may be prepared
"neat" or in a conventional solvent such as water, low molecular
weight alcohol or hydrocarbon, or a mixture thereof, to produce a
solution of the polymerizable surface active agent. The present
invention encompasses polymerizable surface active agents as salts
in dry form and as aqueous solutions. The polymerizable surface
active agents may be isolated by drying a solution of the surface
active agents; a solution of polymerizable surface active agents
may be prepared by dissolving a solid form of the polymerizable
surface active agent (i.e. a salt) in water, low molecular weight
alcohol or hydrocarbon, or a mixture thereof.
[0068] Polymerizable surface active agents of the present invention
may be prepared and mixed together to produce a surface active
mixture comprising "neat" surface active agents or an aqueous
surfactant blend. Additionally, neat or aqueous blends of the
polymerizable surface active agents may be prepared by contacting a
blend of two or more nitrogenous bases with one acid, or by
contacting a blend of two or more nitrogenous bases with a blend of
2 or more acids. Conversely, blends of the polymerizable surface
active agents may be prepared by contacting a blend of two or more
acids with one nitrogenous base, or by contacting a blend of two or
more acids with a blend of two or more nitrogenous bases.
[0069] The polymerizable surface active agents utilized in the
present invention may be homopolymerized (i.e. polymerized with
themselves), or partially homopolymerized, prior to use in the
polymerization, to form a homopolymeric surface active agent or a
blend of homopolymeric surface active agent(s) and polymerizable
surface active agents.
[0070] Further, the polymerizable surface active agents utilized in
the present invention are also useful, for example, in detergents
(e.g., laundry detergents, dish detergents, automatic dishwasher
detergents, etc.), shampoos, 2-in-1 shampoos, 3-in-1 shampoos,
cleansers, soaps, liquid hand soaps, body washes, agricultural
herbicide and pesticide formulations and the like.
[0071] The acids useful in the present invention are generally
sulfonic acids, polysulfonic acids, sulfonic acids of oils,
paraffin sulfonic acids, lignin sulfonic acids, petroleum sulfonic
acids, tall oil acids, olefin sulfonic acids, hydroxyolefin
sulfonic acids, polyolefin sulfonic acids, polyhydroxy polyolefin
sulfonic acids, carboxylic acids, perfluorinated carboxylic acids,
carboxylic acid sulfonates, alkoxylated carboxylic acid sulfonic
acids, polycarboxylic acids, polycarboxylic acid polysulfonic
acids, alkoxylated polycarboxylic acid polysulfonic acids,
phosphoric acids, alkoxylated phosphoric acids, polyphosphoric
acids, and alkoxylated polyphosphoric acids, fluorinated phosphoric
acids, phosphoric acid esters of oils, phosphinic acids,
alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids,
vinyl phosphinic acids, phosphonic acids, polyphosphonic acids,
phosphonic acid alkyl esters, .alpha.-phosphono fatty acids,
oragnoamine polymethylphosphonic acids, organoamino dialkylene
phosphonic acids, alkanolamine phosphonic acids, trialkyledine
phosphonic acids, acylamidomethane phosphonic acids,
alkyliminodimethylene diphosphonic acids, polymethylene-bis(nitrilo
dimethylene)tetraphosphonic acids, alkyl bis(phosphonoalkylidene)
amine oxide acids, esters of substituted aminomethylphosphonic
acids, phosphonamidic acids, acylated amino acids (e.g., amino
acids reacted with alkyl acyl chlorides, alkyl esters or carboxylic
acids to produce N-acylamino acids), N-alkyl acylamino acids, and
acylated protein hydrolysates, and mixtures thereof.
[0072] Other acids which are useful in the present invention are
selected from the group comprising linear or branched alkylbenzene
sulfonic acids, alkyl sulfuric acid esters, alkoxylated alkyl
sulfuric acid esters, .alpha.-sulfonated alkyl ester acids,
.alpha.-sulfonated ester diacids, alkoxylated .alpha.-sulfonated
alkyl ester acids, .alpha.-sulfonated dialkyl diester acids,
di-.alpha.-sulfonated dialkyl diester acids, .alpha.-sulfonated
alkyl acetate acids, primary and secondary alkyl sulfonic acids,
perfluorinated alkyl sulfonic acids, sulfosuccinic mono- and
diester acids, polysulfosuccinic polyester acids, sulfoitaconic
diester acids, sulfosuccinamic acids, sulfosuccinic amide acids,
sulfosuccinic imide acids, phthalic acids, sulfophthalic acids,
sulfoisophthalic acids, phthalamic acids, sulfophthalamic acids,
alkyl ketone sulfonic acids, hydroxyalkane-1-sulfonic acids,
lactone sulfonic acids, sulfonic acid amides, sulfonic acid
diamides, alkyl phenol sulfric acid esters, alkoxylated alkyl
phenol sulfuric acid esters, alkylated cycloalkyl sulfuric acid
esters, alkoxylated alkylated cycloalkyl sulfuric acid esters,
dendritic polysulfonic acids, dendritic polycarboxylic acids,
dendritic polyphosphoric acids, sarcosinic acids, isethionic acids,
and tauric acids, and mixtures thereof.
[0073] Additionally in accordance with the present invention,
suitable acids of the present invention include fluorinated
carboxylic acids, fluorinated sulfonic acids, fluorinated sulfate
acids, fluorinated phosphonic and phosphinic acids, and mixtures
thereof.
[0074] Due to their inherent hydrolytic instability, the sulfuric
acid esters are preferably immediately converted to ethylenically
unsaturated amine salts. For example, linear dodecyl alcohol is
sulfated with SO.sub.3 to produce an intermediate, hydrolytically
unstable, dodecyl alcohol sulfate acid as shown in Scheme I below.
The intermediate acid is neutralized with an ethylenically
unsaturated nitrogenous base, such as allyl amine, to produce a
dodecyl sulfate ethylenically unsaturated amine salt.
Scheme I: Formation of Dodecyl Sulfate Ethylenically Unsaturated
Amine Salt
CH.sub.3(CH.sub.2).sub.11OH+SO.sub.3.fwdarw.[CH.sub.3(CH.sub.2).sub.11OSO.-
sub.3H]+H.sub.2NCH.sub.2CH.dbd.CH.sub.2.fwdarw.[CH.sub.3(CH.sub.2).sub.11O-
SO.sub.3].sup.-[NH.sub.3CH.sub.2CH.dbd.CH.sub.2].sup.+
[0075] Additionally, for example, methyl laurate is sulfonated with
SO.sub.3 to produce an intermediate .alpha.-sulfonated lauryl
methyl ester acid, as shown in Scheme II below. This acid is
neutralized with an ethylenically unsaturated nitrogenous base,
such as allyl amine, to produce an .alpha.-sulfonated lauryl methyl
ester ethylenically unsaturated amine salt. Additionally, an
.alpha.-sulfonated lauryl methyl ester ethylenically unsaturated
amine di-salt may be produced as shown below in Scheme III. The
.alpha.-sulfonated lauryl methyl ester ethylenically unsaturated
amine salt and the .alpha.-sulfonated lauryl fatty acid
ethylenically unsaturated amine di-salt may be formed as a mixture
depending on the sulfonation conditions employed. The ratio of
unsaturated amine salt to unsaturated amine di-salt is readily
controlled by sulfonation conditions, well known to those skilled
in the art. 1 2
[0076] Ethylenically unsaturated amine salts of sulfosucinnate
ester acids are typically produced by sulfitation of a succinic
acid alkyl diester with sodium bisulfite, followed by, for example,
ionic exchange with an ethylenically unsaturated nitrogenous base,
such as allyl amine, as shown in Scheme IV below. 3
[0077] The sarcosinic acid ethylenically unsaturated amine salts
are prepared by the amidation of a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride with sarcosine, followed by addition
of an ethylenically unsaturated nitrogenous base, such as allyl
amine, as shown in Scheme V below. Optionally, and somewhat less
preferably, the ethylenically unsaturated nitrogenous base is
combined with sarcosine to produce the corresponding sarcosine
salt, which is then be used to amidate the fatty acid, fatty acid
alkyl ester or fatty acid chloride. 4
[0078] The isethionic acid ethylenically unsaturated amine salts
may be prepared by the esterification of a fatty acid, a fatty acid
alkyl ester or a fatty acid chloride with isethionic acid, followed
by addition of an ethylenically unsaturated nitrogenous base, such
as allyl amine, as shown in Scheme VI below. Additionally,
isethionic acid ethylenically unsaturated amine salts may be
prepared by esterifying a fatty acid, a fatty acid alkyl ester or a
fatty acid chloride with the sodium salt of isethionic acid,
followed by ion exchange with the ethylenically unsaturated
nitrogenous base, such as allyl amine. Optionally, isethionic acid,
or its sodium salt, may be combined with the ethylenically
unsaturated nitrogenous base, such as allyl amine, to produce the
isethionic acid allyl amine salt, which may then be esterified with
a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
5
[0079] The preferred acids of the present invention are branched or
linear alkylbenzene sulfonic acids, alkyl sulfuric acid esters,
alkoxylated alkyl sulfuric acid esters, .alpha.-sulfonated alkyl
ester acids, fatty carboxylic acids and phosphoric acid esters, and
mixtures thereof. The most preferred acids of the present invention
are branched or linear alkylbenzene sulfonic acids, alkyl sulfuric
acid esters, and alkoxylated alkyl sulfuric acid esters, and
mixtures thereof.
[0080] Other useful surfactants in accordance with the present
invention include sulfonic acid salts of ethylenically unsaturated
amines, derived from sultone precursors, such as cyclic alkyl
sultones. Examples of these sultone-derived sulfonic acid salts
(e.g., allyl amine salts) include 2-acetamidoalkyl-1-sulfonates and
amino carboxy acid alkyl sulfonates, as shown in Scheme VII and
Scheme VIII below. 6 7
[0081] In general, nitrogenous bases, which are useful in the
present invention are any nitrogenous base which contains an
ethylenically unsaturated moiety, including various vinyl amines.
The nitrogenous base useful in accordance with the present
invention is a compound of the formula 8
[0082] wherein R.sub.1, R.sub.2 and R.sub.3 are independently
hydrogen or organic groups containing an ethenylene group, provided
that at least one of R.sub.1-R.sub.3 is a straight or branched
chain alkyl group containing 1-8 carbon atoms and an ethenylene
functionality.
