U.S. patent application number 10/964219 was filed with the patent office on 2005-03-17 for continuous bulk polymerization and esterification process and compositions.
Invention is credited to Andrist, Kevin M., Blasko, John E., Calhoun, Glenn C., Hansen, Frederick C., Hellwig, Dean R., Hessenius, Kurt A., Hurley, Steven M., Jayasuriya, D. Sunil, Lee, Matthew G., Maccani, Stephen J., Mills, H. Thomas JR., Peterson, Gregory R., Sandvick, Paul E., Wilson, Dennis M., Wiruth, John P..
Application Number | 20050059782 10/964219 |
Document ID | / |
Family ID | 22233058 |
Filed Date | 2005-03-17 |
United States Patent
Application |
20050059782 |
Kind Code |
A1 |
Andrist, Kevin M. ; et
al. |
March 17, 2005 |
Continuous bulk polymerization and esterification process and
compositions
Abstract
A continuous bulk polymerization and esterification process
includes continuously charging into a reaction zone at least one
ethylenically unsaturated acid-functional monomer and at least one
linear or branched chain alkanol having greater than 11 carbon
atoms. The process includes maintaining a flow rate through the
reaction zone sufficient to provide an average residence time of
less than 60 minutes and maintaining a temperature in the reaction
zone sufficient to produce a polymeric product incorporating at
least some of the alkanol as an ester of the polymerized
ethylenically unsaturated acid-functional monomer. The polymeric
product is used in various processes to produce water-based
compositions including emulsions and dispersions such as oil
emulsions, wax dispersions, pigment dispersions, surfactants and
coatings which contain the polymeric product. A polymeric
surfactant includes at least one ethylenically unsaturated
acid-functional monomer which has been radically incorporated into
the polymeric surfactant and at least one ester of the incorporated
ethylenically unsaturated acid-functional monomer which has a
linear or branched chain alkyl group with greater than 11 carbon
atoms. The molar critical micelle concentration of the polymeric
surfactant is less than 1.0.times.10.sup.-2 moles/liter. Aqueous 2
percent solutions of certain polymeric surfactants have a surface
tension of less than 45 mN/m at 30.degree. C. and exhibit a
decrease in surface tension of at least 5 mN/m as the temperature
warms from 30.degree. C. to 50.degree. C.
Inventors: |
Andrist, Kevin M.; (Racine,
WI) ; Blasko, John E.; (Racine, WI) ; Calhoun,
Glenn C.; (Racine, WI) ; Hansen, Frederick C.;
(Union Grove, WI) ; Hellwig, Dean R.; (Racine,
WI) ; Hessenius, Kurt A.; (Sturtevant, WI) ;
Hurley, Steven M.; (Racine, WI) ; Jayasuriya, D.
Sunil; (Racine, WI) ; Lee, Matthew G.;
(Boonville, IN) ; Maccani, Stephen J.; (Racine,
WI) ; Mills, H. Thomas JR.; (Racine, WI) ;
Peterson, Gregory R.; (Franksville, WI) ; Sandvick,
Paul E.; (Racine, WI) ; Wilson, Dennis M.;
(Kenosha, WI) ; Wiruth, John P.; (Racine,
WI) |
Correspondence
Address: |
JOHNSON POLYMER, INC.
8310 16TH STREET- M/S 510
P.O. BOX 902
STURTEVANT
WI
53177-0902
US
|
Family ID: |
22233058 |
Appl. No.: |
10/964219 |
Filed: |
October 13, 2004 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10964219 |
Oct 13, 2004 |
|
|
|
10013752 |
Oct 29, 2001 |
|
|
|
10013752 |
Oct 29, 2001 |
|
|
|
09347035 |
Jul 2, 1999 |
|
|
|
6355727 |
|
|
|
|
60092405 |
Jul 10, 1998 |
|
|
|
Current U.S.
Class: |
525/330.1 ;
524/560; 524/561; 524/562; 525/384; 526/271; 526/317.1; 526/318.1;
526/318.3; 526/75 |
Current CPC
Class: |
D21H 17/28 20130101;
C08F 220/06 20130101; B01F 17/005 20130101; C09G 1/16 20130101;
C08F 20/04 20130101; C08F 22/06 20130101; D21H 17/37 20130101; B01F
17/0028 20130101; D21H 21/16 20130101; C08F 2/02 20130101; B01F
17/0085 20130101; C08F 220/18 20130101 |
Class at
Publication: |
525/330.1 ;
525/384; 524/560; 524/561; 524/562; 526/075; 526/271; 526/317.1;
526/318.1; 526/318.3 |
International
Class: |
C08F 008/14 |
Claims
1. (Cancelled)
2. (Cancelled)
3. (Cancelled)
4. (Cancelled)
5. (Cancelled)
6. (Cancelled)
7. (Cancelled)
8. (Cancelled)
9. (Cancelled)
10. (Cancelled)
11. (Cancelled)
12. (Cancelled)
13. A water-based composition, comprising: (a) water; (b) from
about 1 to about 100 percent by weight based on the total weight of
the composition, disregarding the water, of the polymeric product
according to claim 1; and (c) up to about 99 percent by weight
based on the total weight of the composition, disregarding the
water, of an adjunct.
14. The water-based composition according to claim 13, wherein the
adjunct is selected from the group consisting of an emulsion
polymer, a coalescing solvent, a plasticizer, a cross-linking
agent, a defoamer, a pigment, a tackifier, a conventional
surfactant, a starch, a wax, a slip aid, a wetting agent, a surface
modifier, an inert filler, an inert extender, and mixtures
thereof.
15. The water-based composition according to claim 13, wherein the
adjunct is present in an amount ranging from about 10 to about 99
percent by weight based on the total weight of the composition
disregarding the water.
16. The water-based composition according to claim 14, wherein the
water-based composition is selected from the group consisting of an
overprint varnish, an ink, a barrier coating material, a coil
coating material, a paper coating material, a foil coating
material, an adhesive, a floor polish, a paint, a primer, and a
paper sizing agent.
17. A water-based composition, comprising: (a) water; (b) from
about 1 to about 100 percent by weight based on the total weight of
the composition, disregarding the water, of a polymeric product
produced by a continuous bulk polymerization and esterification
process comprising: continuously charging at least one
ethylenically unsaturated acid-functional monomer and at least one