[0083] Additionally, other examples of nitrogenous bases that are
useful in the present invention are ethylenically unsaturated
amines selected from the group comprising vinyl amine, N-methyl
N-allyl amine, C.sub.1-C.sub.24 alkyl allyl amine, C.sub.1-C.sub.24
alkyl ethoxylated and/or propoxylated allyl amine, C.sub.1-C.sub.24
dialkyl allyl amine, ethoxylated and/or propoxylated allyl amine
diallyl amine, C.sub.1-C.sub.24 alkyl diallyl amine, ethoxylated
and/or propoxylated diallyl amine, triallyl amine,
1,2-diaminoethene, aminocrotonitrile, diaminomaleonitrile,
N-allylcyclopentylamine, N-allylaniline, allylcyclohexylamine,
[1-(2-allylphenoxy)-3-(isopropylamino)-2-propanol],
3-amino-2-butenethioamide,
bis[4-(dimethylamino)-benzylidene]acetone, 1,4-butanediol
bis(3-aminocrotonate), 3-amino-1-propanol vinyl ether,
2-(diethylamino)ethanol vinyl ether,
4-(diethylamino)cinnamaldehyde, 4-(diethylamino)cinnamonitrile,
2-(diethylamino)ethyl methacrylate, diethyl
(6-methyl-2-pyridylaminomethylene)maleate,
3-(dimethylamino)acrolein, 2-(dimethylamino)ethyl methacrylate,
4-dimethylaminocinnamaldehyde, 2-(dimethylamino)ethyl acrylate,
3-(dimethylamino)-2-methyl-2-propenal, 9-vinylcarbazole,
N-vinylcaprolactam, 1-vinylimidazole, 2-vinylpyridine,
4-vinylpyridine, allylcyclohexylamine, N-allylcyclopentylamine,
allyl(diisopropylamino)dim- ethylsilane, 1-allylimidazole,
1-vinyl-2-pyrrolidinone, N-[3-(dimethylamino)propyl]methacrylamide,
4-[4-(dimethylamino)styryl]pyr- idine,
2-[4-(dimethylamino)styryl]pyridine,
2-[4-(1,2-diphenyl-1-butenyl)p- henoxy]-N,N-dimethylethylamine,
2-[4-dimethylamino)styryl]-benzothiozole,
5-[4-(dimethylamino)phenyl]-2,4-pentandienal,
(dimethylamino-methylene)ma- lononitrile,
4-dimethylaminocinnamonitrile, 4-(dimethylamino)chalcone,
[6-(3,3-dimethylallylamino-purine riboside,
3,7-dimethyl-2,6-octadien-1-y- lamine, 2-isopropenylaniline,
isopropyl 3-aminocrotonate,
S-{2-[3-(hexyloxy)benzoyl]-vinyl}glutathione, methyl
3-aminocrotonate, N-methylallylamine,
N-methyl-1-(methylthio)-2-nitroetheneamine, oleylamine,
tetrakis(dimethylamino)ethylene, 5-[(6,7,8-trimethoxy-4-quina-
zolinyl)amino]-1-pentanol nitrate ester, tris(2-methylallyl)amine,
N,N,N',N'-tetramethyl-2-butene-1,4-diamine,
S-{2-[3-(octyloxy)benzoyl]vin- yl}-glutathione,
4,4'-vinylidene-(N,N-dimethylaniline),
2',5'-dimethoxy-4-stilbenamine, 3-(dimethylanino)propyl acrylate,
3-dimethylaminoacrylonitrile, 4-(dimethylamino)-cinnamic acid,
2-amino-1-propene-1,1,3-tricarbonitrile, 2-amino-4-pentenoic acid,
N,N'-diethyl-2-butene-1,4-diamine,
10,11-dihyro-N,N-dimethyl-5-methylene--
5H-dibenzo[a,d]-cyclohepene-10-ethanamine maleate,
4-(dicyanomethylene)-2--
methyl-6-(4-dimethyl-aminostyryl)-4H-pyran,
N-ethyl-2-methylallylamine, ethyl 3-aminocrotonate,
ethyl-.alpha.-cyano-3-indoleacrylate,
ethyl-3-amino-4,4-dicyano-3-butenoate,
1,3-divinyl-1,1,3,3-tetramethyldis- ilazane,
N-(4,5-dihydro-5-oxo-1-phenyl-1H-pyrazol-3-yl)-9-octadecen-amide,
and N-oleoyl-tryptophan ethyl ester, and mixtures thereof
[0084] More preferred nitrogenous bases of the present invention
are allyl amine, diallyl amine, triallyl amine, methylallyl amine,
allyldimethyl amine, methyl 3-amino crotonate, 3-amino
crotononitrile, 3-amino-1-propanol vinyl ether, N-methyl N-allyl
amine, 2-(dimethylamino)ethyl acrylate, or 1,4-diamino-2-butene,
and mixtures thereof. The most preferred nitrogenous bases of the
present invention are allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-methyl N-allyl amine, and 2-(dimethylamino)ethyl
acrylate, and mixtures thereof.
[0085] Accordingly, the present invention utilizes surface active
agents of the formula:
(R.sub.1).sub.n--Ar(SO.sub.3.sup.-M.sup.+).sub.m
[0086] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein Ar is a phenyl,
polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, or a
mixture thereof; wherein M.sup.+ is a conjugate acid of the
nitrogenous base; wherein n=1-5 and m=1-8; and wherein the total
number of carbon atoms represented by (R.sub.1).sub.n is at least
5. In a preferred embodiment R.sub.1 is a saturated or unsaturated
hydrocarbon group having from about 6-24 carbon atoms, Ar is a
phenyl, M.sup.+ is a conjugate acid of the nitrogenous base, the
nitrogenous base selected from the group consisting of allyl amine,
diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl
amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof and
n=1 and m=1. In another preferred embodiment, the surface active
agent is of the formula: 9
[0087] wherein n1=4-18; and wherein R' is hydrogen or saturated or
unsaturated hydrocarbon group having from about 1-8 carbon
atoms.
[0088] The present invention further utilizes surface active agents
of the formula
(R.sub.1).sub.n1--{Ar(SO.sub.3.sup.-M.sup.+).sub.m1}--O--{Ar(SO.sub.3.sup.-
-M.sup.+)}-(R.sub.2).sub.n2
[0089] wherein R.sub.1 and R.sub.2 are independently hydrogen, or
saturated or unsaturated hydrocarbon groups having from about 1-24
carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl,
polynapthyl, styryl, or polystyryl group, or a mixture thereof;
wherein M.sup.+ is a conjugate acid of the nitrogenous base;
wherein n1 and n2 are independently 0-5, provided that n1 and n2
are not both equal to zero; and wherein m1 and m2 are independently
0-8, provided that m1 and m2 are not both equal to zero. In a
preferred embodiment, R.sub.1 is hydrogen and R.sub.2 is a
saturated or unsaturated hydrocarbon group having from about 6-24
carbon atoms, Ar is phenyl, M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof, n1=4, n2=1, and m1 and m2 both equal one. In
another preferred embodiment, R.sub.1 and R.sub.2 are independently
saturated or unsaturated hydrocarbon groups having from about 6-24
carbon atoms, Ar is phenyl, M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof, n1 and n2 both equal one, and m1 and m2 both
equal one. In another preferred embodiment, the surface active
agent is of the formula: 10
[0090] wherein n and n' are independently 4-18; and wherein R' and
R" are independently hydrogen, methyl, ethyl or propyl.
[0091] The present invention further utilizes surface active agents
of the formula:
R.sub.1--CH(SO.sub.3.sup.-M.sup.+) CO.sub.2R.sub.2
[0092] wherein R.sub.1 and R.sub.2 are independently saturated or
unsaturated hydrocarbon groups having from about 1-24 carbon atoms;
and wherein M.sup.+ is a conjugate acid of the nitrogenous base. In
a preferred embodiment, R.sub.1 is a saturated or unsaturated
hydrocarbon group having from about 6-24 carbon atoms, R.sub.2 is
methyl, ethyl, or propyl, or a mixture thereof, and M.sup.+ is a
conjugate acid of the nitrogenous base, the nitrogenous base
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof. In another
preferred embodiment, the surface active agent is of the formula:
11
[0093] wherein n=3-18.
[0094] The present invention further utilizes surface active agents
of the formula:
R.sub.1--CH(SO.sub.3.sup.31 M.sup.+)CO.sub.2M.sup.+
[0095] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 3-24 carbon atoms; and wherein M.sup.+ is a
conjugate acid of the nitrogenous base. In a preferred embodiment,
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 6-24 carbon atoms, M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof. In another preferred embodiment, the surface
active agent is of the formula: 12
[0096] wherein n=3-18.
[0097] The present invention further utilizes surface active agents
of the formula:
R.sub.1--CH(SO.sub.3.sup.-M.sup.+)C(O)O(CH.sub.2CH(R')O).sub.nR.sub.2
[0098] wherein R.sub.1 and R.sub.2 are independently saturated or
unsaturated hydrocarbon groups having from about 1-24 carbon atoms;
wherein R' is methyl or hydrogen; wherein n=1-100; and wherein
M.sup.+ is a conjugate acid of the nitrogenous base. In a preferred
embodiment, R.sub.1 is a saturated or unsaturated hydrocarbon group
having from about 4-24 carbon atoms, R' is methyl or hydrogen,
R.sub.2 is methyl, ethyl, or propyl, and mixtures thereof, M.sup.+
is a conjugate acid of the nitrogenous base, the nitrogenous base
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof, and n=1-100.
In another preferred embodiment, the surface active agent is of the
formula: 13
[0099] wherein n1=2-18; and wherein n2=1-20.
[0100] The present invention further utilizes surface active agents
of the formula:
R.sub.1--(SO.sub.3.sup.-M.sup.+)
[0101] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 6-24 carbon atoms and wherein M.sup.++is a
conjugate acid of the nitrogenous base. In a preferred embodiment,
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 6-24 carbon atoms, and M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof. In another preferred embodiment, the surface
active agent is of the formula: 14
[0102] wherein n=5-17.
[0103] The present invention further utilizes surface active agents
of the formula:
R.sub.1CO.sub.2(CH.sub.2).sub.nCH(SO.sub.3.sup.-M.sup.+)CO.sub.2R.sub.2
[0104] wherein R.sub.1 and R.sub.2 are independently saturated or
unsaturated hydrocarbon groups having from about 1-24 carbon atoms;
wherein n=0-10; and wherein M.sup.+ is a conjugate acid of the
nitrogenous base. In a preferred embodiment, R.sub.1 and R.sub.2
are independently saturated or unsaturated hydrocarbon groups
having from about 1-24 carbon atoms, n=1-6, and M.sup.+ is a
conjugate acid of the nitrogenous base, the nitrogenous base
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof. In another
preferred embodiment, the surface active agent is of the formula:
15
[0105] wherein n1=0-17
[0106] The present invention further utilizes surface active agents
of the formula:
R.sub.1CO.sub.2(CH.sub.2).sub.nSO.sub.3.sup.-M.sup.+
[0107] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein n=1-10; and
wherein M.sup.+ is a conjugate acid of the nitrogenous base. In a
preferred embodiment, R.sub.1 is a saturated or unsaturated
hydrocarbon group having from about 6-24 carbon atoms, n=1-5, and
M.sup.+ is a conjugate acid of the nitrogenous base, the
nitrogenous base selected from the group consisting essentially of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, or a
mixture thereof. In another preferred embodiment, the surface
active agent is of the formula: 16
[0108] wherein n1=2-18.
[0109] The present invention further utilizes surface active agents
of the formula:
(R.sub.1).sub.n--Ar--O(CH.sub.2CH(R.sub.40
)O).sub.m(SO.sub.3.sup.-M.sup.+- )
[0110] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein Ar is a phenyl,
polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, and
mixtures thereof; wherein R' is methyl or hydrogen; wherein M.sup.+
is a conjugate acid of the nitrogenous base; wherein n=1-4; wherein
the total number of carbon atoms represented by R.sub.1).sub.n is
at least 5; and wherein m=0-100. In a preferred embodiment, R.sub.1
is a saturated or unsaturated hydrocarbon group having from about
6-24 carbon atoms, Ar is phenyl; M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof, n=1, and m=0-100. In another preferred
embodiment, the surface active agent is of the formula: 17
[0111] wherein n1=5-18; and wherein n2=0-20.
[0112] The present invention further utilizes surface active agents
of the formula:
R.sub.1O(CH.sub.2CH(R')O).sub.n(SO.sub.3.sup.-M.sup.+)
[0113] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein R' is methyl or
hydrogen; wherein n=0-100; and wherein M.sup.+ is a conjugate acid
of the nitrogenous base. In a preferred embodiment, R.sub.1 is a
saturated or unsaturated hydrocarbon group having from about 6-24
carbon atoms, R' is methyl or hydrogen, n=0-100, and M.sup.+ is a
conjugate acid of the nitrogenous base, the nitrogenous base
selected from the group consisting of allyl amine, diallyl amine,
triallyl amine, methallyl amine, N-methyl N-allyl amine, or
2-(dimethylamino)ethyl acrylate, and mixtures thereof. In another
preferred embodiment, the surface active agent is of the formula:
18
[0114] wherein n1=5-18. In another preferred embodiment, the
surface active agent is of the formula: 19
[0115] wherein n1=5-18; and wherein n=1 -20.
[0116] The present invention further utilizes surface active agents
of the formula:
R.sub.1CO.sub.2.sup.-M.sup.+
[0117] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 4-24 carbon atoms; and wherein M.sup.+ is a
conjugate acid of the nitrogenous base. In a preferred embodiment,
R.sub.1 is a saturated or unsaturated hydrocarbon group having from
about 6-24 carbon atoms, and M.sup.+ is a conjugate acid of the
nitrogenous base, the nitrogenous base selected from the group
consisting of allyl amine, diallyl amine, triallyl amine, methallyl
amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate,
and mixtures thereof. In another preferred embodiment, the surface
active agent is of the formula: 20
[0118] wherein n=5-18.
[0119] The present invention further utilizes surface active agents
of the formula:
R.sub.1CON(R')(CH.sub.2).sub.nCO.sub.2.sup.-M.sup.+
[0120] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein R' is methyl,
ethyl, propyl or hydrogen; wherein M.sup.+ is a conjugate acid of
the nitrogenous base; and wherein n=1-10. In a preferred
embodiment, M.sup.+ is a conjugate acid of the nitrogenous base,
the nitrogenous base selected from the group consisting of allyl
amine, diallyl amine, triallyl amine, methallyl amine, N-methyl
N-allyl amine, or 2-dimethylamino)ethyl acrylate, and mixtures
thereof, R' is methyl, ethyl, propyl or hydrogen, and n=2-5. In
another preferred embodiment, the surface active agent is of the
formula: 21
[0121] wherein n1=2-18.
[0122] The present invention further utilizes surface active agents
of the formula:
R.sub.1CON(R')(CH.sub.2).sub.nSO.sub.3M.sup.+
[0123] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein R' is methyl,
ethyl, propyl or hydrogen; wherein M.sup.+ is a conjugate acid of
the nitrogenous base; and wherein n=1-10. In a preferred
embodiment, M.sup.+ is a conjugate acid of the nitrogenous base,
the nitrogenous base selected from the group consisting of allyl
amine, diallyl amine, triallyl amine, methallyl amine, N-methyl
N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures
thereof, R' is methyl, ethyl, propyl or hydrogen, and n=2-5. In
another preferred embodiment, the surface active agent is of the
formula: 22
[0124] wherein n1=2-18.
[0125] The present invention further utilizes surface active agents
of the formula:
R.sub.1O(CH.sub.2CH(R')O).sub.nCOCH.sub.2SO.sub.3.sup.-M.sup.+
[0126] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein R' is methyl or
hydrogen; wherein n=0-100; wherein M.sup.+ is a conjugate acid of
the nitrogenous base. In a preferred embodiment, R.sub.1 is a
saturated or unsaturated hydrocarbon group having from about 6-24
carbon atoms; R' is methyl or hydrogen, M.sup.+ is a conjugate acid
of the nitrogenous base, the nitrogenous base selected from the
group consisting of allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl
acrylate, and mixtures thereof; and n=0-100. In another preferred
embodiment, the surface active agent is of the formula: 23
[0127] wherein n1=5-17; and wherein n=0-20.
[0128] The present invention further utilizes surface active agents
of the formula:
R.sub.1O(PO.sub.3).sup.x-M.sup.+.sub.y
[0129] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms, phenyl, polyphenyl,
napthyl, polynapthyl, styryl, or polystyryl group, an
alkyl/alkoxylate substituted phenyl, an alkyl/alkoxylate
substituted or poly-substituted polyphenyl, an alkyl/alkoxylate
substituted or poly-substituted napthyl, an alkyl/alkoxylate
substituted or poly-substituted polynapthyl, an alkyl/alkoxylate
substituted or poly-substituted styryl, or an alkyl/alkoxylate
substituted or poly-substituted polystyryl group, and mixtures
thereof; wherein M.sup.+ is a conjugate acid of the nitrogenous
base; wherein x=1 or 2; and wherein y=1 or2.
[0130] The present invention further utilizes surface active agents
of the formula:
[R.sub.1O(CH.sub.2CH(R')O).sub.m].sub.nP(O).sub.p.sup.x-5
M.sup.+.sub.y
[0131] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein R' is methyl or
hydrogen; wherein M.sup.+ is a conjugate acid of the nitrogenous
base, the nitrogenous base selected from the group consisting of
allyl amine, diallyl amine, triallyl amine, methallyl amine,
N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and
mixtures thereof; m=0-100; wherein n=1 or 2; wherein p=2 or 3;
wherein x=1 or 2; and wherein y=1 or 2.
[0132] The present invention further utilizes surface active agents
of the formula:
[(R.sub.1).sub.nArO(CH.sub.2CH(R')O).sub.m].sub.qP(O).sub.p.sup.x-M.sup.+.-
sub.y
[0133] wherein R.sub.1 is a saturated or unsaturated hydrocarbon
group having from about 1-24 carbon atoms; wherein Ar is phenyl;
wherein R' is methyl or hydrogen; wherein M.sup.+ is a conjugate
acid of the nitrogenous base, the nitrogenous base selected from
the group consisting of allyl amine, diallyl amine, triallyl amine,
methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl
acrylate, and mixtures thereof; wherein n=1-4; wherein m=0-100;
wherein q=1 or 2; wherein p=2 or 3; wherein x=1 or 2; and wherein
y=1 or 2.
[0134] The present invention further utilizes polymerizable surface
active agents which are quaternary ammonium salts of the general
formula: 24
[0135] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently, substituted or unsubstituted hydrocarbyl groups of
from about 1 to about 30 carbon atoms, or hydrocarbyl groups having
from about 1 to about 30 carbon atoms and containing one or more
aromatic, ether, ester, amido, or amino moieties present as
substituents or as linkages in the radical chain, wherein at least
one of the R.sub.1-R.sub.4 groups contains at least one or more
ethenylene groups; and wherein X.sup.- is an anion group selected
from the group consisting of sulfonate, sulfate, sulfinate,
sulfenate, phosphate, carboxylate, nitrate, and acetate.
Additionally, useful polymerizable surface active agents include
those of the above general formula in the form of ring structures
formed by covalently linking two of the R.sub.1-R.sub.4 groups.
Examples include unsaturated imidazolines, imidazoliniums, and
pyridiniums, and the like. These quaternary ammonium salts may be
prepared by a variety of methods known to the art, for example,
halide exchange, wherein a halide based quaternary ammonium
compound is ion exchanged with X.sup.-; where X.sup.- is defined
above.
[0136] The present invention encompasses amine oxide-derived
polymerizable surface active agents, formed as shown in Scheme IX,
wherein R.sub.1, R.sub.2, R.sub.3 are independently, substituted or
unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon
atoms, or hydrocarbyl groups having from about 1 to about 30 carbon
atoms and containing one or more aromatic, ether, ester, amido, or
amino moieties present as substituents or as linkages in the
radical chain, wherein at least one of the R.sub.1-R.sub.3 groups
contains at least one or more ethenylene groups; and wherein
X.sup.- is an anion group selected from the group consisting of
sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate,
nitrate, and acetate. Additionally, useful polymerizable surface
active agents include those of the above general formula in the
form of ring structures formed by covalently linking two of the
R.sub.1-R.sub.4 groups. Examples include unsaturated imidazolines,
imidazoliniums, and pyridiniums, and the like. 25
[0137] The present invention further encompasses quaternary
halide-derived polymerizable surface active agents, formed as shown
in Scheme X, wherein R.sub.1, R.sub.2, R.sub.3 are independently,
substituted or unsubstituted hydrocarbyl groups of from about 1 to
about 30 carbon atoms, or hydrocarbyl groups having from about 1 to
about 30 carbon atoms and containing one or more aromatic, ether,
ester, amido, or amino moieties present as substituents or as
linkages in the radical chain, wherein at least one of the
R.sub.1-R.sub.3 groups contains at least one or more ethenylene
groups; and wherein X.sup.- is an anion group selected from the
group consisting of sulfonate, sulfate, sulfinate, sulfenate,
phosphate, carboxylate, nitrate, and acetate. Additionally, useful
polymerizable surface active agents include those of the above
general formula in the form of ring structures formed by covalently
linking two of the R.sub.1-R.sub.4 groups. Examples include
unsaturated imidazolines, imidazoliniums, and pyridiniums, and the
like.
[0138] The present invention further encompasses polymerizable
onium compounds, particularly ammonium salts, sulfonium salts,
sulfoxonium salts, oxonium salts, nitronium salts, and phosphonium
salts of various anions, including for example, anions group
selected from the group consisting of sulfonate, sulfate,
sulfinate, sulfenate, phosphate, carboxylate, nitrate, acetate and
various halides; wherein the onium compound contains at least one
ethenylene functionality.
"Reverse" Polymerizable Surface Active Agents
[0139] Although somewhat less preferred, the polymerizable, surface
active agents utilized in the present invention may be "reverse"
polymerizable surface active agents. Reverse polymerizable surface
active agents utilized in the present invention are salts or
quaternary nitrogen compounds comprising: (1) at least one
ethylenically unsaturated acid, wherein the acid contains at least
one ethylenically unsaturated moiety and is a sulfonic acid, a
carboxylic acid, or a phosphoric acid, or a mixture thereof; and
(2) at least one substantially saturated nitrogenous base, wherein
the nitrogenous base contains at least one nitrogen atom and a
C.sub.1-C.sub.24 alkyl group. By substantially saturated
nitrogenous base, it is meant that the nitrogenous base contains
less than about 5% unsaturation in the alkyl group(s).
[0140] In general, the ethylenically unsaturated acids of the
present invention are any sulfonic acids, carboxylic acids, or
phosphoric acids which contain at least one unsaturated moiety.
More specifically, the ethylenically unsaturated acids useful in
the present invention are generally vinyl sulfonic acids, vinyl
sulfinic acids, vinyl sulfenic acids, vinyl sulfonic acid esters,
vinyl carboxylic acids, vinyl, phosphoric acids, vinyl phosphonic
acids, vinyl phosphinic, vinyl phosphenic acids, unsaturated
sulfonic acids, unsaturated polysulfonic acids, unsaturated
sulfonic acids of oils, unsaturated paraffin sulfonic acids,
unsaturated lignin sulfonic acids, unsaturated petroleum sulfonic
acids, unsaturated tall oil acids, unsaturated olefin sulfonic
acids, unsaturated hydroxyolefin sulfonic acids, unsaturated
polyolefin sulfonic acids, unsaturated polyhydroxy polyolefin
sulfonic acids, unsaturated carboxylic acids, unsaturated
perfluorinated carboxylic acids, unsaturated carboxylic acid
sulfonates, unsaturated alkoxylated carboxylic acid sulfonic acids,
unsaturated polycarboxylic acids, unsaturated polycarboxylic acid
polysulfonic acids, unsaturated alkoxylated polycarboxylic acid
polysulfonic acids, unsaturated phosphoric acids, unsaturated
alkoxylated phosphoric acids, unsaturated polyphosphoric acids, and
unsaturated alkoxylated polyphosphoric acids, unsaturated
fluorinated phosphoric acids, unsaturated phosphoric acid esters of
oils, unsaturated phosphinic acids, unsaturated alkylphosphinic
acids, unsaturated aminophosphinic acids, unsaturated
polyphosphinic acids, unsaturated vinyl phosphinic acids,
unsaturated phosphonic acids, unsaturated polyphosphonic acids,
unsaturated phosphonic acid alkyl esters, unsaturated
.alpha.-phosphono fatty acids, unsaturated oragnoamine
polymethylphosphonic acids, unsaturated organoamino dialkylene
phosphonic acids, unsaturated alkanolamine phosphonic acids,
unsaturated trialkyledine phosphonic acids, unsaturated
acylamidomethane phosphonic acids, unsaturated
alkyliminodimethylene diphosphonic acids, unsaturated
polymethylene-bis(nitrilodimethylene)tetraphosphonic acids,
unsaturated alkyl bis(phosphonoalkylidene)amine oxide acids,
unsaturated esters of substituted aminomethylphosphonic acids,
unsaturated phosphonamidic acids, unsaturated acylated amino acids
(e.g., amino acids reacted with alkyl acyl chlorides, alkyl esters
or carboxylic acids to produce N-acylamino acids), unsaturated
N-alkyl acylamino acids, and unsaturated acylated protein
hydrolysates, and mixtures thereof.
[0141] Other ethylenically unsaturated acids which are useful in
the present invention are selected from the group comprising
unsaturated linear or branched alkylbenzene sulfonic acids,
unsaturated alkyl sulfuric acid esters, unsaturated alkoxylated
alkyl sulfuric acid esters, unsaturated .alpha.-sulfonated alkyl
ester acids, unsaturated .alpha.-sulfonated ester diacids,
unsaturated alkoxylated .alpha.-sulfonated alkyl ester acids,
unsaturated .alpha.-sulfonated dialkyl diester acids, unsaturated
di-.alpha.-sulfonated dialkyl diester acids, unsaturated
.alpha.-sulfonated alkyl acetate acids, unsaturated primary and
secondary alkyl sulfonic acids, unsaturated perfluorinated alkyl
sulfonic acids, unsaturated sulfosuccinic mono- and diester acids,
unsaturated polysulfosuccinic polyester acids, unsaturated
sulfoitaconic diester acids, unsaturated sulfosuccinamic acids,
unsaturated sulfosuccinic amide acids, unsaturated sulfosuccinic
imide acids, unsaturated phthalic acids, unsaturated sulfophthalic
acids, unsaturated sulfoisophthalic acids, unsaturated phthalamic
acids, unsaturated sulfophthalamic acids, unsaturated alkyl ketone
sulfonic acids, unsaturated hydroxyalkane-1-sulfonic acids,
unsaturated lactone sulfonic acids, unsaturated sulfonic acid
amides, unsaturated sulfonic acid diamides, unsaturated alkyl
phenol sulfuric acid esters, unsaturated alkoxylated alkyl phenol
sulfuric acid esters, unsaturated alkylated cycloalkyl sulfuric
acid esters, unsaturated alkoxylated alkylated cycloalkyl sulfuric
acid esters, unsaturated dendritic polysulfonic acids, unsaturated
dendritic polycarboxylic acids, unsaturated dendritic
polyphosphoric acids, unsaturated sarcosinic acids, unsaturated
isethionic acids, and unsaturated tauric acids, and mixtures
thereof.
[0142] Additionally in accordance with the present invention,
suitable ethylenically unsaturated acids of the present invention
include unsaturated fluorinated carboxylic acids, unsaturated
fluorinated sulfonic acids, unsaturated fluorinated sulfate acids,
unsaturated fluorinated phosphonic and phosphinic acids, and
mixtures thereof.
[0143] In general, the substantially saturated nitrogenous bases of
the present invention are any bases which contain at least one
nitrogen atom, and are capable of forming a salt with the
ethylenically unsaturated acid. The saturated nitrogenous bases
suitable for use in the present invention include any primary,
secondary or tertiary amine, which has at least one
C.sub.1-C.sub.24 alkyl group. Preferably, the alkyl groups of such
amines have from about 12 to about 22 carbon atoms, and may be
substituted or unsubstituted. Such amines, include for example,
stearamido propyl dimethyl amine, diethyl amino ethyl stearamide,
dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine,
tridecyl amine, ethyl stearylamine, N-tallowpropane diamine,
ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl
stearylamine, and arachidylbehenylamine and mixtures thereof.
Auxiliary Polymerizable Surface Active Agents
[0144] The present invention encompasses the use of auxiliary
polymerizable surface active agents, i.e. polymerizable surface
active agent known to those skilled in the art, in combination with
the polymerizable surface active agents, homopolymeric surface
active agents, and supplemental surface active agents described
herein. Examples of auxiliary polymerizable surface active agents
useful in the present invention are shown below in Table I.
1TABLE I Auxillary Polymerizable Surface Active Agents Diallyl
Amine Pluronics - BASF 26 Linoleic Alcohol Derivatives - ICI 27
Allyl Alkyl Phenol Derivatives - DKS (Japan) 28 Acrylate
Derivatives - PPG 29 Allyl Alcohol Alkenyl Succinic Anhydride
Derivatives - KAO (Japan) 30 Polystep RA Series (Maleic
Derivatives) - Stepan Co. 31 Maleic Derivatives - Rhone Poulenc 32
Trem LF-40 Allyl Sulfosuccinate Derivatves - Henkel 33
[0145] Additional auxiliary polymerizable surfactants useful
herein, for example, are generally disclosed in Polymerizable
Surfactants Guyot, A. Current Opinions in Colloid and Surface
Science, 1996, pg. 580-585; Reactive Surfactants in Emulsion
Polymerization Guyot, A.; et. al; Advances in Polymer Science, Vol.
11, Springer-Verlag, Berlin, 1994, pg.43-65; and Polymerizable
Surfactant Holmber, K. Progress in Organic Coatings, 20 (1992)
325-337 (all incorporated herein in their entirety).
Supplemental Surface Active Agents
[0146] Generally, it is advantageous to not use conventional,
non-polymerizable surface active agents in the present invention.
However, if so desired, the polymerizable surface active agents of
the present invention may be used in the polymerization in
combination with minor amounts of a conventional polymerization
surfactants, i.e. supplemental surface active agents, that are not
polymerizable. Without being bound by any particular theory, these
supplemental surface active agents may allow for the varying of
particle size of the resulting discrete, solid, polymeric
particles. The supplemental surface active agents are generally
anionic, nonionic, cationic or amphoteric surfactants or mixtures
thereof, and are typically used as in a concentration of about 0.01
to about 20.0 percent by weight, based on the total weight of
surface active agents (i.e. both polymerizable and
non-polymerizable). Somewhat more preferably, the supplemental
surface active agents are used in a concentration of about 0.01 to
about 5.0 percent by weight, based on the total weight of
supplemental surface active agents (i.e. both polymerizable and
non-polymerizable).
[0147] Suitable supplemental nonionic surface active agents are
generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al.,
issued Dec. 30, 1975, at column, 13 line 14 through column 16, line
6, incorporated herein by reference. Generally, the supplemental
nonionic surface active agent is selected from the group comprising
polyoxyethylenated alkylphenols, polyoxyethyleneated straight chain
alcohols, polyoxyethyleneated branched chain alcohols,
polyoxyethyleneated polyoxypropylene glycols, polyoxyethyleneated
mercaptans, fatty acid esters, glyceryl fatty acid esters,
polyglyceryl fatty acid esters, propylene glycol esters, sorbitol
esters, polyoxyethyleneated sorbitol esters, polyoxyethylene glycol
esters, polyoxyethyleneated fatty acid esters, primary
alkanolamides, ethoxylated primary alkanolamides, secondary
alkanolamides, ethoxylated secondary alkanolamides, tertiary
acetylenic glycols, polyoxyethyleneated silicones,
N-alkylpyrrolidones, alkylpolyglycosides, alkylpolylsaccharides,
EO-PO block polymers, polyhydroxy fatty acid amides, amine oxides
and mixtures thereof. Further, exemplary, non-limiting classes of
useful supplemental nonionic surface active agents are listed
below:
[0148] 1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from
about 6 to 12 carbon atoms in either a straight or branched chain
configuration with the alkylene oxide. In a preferred embodiment,
the ethylene oxide is present in an amount equal to from about 1 to
about 25 moles of ethylene oxide per mole of alkyl phenol.
Commercially available nonionic surfactants of this type include
Igepal.RTM. CO-630, marketed by Stepan Company, Canada; and
Triton.RTM. X-45, X-114, X-100 and X-102, all marketed by the Union
Carbide Company.
[0149] 2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or
secondary, and generally contain from about 8 to about 22 carbon
atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 6 to about 11
carbon atoms with from about 2 to about 10 moles of ethylene oxide
per mole of alcohol. Examples of commercially available nonionic
surfactants of this type include Tergitol.RTM. 15-S-9 (the
condensation products of C.sub.11-C.sub.15 linear alcohol with 9
moles of ethylene oxide), Tergitol.RTM. 24-L-6 NMW (the
condensation products of C.sub.2-C.sub.4 primary alcohol with 6
moles of ethylene oxide with a narrow molecular weight
distribution), both marketed by Union Carbide Corporation;
Neodol.RTM. 91-8 (the condensation product of C.sub.9-C.sub.11,
linear alcohol with 8 moles of ethylene oxide), Neodol.RTM. 23-6.5
(the condensation product of C.sub.12-C.sub.13 linear alcohol with
6.5 moles of ethylene oxide), Neodol.RTM. 45-7 (the condensation
product of C.sub.14-C.sub.15 linear alcohol with 7 moles of
ethylene oxide), Neodol.RTM. 91-6 (the condensation product of
C.sub.9-C.sub.11 linear alcohol with 6 moles of ethylene oxide),
marketed by Shell Chemical Company, and Kyro.RTM. EOB (the
condensation product of C.sub.13-C.sub.15 linear alcohol with 9
moles of ethylene oxide), marketed by the Procter and Gamble
Company.
[0150] 3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1880
and exhibits water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water
solubility of the molecule as a whole, and the liquid character of
the product is retained up to the point where the polyoxyethylene
content is about 50% of the total weight of the condensation
product, which corresponds to condensation with up to about 40
moles of ethylene oxide. Examples of compounds of this type include
certain of the commercially available Pluronic.RTM. surfactants,
marketed by BASF.
[0151] 4. The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists
of the reaction product of ethylenediamine and excess propylene
oxide, and generally has a molecular weight of from about 2500 to
about 3000. This hydrophobic moiety is condensed with ethylene
oxide to the extent that the condensation product contains from
about 40% to about 80% by weight of polyoxyethylene and has a
molecular weight of from about 5,000 to about 11,000. Examples of
this type of nonionic surfactant include certain of the
commercially available Tetronic.RTM. compounds, marketed by
BASF.
[0152] 5. Semi-polar nonionic surfactants are a special category of
supplemental nonionic surface active agents which include
water-soluble amine oxides containing on alkyl moiety of from about
10 to about 18 carbon atoms and 2 moieties selected from the group
comprising alkyl groups and hydroxyalkyl groups containing from
about 1 to about 3 carbon atoms; and water-soluble sulfoxides
containing alkyl moieties of from about 10 to about 18 carbon atoms
and a moiety selected from the group comprising alkyl groups and
hydroxyalkyl groups of from about 1 to about 3 carbon atoms.
[0153] 6. Alkylpolysaccharides disclosed in U.S. Pat. No.
4,565,647, Lenado, issued Jan. 21, 1986, incorporated herein by
reference, having a hydrophobic group containing from about 6 to
about 30 carbon atoms, preferably from about 10 to about 16 carbon
atoms and a polysaccharide, e.g., a polyglucoside, hydrophilic
group containing from about 1.3 to about 10, preferably from about
1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units. Any reducing saccharide containing 5 or 6 carbon
atoms can be used, e.g., glucose, galactose and galactosyl moieties
can be substituted for the glucosyl moieties. (Optionally, the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions
thus giving a glucose or galactose as opposed to a glucoside or
galactoside.) The intersaccharide bonds can be, e.g., between the
one position of the additional saccharide units and the 2-, 3-, 4-,
and/or 6-positions on the preceding saccharide units.
[0154] 7. An ethyl ester ethoxylate and/or alkoxylate such as those
described in U.S. Pat. No. 5,220,046, incorporated herein by
reference. These material may be prepared according to the
procedure set forth in Japanese Kokai patent application No. HEI 5
[1993]-222396. For example, they may be prepared by a one-step
condensation reaction between an alkyl ester and an alkylene oxide
in the present of a catalytic amount of magnesium together with
another ion selected from the group of Al.sup.+3, Ga.sup.+3,
In.sup.+3, Co.sup.+3, Sc.sup.+3, La.sup.+3 and Mn.sup.+3.
Optionally, and less less desirably, there can be a
polyalkyleneoxide chain joining the hydrophobic moiety and the
polysaccharide moiety. The preferred alkyleneoxide is ethylene
oxide. Typical hydrophobic groups include alkyl groups, either
saturated or unsaturated, branched or unbranched, containing from
about 8 to about 18, preferably from about 12 to about 14 carbon
atoms; n is 2 or 3, preferably 2; t is from about 0 to about 10,
preferably 0; and x is from about 1.3 to about 10, preferably from
about 1.3 to 3, most preferably from about 1.3 to about 2.7. The
glycosyl is preferably derived from glucose. To prepare these
compounds, the alcohol or alkylpolyethoxy alcohol is formed first
and then reacted with glucose, or a source of glucose, to form the
glucoside (attachment at the 1-position). The additional glucosyl
units can then be attached between their 1-position and the
preceding glycosyl units 2-, 3-, 4-, and/or 6-position, preferably
predominately the 2-position.
[0155] Examples of suitable supplemental amphoteric surface active
agents are selected from the group comprising alkyl glycinates,
propionates, imidazolines, amphoalkylsulfonates sold as
"Miranol".RTM. by Rhone Poulenc, N-alkylaminopropionic acids,
N-alkyliminodipropionic acids, imidazoline carboxylates,
N-alkylbetaines, amido propyl betaines, sarcosinates,
cocoamphocarboxyglycinates, amine oxides, sulfobetaines, sultaines
and mixtures thereof. Additional suitable amphoteric surfactants
include cocoamphoglycinate, cocoamphocarboxyglycinate,
lauramphocarboxyglycinate, cocoamphopropionate,
lauramphopropionate, stearamphoglycinate,
cocoamphocarboxy-propionate, tallowamphopropionate,
tallowamphoglycinate, oleoamphoglycinate, caproamphoglycinate,
caprylamphopropionate, caprylamphocarboxyglycinate, cocoyl
imidazoline, lauryl imidazoline, stearyl imidazoline, behenyl
imidazoline, behenylhydroxyethyl imidazoline,
caprylamphopropylsulfonate, cocamphopropylsulfonate,
stearamphopropyl-sulfonate, oleoamphopropylsulfonate and the
like.
[0156] Examples of supplemental amine oxide surface active agents
which are generally suitable for use in the present invention are
alkylamine and amidoamine oxides. Examples of supplemental betaine
and sultaine surface active agents which are suitable for use in
the present invention are alkyl betaines and sultaines sold as
"Mirataine".RTM. by Rhone Poulenc, "Lonzaine".RTM. by Lonza, Inc.,
Fairlawn, N.J. Examples of supplemental betaines and sultaines are
cocobetaine, cocoamidoethyl betaine, cocoamidopropyl betaine,
lauryl betaine, lauramidopropyl betaine, palmamidopropyl betaine,
stearamidopropyl betaine, stearyl betaine, coco-sultaine, lauryl
sultaine, tallowamidopropyl hydroxysultaine and the like.
[0157] Examples of supplemental cationic surface active agents
useful in the present invention are fatty amine salts, fatty
diamine salts, polyamine salts, quaternary ammonium compounds,
polyoxyethyleneated fatty amines, quaternized polyoxyethyleneated
fatty amines, amine oxides and mixtures thereof.
[0158] Examples of suitable supplemental cationic surface active
agents are disclosed in the following documents, all incorporated
by reference herein: M. C. Publishing Co., McCutcheon's Detergents
& Emulsifiers, (North American Ed., 1993); Schwartz et al.,
Surface Active Agents, Their Chemistry and Technology, New York;
Interscience Publisher, 1949; U.S. Pat. No. 3,155,591, Hilfer,
issued Nov. 3, 1964; U.S. Pat. No. 3,929,678, Laughlin et al.,
issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey et al.,
issued May 25, 1976; and U.S. Pat. No. 4,387,090, Bolich, Jr.,
issued Jun. 7, 1983.
[0159] Examples of supplemental cationic surface active agents in
the form of quaternary ammonium salts include dialkyldiethyl
ammonium chlorides and trialkyl methyl ammonium chlorides, wherein
the alkyl groups have from about 12 to about 22 carbon atoms and
are derived from long-chain fatty acids, such as hydrogenated
tallow fatty acid (tallow fatty acids yield quaternary compounds
wherein R.sub.1 and R.sub.2 have predominately from about 16 to
about 18 carbon atoms). Examples of supplemental quaternary
ammonium salts usefull herein include ditallowdimethyl ammonium
chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl
dimethyl ammonium chloride, di-(hydrogenated tallow) dimethyl
ammonium chloride, dioctadecyl dimethyl ammonium chloride,
dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium
chloride, di-(hydrogenated tallow) dimethyl ammonium acetate,
dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyol
ammonium acetate, ditallow dipropyl ammonium phosphate, ditallow
dimethyl ammonium nitrate, di-(coconutalkyl)dimethyl ammonium
chloride, and stearyl dimethyl benzyl ammonium chloride.
[0160] Salts of primary, secondary and tertiary fatty amines are
also suitable supplemental cationic surface active agents. The
alkyl groups of such supplemental amines preferably have from about
12 to about 22 carbon atoms, and may be substituted or
unsubstituted. Such amines, useful herein, include stearamido
propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl
stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl
amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5
moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and
arachidylbehenylamine. Suitable supplemental amine salts include
the halogen, acetate, phosphate, nitrate, citrate, lactate and
alkyl sulfate salts. Such supplemental salts include stearylamine
hydrogen chloride, soyamine chloride, stearylamine formate,
N-tallowpropane diamine dichloride and stearamidopropyl
dimethylamine citrate. Supplemental cationic amine surfactants
included among those useful in the present invention are also
disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued
Jun. 23, 1981, incorporated herein by reference.
[0161] Supplemental cationic surface active agents which are
especially useful are quaternary ammonium or amino compounds having
at least one N-radical containing one or more nonionic hydrophilic
moieties selected from the group comprising alkoxy,
polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties,
and combinations thereof The compounds contain at least one
hydrophilic moiety within 4, preferably within 3, carbon atoms
(inclusive) of the quaternary nitrogen or cationic amino nitrogen.
Additionally, carbon atoms that are part of a hydrophilic moiety,
e.g., carbon atoms in a hydrophilic polyoxyalkylene
(e.g.,--CH.sub.2--CH.sub.2--O--), that are adjacent to other
hydrophilic moieties are not counted when determining the number of
hydrophilic moieties within 4, or preferably 3, carbon atoms of the
cationic nitrogen. In general, the alkyl portion of any hydrophilic
moiety is preferably a C.sub.1-C.sub.3 alkyl. Suitable
hydrophile-containing radicals include, for example, ethoxy,
propoxy, polyoxyethylene, polyoxypropylene, ethylamido,
propylamido, hydroxymethyl, hydroxyethyl, hydroxypropyl, methyl
ester, ethyl ester, propyl ester, or mixtures thereof, as nonionic
hydrophile moieties.
[0162] Among the supplemental cationic surface active agents useful
herein are those of the general formula: 34
[0163] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 comprise,
independently, substituted or unsubstituted substantially saturated
hydrocarbyl chains of from about 1 to about 30 carbon atoms, or a
hydrocarbyl having from about 1 to about 30 carbon atoms and
containing one or more aromatic, ether, ester, amido, or amino
moieties present as substituents or as linkages in the radical
chain, wherein at least on of the R.sub.1-R.sub.4 groups contains
one or more hydrophilic moieties selected from the group comprising
alkoxy (preferably C.sub.1-C.sub.3 alkoxy), polyoxyalkylene
(preferably C.sub.1-C.sub.3 polyoxyalkylene), alkylamido,
hydroxyalkyl, alkylester and combination thereof. Preferably, the
cationic conditioning surfactant contains from about 2 to about 10
nonionic hydrophile moieties located within the about stated
ranges. For purposes herein, each hydrophilic amido, alkoxy,
hydroxyalkyl, alkylester, alkylamido or other unit is considered to
be a distinct nonionic hydrophile moiety. X.sup.- is a
substantially saturated soluble salt forming anion preferably
selected from the group comprising halogens (especially chlorine),
acetate, phosphate, nitrate, sulfonate, and alkyl sulfate
radicals.
[0164] Preferred supplemental cationic surface active agents
include polyoxyethylene (2) stearyl methyl ammonium chloride,
methyl bis-(hydrogenated tallowamidoethyl) 2-hydroxyethyl ammonium
methyl sulfate, polyoxypropylene (9) diethyl methyl ammonium
chloride, tripolyoxyethylene (total PEG-10) stearyl anunonium
phosphate, bis-(N-hydroxyethyl-2-oleyl imidazolinium chloride)
polyethylene glycol (1), and isododecylbenzyl triethanolammonium
chloride.
[0165] Other supplemental ammonium quaternary and amino surface
active agents include those of the above general formula in the
form of ring structures formed by covalently linking two of the
radicals. Examples include imidazolines, imidazoliniums, and
pyridiniums, etc., wherein said compound has at least one nonionic
hydrophile-containing radical as set forth above. Specific examples
include 2-heptadecyl-4,5-dihydro-lH-imidaz- ol-1-ethanol,
4,5-dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl-1-phenylmethy-
limidazolium chloride, and
1-[2-oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]amino]- ethyl]pyridinium
chloride.
[0166] Salts of primary, secondary and tertiary fatty amines are
also preferred supplemental cationic surfactant materials. The
alkyl groups of such amines preferably have from about 1 to about
30 carbon atoms and must contain at least one, preferably about 2
to about 10, nonionic hydrophilic moieties selected from the group
comprising alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and
alkylester groups, and mixtures thereof.
[0167] The supplemental anionic surface active agents suitable for
use in the present invention are generally the sodium, potassium,
calcium, ammonium or alkanolamine salts of any substantially
saturated sulfonic acid, carboxylic acid, or phosphoric acid, or a
mixture thereof. More specifically, supplemental anionic surface
active agents suitable for use in the present invention are
generally the sodium, potassium, calcium, ammonium or alkanolamine
salts of saturated sulfonic acids, sulfinic acids, sulfenic acids,
sulfonic acid esters, carboxylic acids, phosphonic acids,
phosphinic, phosphenic acids, polysulfonic acids, sulfonic acids of
oils, paraffin sulfonic acids, lignin sulfonic acids, petroleum
sulfonic acids, tall oil acids, olefin sulfonic acids,
hydroxyolefin sulfonic acids, polyolefin sulfonic acids,
polyhydroxy polyolefin sulfonic acids, carboxylic acids,
perfluorinated carboxylic acids, carboxylic acid sulfonates,
alkoxylated carboxylic acid sulfonic acids, polycarboxylic acids,
polycarboxylic acid polysulfonic acids, alkoxylated polycarboxylic
acid polysulfonic acids, phosphoric acids, alkoxylated phosphoric
acids, polyphosphoric acids, and alkoxylated polyphosphoric acids,
fluorinated phosphoric acids, phosphoric acid esters of oils,
phosphinic acids, alkylphosphinic acids, aminophosphinic acids,
polyphosphinic acids, vinyl phosphinic acids, phosphonic acids,
polyphosphonic acids, phosphonic acid alkyl esters,
.alpha.-phosphono fatty acids, oragnoamine polymethylphosphonic
acids, organoamino dialkylene phosphonic acids, alkanolamine
phosphonic acids, trialkyledine phosphonic acids, acylamidomethane
phosphonic acids, alkyliminodimethylene diphosphonic acids,
polymethylene-bis(nitrilodimeth- ylene)tetraphosphonic acids, alkyl
bis(phosphonoalkylidene)amine oxide acids, esters of substituted
aminomethylphosphonic acids, phosphonamidic acids, acylated amino
acids (e.g., amino acids reacted with alkyl acyl chlorides, alkyl
esters or carboxylic acids to produce N-acylamino acids), N-alkyl
acylamino acids, and acylated protein hydrolysates, and mixtures
thereof.
[0168] Other supplemental anionic surface active agents suitable
for use in the present invention are the sodium, potassium,
calcium, ammonium or alkanolamine salts of saturated linear or
branched alkylbenzene sulfonic acids, alkyl sulfuric acid esters,
alkoxylated alkyl sulfuric acid esters, .alpha.-sulfonated alkyl
ester acids, .alpha.-sulfonated ester diacids, alkoxylated
.alpha.-sulfonated alkyl ester acids, .alpha.-sulfonated dialkyl
diester acids, di-.alpha.-sulfonated dialkyl diester acids,
.alpha.-sulfonated alkyl acetate acids, primary and secondary alkyl
sulfonic acids, perfluorinated alkyl sulfonic acids, sulfosuccinic
mono- and diester acids, polysulfosuccinic polyester acids,
sulfoitaconic diester acids, sulfosuccinamic acids, sulfosuccinic
amide acids, sulfosuccinic imide acids, phthalic acids,
sulfophthalic acids, sulfoisophthalic acids, phthalamic acids,
sulfophthalamic acids, alkyl ketone sulfonic acids,
hydroxyalkane-1-sulfonic acids, lactone sulfonic acids, sulfonic
acid amides, sulfonic acid diamides, alkyl phenol sulfuric acid
esters, alkoxylated alkyl phenol sulfuric acid esters, alkylated
cycloalkyl sulfuric acid esters, alkoxylated alkylated cycloalkyl
sulfuric acid esters, dendritic polysulfonic acids, dendritic
polycarboxylic acids, dendritic polyphosphoric acids, sarcosinic
acids, isethionic acids, and tauric acids, and mixtures
thereof.
[0169] Additionally in accordance with the present invention,
supplemental anionic surface active agents suitable for use in the
present invention are generally the sodium, potassium, calcium,
ammonium or alkanolamine salts of saturated fluorinated carboxylic
acids, fluorinated sulfonic acids, fluorinated sulfate acids,
fluorinated phosphonic and phosphinic acids, and mixtures
thereof.
[0170] In a preferred embodiment of the present invention, the
polymerization process is conducted in the absence of any
non-polymerizable, supplemental surfactant, as the polymerizable
surface active agents of the present invention display excellent
capacity for producing emulsion stability characteristics in an
emulsion polymerization.
[0171] In another embodiment of the present invention, the
polymerizable surface active agents of the present invention may be
used as co-monomers with the ethylenically unsaturated monomer(s)
to modify the physical properties of the resulting polymer. In this
embodiment, supplemental surface active agents also may be used as
additives to the polymerization, e.g., in amounts of from about 3
to 6 weight percent, based on the total weight of monomer. Although
somewhat less preferred, in a further embodiment of the present
invention, any conventional organic solvent, which may be a solvent
for both the monomer(s) and/or polymer, or just the monomer(s) may
be used.
Initiators and Additives
[0172] Organic or inorganic initiators may be used to initiate the
polymerization reaction. A sufficient quantity of a polymerization
initiator (such as a conventional free radical initiator) is
typically introduced into the polymerization medium to cause
polymerization of the monomer(s) at the particular temperatures
employed. Initiators used in polymerization processes may be of the
type which produce free radicals and conveniently are peroxygen
compounds, for example: inorganic peroxides such as hydrogen
peroxide and inorganic persulfate compounds such as ammonium
persulfate, sodium persulfate and potassium per-sulfate; organic
hydroperoxides such as cumene hydroperoxide and tertiary butyl
hydroperoxide; organic peroxides such as benzoyl peroxide, acetyl
peroxide, lauroyl peroxide, peroxydicarbonate esters such as
diisopropyl peroxydicarbonate, peracetic acid and per-benzoic acid,
sometimes activated by water-soluble reducing agents such as
ferrous compounds, sodium bisulfite or hydroxylamine hydrochloride,
and other free radical producing materials such as
2,2'-azobisisobutyronitrile.
[0173] A further additive which may be added to the mixture
contents is a conventional chain transfer agent, such as an alkyl
polyhalide or mercaptan. Examples of suitable chain transfer agents
include bromoform, carbon tetrachloride, carbontetrabromide,
bromoethane, C1-C.sub.12 alkyl mercaptans, e.g., dodecylmercaptan,
thiophenol, and hydroxyalkyl mercaptans, e.g., mercaptoethanol.
[0174] All documents, e.g., patents and journal articles, cited
above or below are hereby incorporated by reference in their
entirety.
[0175] In the following examples, all amounts are stated in percent
by weight unless indicated otherwise.
[0176] One skilled in the art will recognize that modifications may
be made in the present invention without deviating from the spirit
or scope of the invention. The invention is illustrated further by
the following examples which are not to be construed as limiting
the invention or scope of the specific procedures or compositions
described herein. All documents, e.g., patents and journal
articles, cited above or below are hereby incorporated by reference
in their entirety.
[0177] As used in the Examples appearing below, the following
designations, symbols, terms and abbreviations have the indicated
meanings:
2 Material Definition Polystep .RTM. A-13 Linear dodecylbenzene
sulfonic acid (commercially available from Stepan Company,
Northfield Illinois) Polystep .RTM. A-16 Branched dodecylbenzene
sulfonic acid, sodium salt (commercially available from Stepan
Company, Northfield Illinois) Polystep .RTM. A-17 Branched
dodecylbenzene sulfonic acid (commercially available from Stepan
Company, Northfleld Illinois) Cedephos CP-610 Nonyl Phenol 9-EO
Phosphoric Acid Ester (commercially available from Stepan Company,
Northfield Illinois)
[0178] The amount of agglomerated polymers, or "coagulum", in the
resulting lattices at the conclusion of the polymerization is
determined by collecting the agglomerated polymers using a 20 mesh
screen that has openings sufficiently large enough to allow the
discrete un-agglomerated polymers to pass, rinsing the collected
agglomerated polymers with water, and weighting the remaining
agglomerated polymers trapped on the screen. The percent coagulum
is calculated by dividing the weight of the coagulum by the
theoretical weight of the entire latex based upon the weights of
the ingredients used for the polymerization reaction.
[0179] The viscosity of the resulting lattices following
polymerization is determined by using a RV Brookfield
synchro-lechtric viscometer equipped with a No. 3 spindle. During
such determinations 950 ml of each latex is placed in a 1000 ml
beaker and the viscometer operated at 25.degree. C. and 60 rpm.
[0180] The mechanical stability of the lattices following exposure
to mechanical stress is evaluated to determine the extent to which
there is a change in the viscosity and/or the visual presence of
coagulum. More specifically, two cups of each latex are placed in a
five-cup stainless steel Hamilton Beach blender, and the blender
operated at medium speed until the latex coagulates. Failure of the
latex is the point at which coagulum separation can be visually
observed; a longer time of blending at medium speed without
coagulum separation, i.e. a longer time before failure, is a highly
desirable characteristic of a latex.
[0181] Solids of lattices were determined by concentrating the
latex at 120.degree. C. in an oven to remove all volitiles, and
subsequently weighing the residue. The pH of each solution was
measured using an Orion 210 pH meter. Particle size was measured
using a Nicomp 370, [submicron analyzer, (up to 2 microns)].
[0182] The particle size of the resulting lattices is determined
with a NICOMP 370C Auto-dilution particle size analyzer using
standard methods and procedures for operation of such equipment and
such data recorded for 50% volume in units of nano-meters.
[0183] The water sensitivity, e.g. hydrophobicity, of the resulting
lattices was determined by ASTM D724-45.
[0184] All .sup.1H NMR spectra were recorded using a 270 MHz Joel
Delta NMR Fourier Transform Spectrometer. Chemical shifts (.delta.)
are reported in parts per million (ppm) down field from
tetramethylsilane (TMS) using internal TMS or residual
non-deuterated solvent as a reference. NMR data for all samples was
acquired by dissolving the solid sample in CD.sub.3OD.
[0185] The allylamine and propyl amine may be obtained from Aldrich
Chemical Company (USA).
[0186] In the following examples, all amounts are stated in percent
by weight of active material unless indicated otherwise. One
skilled in the art will recognize that modifications may be made in
the present invention without deviating from the spirit or scope of
the invention. The invention is illustrated further by the
following examples which are not to be construed as limiting the
invention or scope of the specific procedures or compositions
described herein.
EXAMPLE 1
[0187] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about 48:49:3), in
combination with the allylamine salt of dodecylbenzenesulfonic acid
(ADDBS), is prepared as follows. About 254 g of deionized water and
about 10.6 g of ADDBS (as a 22% active aqueous solution), are
placed in a reactor suitable for emulsion polymerization, equipped
with agitation means, heating means and cooling means. With
agitation, the reactor is purged with nitrogen (99% pure), and
heated to about 80-82.degree. C. The temperature of the reactor
contents is adjusted to about 77-79.degree. C., and about 75 g of
the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA
monomer mixture in the ratio above) is added to the reactor. After
10 minutes, 16.9 g of a solution of ammonium persulfate (20% of the
total solution of 1.9 g of ammonium persulfate dissolved in 82.5 g
of water) is added to the reactor over a period of about 7 minutes
with continued agitation, during which time there is an exotherm of
about 7-10.degree. C. After the exotherm is complete, about 299 g
of the monomer mixture (the remaining 80% MMA/BA/MMA monomer
mixture), 64.5 g of the ammonium persulfate solution (the remaining
80%), and 15.55 g of ADDBS (as the 22% active aqueous solution) are
simultaneously charged to the reactor over a period of 2 hours with
continued agitation, while keeping the reactor contents at a
temperature of about 78-81.degree. C. The reactor temperature is
then elevated to about 82-84.degree. C. with continued agitation,
for about 15 minutes. After this 15 minute period, the reactor is
cooled to about 30.degree. C. The resulting latex product is
completely removed from the reactor and gravity filtered using a
first 20 mesh screen and then a second 250 mesh screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected,
combined and weighed. Various physiochemical properties of the
latex are reported in Table II.
[0188] FIG. I depicts the partial .sup.1H NMR spectrum, showing the
region of .delta.5.0-8.0, of the allylamine salt of
dodecylbenzenesulfonic acid (ADDBS). The peaks centered around 7.4
ppm are signals corresponding to the aromatic protons of the
benzene ring. The signals at about 5.9 ppm and 5.3 ppm correspond
to the protons of the double bond in the allyl amine portion of the
compound.
[0189] FIG. II depicts the partial .sup.1H NMR spectrum, showing
the region of .delta.5.0-8.0, of a latex formulation prepared
according to Example # 1 above. As can be seen in FIG. II, the
double bond signals from he allyl amine portion of the compound, at
5.9 ppm and 5.3 ppm, are absent from the spectrum. Without being
bound by any particular theory, the double bond has been
substantially completely consumed during the polymerization
reaction.
EXAMPLE 2
(Comparative Example)
[0190] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about 48:49:3), in
combination with the propylamine salt of dodecylbenzenesulfonic
acid (PDDBS), is prepared as follows. About 330 g of deionized
water and about 25 g of PDDBS (as a 20% active aqueous solution)
are placed in a reactor suitable for emulsion polymerization,
equipped with agitation means, heating means and cooling means.
With agitation, the reactor is purged with nitrogen (99% pure), and
heated to about 80-82.degree. C. The temperature of the reactor
contents is adjusted to about 77-79.degree. C., and about 75 g of
the monomer mixture (20% of a total of 374 g of the MMA/BA/MMA
monomer mixture in the ratio above) is added to the reactor. After
10 minutes, 15.5 g of a solution of ammonium persulfate (20% of the
total solution of 1.9 g of ammonium persulfate dissolved in 75.6 g
of water), is added to the reactor over a period of about 5 minutes
with continued agitation, during which time there is an exotherm of
about 3-5.degree. C. After the exotherm is complete, about 299 g of
the monomer mixture (the remaining 80%) and 62 g of the ammonium
persulfate solution (the remaining 80%) are simultaneously charged
tot he reactor over a period of 2 hours with continued agitation,
while keeping the reactor contents at a temperature of about
78-82.degree. C. The reactor temperature is then elevated to about
82-84.degree. C. with continued agitation, for about 15 minutes.
After this 15 minute period, the reactor is cooled to about
30.degree. C. The resulting latex product is completely removed
from the reactor and gravity filtered using a first 20 mesh screen
and then a second 250 mesh screen. The total latex coagulum (i.e.
solids) from both mesh screens is collected, combined and weighed.
Various physiochemical properties of the latex are reported in
Table II.
EXAMPLE 3
[0191] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about 46.1:50.8:3.1)
in combination with the allylamine salt of nonyl phenol 9-EO
phosphate acid ester (Cedephos CP-610) is prepared as follows.
About 249 g of deionized water and about 11.0 g of the allyl amine
salt of Cedephos CP-610 (as a 20% active aqueous solution), are
placed in a reactor suitable for emulsion polymerization, equipped
with agitation means, heating means and cooling means. With
agitation, the reactor is purged with nitrogen (99% pure), and
heated to about 75 77.degree. C. The temperature of the reactor
contents is adjusted to about 71-74.degree. C., and about 74 g of
the monomer mixture (20% of a total of 371 g of the MMA/BA/MMA
monomer mixture in the ratio above) is added to the reactor. After
10 minutes, 15 g of a solution of ammonium persulfate (20% of the
total solution of 1.9 g of ammonium persulfate dissolved in 74.0 g
of water) is added to the reactor over a period of about 10 minutes
with continued agitation, during which time there is an exotherm of
about 5-8.degree. C. After the exotherm is complete, about 299 g of
the monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture),
60.7 g of the ammonium persulfate solution (the remaining 80%), and
15.3 g of the allyl amine salt of Cedephos CP-610 (as a 20% active
aqueous solution) are simultaneously charged to the reactor over a
period of 2 hours with continued agitation, while keeping the
reactor contents at a temperature of about 78-81.degree. C. The
reactor temperature is then elevated to about 82-84.degree. C. with
continued agitation, for about 15 minutes. After this 15 minute
period, the reactor is cooled to about 30.degree. C. The resulting
latex product is completely removed from the reactor and gravity
filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh
screens is collected, combined and weighed. Various physiochemical
properties of the latex are reported in Table II.
EXAMPLE 4
(Comparative Example)
[0192] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about 46:51:3), in
combination with the propylamine salt of nonyl phenol 9-EO
phosphate acid ester (Cedephos CP-610) is prepared as follows.
About 251 g of deionized water and about 10.2 g of propylamine salt
of Cedephos CP-610 (as a 20% active aqueous solution), are placed
in a reactor suitable for emulsion polymerization, equipped with
agitation means, heating means and cooling means. With agitation,
the reactor is purged with nitrogen (99% pure), and heated to about
75 77.degree. C. The temperature of the reactor contents is
adjusted to about 71-74.degree. C., and about 75 g of the monomer
mixture (20% of a total of 375 g of the MMA/BA/MMA monomer mixture
in the ratio above) is added to the reactor. After 10 minutes, 15 g
of a solution of ammonium persulfate (20% of the total solution of
1.9 g of ammonium persulfate dissolved in 75.0 g of water) is added
to the reactor over a period of about 10 minutes with continued
agitation, during which time there is an exotherm of about
8-10.degree. C. After the exotherm is complete, about 300 g of the
monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture),
61.5 g of the ammonium persulfate solution (the remaining 80%), and
15.3 g of the propylamine salt of Cedephos CP-610 (as a 20% active
aqueous solution) are simultaneously charged to the reactor over a
period of 2 hours with continued agitation, while keeping the
reactor contents at a temperature of about 78-80.degree. C. The
reactor temperature is then elevated to about 82-84.degree. C. with
continued agitation, for about 15 minutes. After this 15 minute
period, the reactor is cooled to about 30.degree. C. The resulting
latex product is completely removed from the reactor and gravity
filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh
screens is collected, combined and weighed. Various physiochemical
properties of the latex are reported in Table II.
EXAMPLE 5
[0193] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about (48:49:3), in
combination with the allylamine salt of lauric acid (ALA) is
prepared as follows. About 205 g of deionized water and about 1.6 g
of ALA (as a 20% active aqueous solution), are placed in a reactor
suitable for emulsion polymerization, equipped with agitation
means, heating means and cooling means. With agitation, the reactor
is purged with nitrogen (99% pure), and heated to about
70-73.degree. C. The temperature of the reactor contents is
adjusted to about 71-73.degree. C., and about 75 g of the monomer
mixture (20% of a total of 374 g of the MMA/BA/MMA monomer mixture
in the ratio above) is added to the reactor. After 10 minutes, 15 g
of a solution of ammonium persulfate (20% of the total solution of
1.8 g of ammonium persulfate dissolved in 75.0 g of water) is added
to the reactor over a period of about 10 minutes with continued
agitation, during which time there is an exotherm of about
2-3.degree. C. After the exotherm is complete, about 299 g of the
monomer mixture (the remaining 80% MMA/BA/MMA monomer mixture),
61.5 g of the ammonium persulfate solution (the remaining 80%), and
29.2 g of the ALA (as a 20% active aqueous solution) are
simultaneously charged to the reactor over a period of 2 hours with
continued agitation, while keeping the reactor contents at a
temperature of about 78-81.degree. C. The reactor temperature is
then elevated to about 83-85.degree. C. with continued agitation,
for about 15 minutes. After this 15 minute period, the reactor is
cooled to about 30.degree. C. The resulting latex product is
completely removed from the reactor and gravity filtered using a
first 20 mesh screen and then a second 250 mesh screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected,
combined and weighed. Various physiochemical properties of the
latex are reported in Table II.
EXAMPLE 6
(Comparative Example)
[0194] A methylmethacrylate/butylacrylate/methacrylic acid
(MMA/BA/MMA) co-polymer (in a weight ratio of about (48:49:3), in
combination with the propylamine salt of lauric acid (PLA) is
prepared as follows. About 206 g of deionized water and about 1.6 g
of PLA (as a 20% active aqueous solution), are placed in a reactor
suitable for emulsion polymerization, equipped with agitation
means, heating means and cooling means. With agitation, the reactor
is purged with nitrogen (99% pure), and heated to about
75-77.degree. C. The temperature of the reactor contents is
adjusted to about 71-73.degree. C., and about 7 g of the monomer
mixture (2% of a total of 373 g of the MMA/BA/MMA monomer mixture
in the ratio above) is added to the reactor. After 10 minutes, 15 g
of a solution of ammonium persulfate (20% of the total solution of
1.8 g of ammonium persulfate dissolved in 75.0 g of water) is added
to the reactor over a period of about 10 minutes with continued
agitation, during which time there is an exotherm of about
2-3.degree. C. After the exotherm is complete, about 366 g of the
monomer mixture (the remaining 98% MMA/BA/MMA monomer mixture),
61.5 g of the ammonium persulfate solution (the remaining 80%), and
28.4 g of the PLA (as a 20% active aqueous solution) are
simultaneously charged to the reactor over a period of 2 hours with
continued agitation, while keeping the reactor contents at a
temperature of about 79-82.degree. C. The reactor temperature is
then elevated to about 83-85.degree. C. with continued agitation,
for about 15 minutes. After this 15 minute period, the reactor is
cooled to about 30.degree. C. The resulting latex product is
completely removed from the reactor and gravity filtered using a
first 20 mesh screen and then a second 250 mesh screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected,
combined and weighed. Various physiochemical properties of the
latex are reported in Table II.
3TABLE II Latexes of Methylmethacrylate/Butylacryla- te/Methacrylic
Acid Mechanical Particle Contact Method Coagulum Viscosity
Stability Size Angle Solids of Surfactant (%) (CPS) (min) (microns)
(deg.) pH (%) Initiation Polymerizable <0.2 11 8 120.5 125 2.43
46.9 Thermal Surfactant ADDBS (Ex. 1) Non-Polymerizable <0.03
220 5 122.5 98 2.23 44 Thermal Surfactant PDDBS (Comparative Ex. 2)
Polymerizable <0.67 90 ND 135 126 3.25 46.6 Thermal Surfactant
Allylamine- Cedephos (Ex. 3) Non-Polymerizable <0.52 115 ND 149
104 2.92 47.7 Thermal Surfactant PDDBS (Comparative Ex. 4)
Polymerizable <0.67 50 >15 1191 ND 5.7 49.7 Thermal
Surfactant ALA (Ex. 5) Non-Polymerizable <0.52 50 >15 1197.7
ND 6.1 48.8 Thermal Surfactant PLA (Comparative Ex. 6)
EXAMPLE 7
[0195] A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a
weight ratio of about 78.9:21.1), in combination with the
allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and
propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared as
follows. About 245 g of deionized water and about 1.5 g of ADDBS
(as a 20% active aqueous solution), 1.5 g of PDDBS (as a 23% active
aqueous solution), and 1.0 g of sodium sulfate are placed in a
reactor suitable for emulsion polymerization, equipped with
agitation means, heating means and cooling means. With agitation,
the reactor is purged with nitrogen (99% pure), and heated to about
65-68.degree. C. The temperature of the reactor contents is
adjusted to about 63-65.degree. C., and about 73.7 g of the monomer
mixture (20% of a total of 369 g of the VA/BA monomer mixture in
the ratio above) is added to the reactor. After 10 minutes, 15 g of
a solution of ammonium persulfate (20% of the total solution of 1.8
g of ammonium persulfate dissolved in 75.0 g of water) is added to
the reactor over a period of about 5 minutes with continued
agitation. The temperature of the reactor is increased to about
82-84.degree. C. Evidence of polymerization is observed by the
appearance of blue tint in the reaction contents and a slight
exotherm of 1-2.degree. C. The temperature of the reaction contents
is adjusted to about 76-78.degree. C. and about 294 g of the BA/VA
monomer mixture (the remaining 80%), 61.5 g of the ammonium
persulfate solution (the remaining 80%), 27.46 g ADDBS (as a 20%
active aqueous solution), and 8.59 g PDDBS (as a 23% active aqueous
solution) are simultaneously charged to the reactor over a period
of 4 hours with continued agitation, while keeping the reactor
contents at a temperature of about 78-82.degree. C. The reactor
temperature is then elevated to about 82-84.degree. C. with
continued agitation, for about 15 minutes. After this 15 minute
period, the reactor is cooled to about 30.degree. C. The resulting
latex product is completely removed from the reactor and gravity
filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh
screens is collected, combined and weighed. Various physiochemical
properties of the latex are reported in Table III.
EXAMPLE 8
(Comparative Example)
[0196] A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a
weight ratio of about 79.1:20.9), in combination with the propyl
amine salt of dodecylbenzenesulfonic acid (PDDBS) is prepared as
follows. About 162 g of deionized water and about 5.4 g of PDDBS
(as a 23% active aqueous solution) are placed in a reactor suitable
for emulsion polymerization, equipped with agitation means, heating
means and cooling means. With agitation, the reactor is purged with
nitrogen (99% pure), and heated to about 65-68.degree. C. The
temperature of the reactor contents is adjusted to about 62.degree.
C., and about 5.0 g of the monomer mixture (2% of a total of 245 g
of the VA/BA monomer mixture in the ratio above) is added to the
reactor. After 10 minutes, 10.1 g of a solution of ammonium
persulfate (20% of the total solution of 1.8 g of ammonium
persulfate dissolved in 75.0 g of water) is added to the reactor
over a period of about 15 minutes with continued agitation. The
temperature of the reactor is increased to about 82-84.degree. C.
Evidence of polymerization is observed by the appearance of blue
tint in the reaction contents and a slight exotherm of 2-4.degree.
C. The temperature of the reaction contents is adjusted to about
76-78.degree. C. and about 240 g of the BA/VA monomer mixture (the
remaining 80%), 40.7 g of the ammonium persulfate solution (the
remaining 80%), 16.8 g PDDBS (as a 23% active aqueous solution) are
simultaneously charged to the reactor over a period of 4 hours with
continued agitation, while keeping the reactor contents at a
temperature of about 78-80.degree. C. The reactor temperature is
then elevated to about 82-84.degree. C. with continued agitation,
for about 15 minutes. After this 15 minute period, the reactor is
cooled to about 30.degree. C. The resulting latex product is
completely removed from the reactor and gravity filtered using a
first 20 mesh screen and then a second 250 mesh screen. The total
latex coagulum (i.e. solids) from both mesh screens is collected,
combined and weighed. Various physiochemical properties of the
latex are reported in Table III.
EXAMPLE 9
[0197] A vinylacetatelbutyl acrylate (VA/BA) co-polymer (in a
weight ratio of about 78.9:21.1), in combination with the
allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and the
ammonium salt of lauryl ether sulphate with 30 EO groups (ALSE) is
prepared as follows. About 245 g of deionized water and about 1.5 g
of ADDBS (as a 19% active aqueous solution) and 1.0 g of sodium
sulfate are placed in a reactor suitable for emulsion
polymerization, equipped with agitation means, heating means and
cooling means. With agitation, the reactor is purged with nitrogen
(99% pure), and heated to about 65-68.degree. C. The temperature of
the reactor contents is adjusted to about 60-63.degree. C., and
about 73.7 g of the monomer mixture (20% of a total of 369 g of the
VA/BA monomer mixture in the ratio above) is added to the reactor.
After 10 minutes, 15 g of a solution of ammonium persulfate (20% of
the total solution of 1.8 g of ammonium persulfate dissolved in
75.0 g of water) is added to the reactor over a period of about 5
minutes with continued agitation. The temperature of the reactor is
increased to about 82-84.degree. C. Evidence of polymerization is
observed by the appearance of blue tint in the reaction contents
and a slight exotherm of 1-2.degree. C. The temperature of the
reaction contents is adjusted to about 78-81.degree. C. and about
294 g of the BA/VA monomer mixture (the remaining 80%), 61.4 g of
the ammonium persulfate solution (the remaining 80%), 27.8 g ADDBS
(as a 20% active aqueous solution), and 6.3 g ALSE (as a 30% active
aqueous solution) are simultaneously charged to the reactor over a
period of 4 hours with continued agitation, while keeping the
reactor contents at a temperature of about 78-82.degree. C. The
reactor temperature is then elevated to about 82-84.degree. C. with
continued agitation, for about 15 minutes. After this 15 minute
period, the reactor is cooled to about 30.degree. C. The resulting
latex product is completely removed from the reactor and gravity
filtered using a first 20 mesh screen and then a second 250 mesh
screen. The total latex coagulum (i.e. solids) from both mesh
screens is collected, combined and weighed. Various physiochemical
properties of the latex are reported in Table III.
EXAMPLE 10
[0198] A vinylacetate/butyl acrylate (VA/BA) co-polymer (in a
weight ratio of about 78.9:21.1), in combination with the
allylamine salt of dodecylbenzenesulfonic acid (ADDBS) and
propylamine salt of dodecylbenzenesulfonic (PDDBS) is prepared,
using redox couple as initiators, as follows. About 251 g of
deionized water and about 1.5 g of ADDBS (as a 19% active aqueous
solution), 0.9 g of PDDBS (as a 23% active aqueous solution), and
0.3 g of sodium hydrogen carbonate are placed in a reactor suitable
for emulsion polymerization, equipped with agitation means, heating
means and cooling means. With agitation, the reactor is purged with
nitrogen (99% pure), and heated to about 65-68.degree. C. The
temperature of the reactor contents is adjusted to about
63-65.degree. C., and about 10.3 g of the monomer mixture (2% of a
total of 513 g of the VA/BA monomer mixture in the ratio above) is
added to the reactor. After 15 minutes, 13.7 g of a solution of
ammonium persulfate (20% of the total solution of 2.0 g of ammonium
persulfate dissolved in 66.5 g of water) and 13.7 g of a solution
of sodium metabisulfite (20% of the total solution of 0.83 g of
sodium metabisulfite dissolved in 67.8 g of water) is added to the
reactor over a period of about 5 minutes with continued agitation.
Evidence of polymerization is observed by the appearance of blue
tint in the reaction contents and a slight exotherm of 1-2.degree.
C. The temperature of the reaction contents is adjusted to about
68-72.degree. C., and 54.9 g of the sodium metabisulphite solution
(the remaining 80%), 54.8 g of the ammonium persulfate solution
(the remaining 80%), 503 g of the BA/VA monomer mixture (the
remaining 98%), 29.3 g of ADDBS (as a 19% active aqueous solution),
and 10.3 g of PDDBS (as a 23% active aqueous solution) are
simultaneously added over a period of three hours with continued
agitation, while keeping the reactor contents at a temperature of
about 68-72.degree. C. The reactor temperature is then elevated to
about 75-78.degree. C. with continued agitation, for about 15
minutes. After this 15 minute period, the reactor is cooled to
about 30.degree. C. The resulting latex product is completely
removed from the reactor and gravity filtered using a first 20 mesh
screen and then a second 250 mesh screen. The total latex coagulum
(i.e. solids) from both mesh screens is collected, combined and
weighed. Various physiochemical properties of the latex are
reported in Table III.
4TABLE III Latexes of Vinylacetate/Butylacrylate Mechanical
Particle Contact Method Coagulum Viscosity Stability Size Angle
Solids of Surfactant (%) (CPS) (min) (microns) (deg.) pH (%)
Initiation Polymerizable/Non- <0.09 220 >13 266/767 86 2.23
45.1 Thermal Polymerizable Surfactants ADDBS & PDDBS (Ex. 7)
Non-Polymerizable <0.05 50 6 98.3 104 2.48 41.2 Thermal
Surfactant PDDBS (Comparative Ex. 8) Polymerizable/Non- <0.03 50
ND 1599 ND 2.63 45.3 Thermal Polymerizable Surfactants ADDBS &
ALSE (Ex. 9) Polymerizable/Non- <0.06 220 ND 410 ND 5.23 46.6
Redox Polymerizable Surfactants ADDBS & PDDBS (Ex. 10)
[0199] The hydrophobicity of a latex prepared using a typical
non-polymerizable surfactant was compared to that of a latex
prepared using a representative polymerizable surfactant of the
present invention. It has been discovered that the latex prepared
in Example 1 (using ADDBS) possess remarkable hydrophobicity, as
compared to the latex prepared according to Example 1 (using the
ammonium salt of dodecylbenzene sulfonic acid, AmDDBS). [Need to
insert ASTM method and description here.] The change in contact
angle as a function of time for a water droplet at each of the
latex film surfaces was measured; the results are shown below.
5 Time (Seconds) Latex Surfactant 5 20 40 60 AmDDBS (non-polymer-
(Contact Angle) 98.degree. 74.degree. 51.degree. 27.degree. izable)
ADDBS (polymerizable) (Contact Angle) 125.degree. 125.degree.
125.degree. 125.degree.
[0200] Without being bound by any particular theory, a rapidly
increasing contact angle as observed from a latex film indicates
that the water droplet is penetrating the film due to surfactant
related imperfections of the film. A constant water droplet contact
angle, as in the case of the ADDBS derived latex, indicates the
desirable result whereby water is unable to penetrate the
hydrophobic film.
[0201] In a test similar to the contact angle measurements, the
hydrophobicity of a latex prepared using a typical
non-polymerizable surfactant was compared to that of a latex
prepared using a representative polymerizable surfactant of the
present invention, whereby the different latex films were coated
and heat cured onto porous filter paper and treated with water. As
observed in the results shown below, water undesirably, readily
penetrated through the film and absorbed into the paper in a few
seconds for the latex derived from the AmDDBS surfactant. However,
the latex film derived from the ADDBS surfactant, did not allow the
water to penetrate or absorb; the water droplet maintained its
original shape on the latex film, prior to being influenced by
evaporation effects (at least thirty minutes).
6 Time (Seconds) Latex Surfactant 5 20 40 60 AmDDBS (non-polymer-
(penetration/ slight total total total izable) absorption ADDBS
(polymerizable) (penetration/ none none none none absorption
[0202] The adhesion properties of a latex prepared using a typical
non-polymerizable surfactant were compared to that of a latex
prepared using a representative polymerizable surfactant of the
present invention. It has been discovered that the latex prepared
in Example 1 (using ADDBS) possess a vastly superior adhesion
profile, as compared to the latex prepared according to Example I
(using the ammonium salt of dodecylbenzene sulfonic acid, AmDDBS).
Adhesion data were collect for each latex acrylic lattice using
ASTM method D897. This test method is a standard test for adhesion
called "block pull"; results from the test are indicated in pounds
per square inch (p.s.i.), wherein the higher the p.s.i. obtained,
the better the adhesion properties of the latex. Adhesive failure
is defined as the point at which the latex, upon application of a
pulling force, no longer adheres to the surface of the substrate.
Cohesive failure is defined as the point at which the latex itself
fails, i.e. where the latex splits into two or more portions, but
remains bound to the substrate. The adhesion tests were conducted
using an Instron Model 1123, with a 5000 pound load cell, a sample
size of 0.5 g of latex, a surface area of 4 in.sup.2, whereby the
treated sample blocks were allowed to dry at room temperature (i.e.
25.degree. C.) for three days under 0.25 p.s.i. external pressure.
Aluminum and steel blocks were prepared by sanding with extra fine
220 grit paper until smooth to the touch. A weighed amount of each
latex (0.5 g) was placed on one surface of one block and another
block place on top for three days. Failure was determined by visual
inspection, with the results indicated below.
7 Latex Surfactant Adhesive Failure (p.s.i.) AmDDBS
(non-polymerizable) 65 ADDBS (polymerizable) 170
[0203] The latex film yellowing properties of a latex prepared
using a typical non-polymerizable surfactant were compared to that
of a latex prepared using a representative polymerizable surfactant
of the present invention. It has been discovered that the latex
prepared in Example 1 (using ADDBS) possess a greatly improved film
yellowing profile, as compared to the latex prepared according to
Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid,
AmDDBS). Latex film yellowing was compared after aging the films
six months at room temperature, at approximately standard
atmospheric conditions. It is highly desirable, as known by one
skilled in the art, to produce a latex film which does not yellow
upon application to a surface, with the passage of time. After a
period of 6 months, the ADDBS-derived latex was plainly observed to
be significantly lighter color than the AmDDBS-derived latex.
Absorbence measurements were taken for each latex at 350 nm and 420
nm; the lower the absorbance at a given wave length, the lighter
the latex (i.e. the less yellow the latex). Results of the
measurements for the two latexes are shown below.
8 Latex Absorbance Latex Surfactant 350 nm 420 nm AmDDBS
(non-polymerizable) 16.9 5.3 ADDBS (polymerizable) 10.0 2.5
[0204] The scrubability properties of a latex prepared using a
typical non-polymerizable surfactant were compared to that of a
latex prepared using a representative polymerizable surfactant of
the present invention. It has been discovered that the latex
prepared in Example 1 (using ADDBS) possess improved scrubability
characteristics, as compared to the latex prepared according to
Example 1 (using the ammonium salt of dodecylbenzene sulfonic acid,
AmDDBS). Scrubability of the latexes was evaluated using ASTM scrub
test D2486. Seven Star Acrylic Flat House Paint, 103A100 White,
from Ace Hardware was utilized in the testing. The ADBBS- and
AmDDBS-derived latexes were individually added to the paint in a
ratio of 2:1 (latex:paint).
[0205] FTIR comparisons were conducting by casting latex films on
glass, derived from both ADDBS and AmiDDBS. The films were dried at
room temperature for several days, removed from the glass and aged
at room temperature, at approximately standard atmospheric
conditions, for six months. The films were individually placed on a
ZnSe plates and the FTIR spectra recorded. Peak heights were
measured on the absorbance peak located at 1035 cm.sup.-1 (i.e. the
S.dbd.O stretch peak) for each film. It has been discovered that
the latex prepared in Example 1 (using ADDBS) possess a much lower
peak height absorbance in the FTIR spectrum, as compared to the
latex prepared according to Example 1 (using the ammonium salt of
dodecylbenzene sulfonic acid, AmDDBS). Without being bound by any
particular theory, a lower the peak height absorbance indicates a
desirable characteristic of the latex, whereby the individual
surfactant molecules are not present at the surface of the latex
film, i.e. they have not migrated to the surface of the film.
9 Latex Surfactant Latex FTIR Absorbance (.times. 10.sup.-4) AmDDBS
(non-polymerizable) 73 ADDBS (polymerizable) 29
[0206] From the foregoing, it will be appreciated that although
specific embodiments of the invention have been described herein
for purposes of illustration, various modifications may be made
without deviating from the spirit or scope of the invention.
* * * * *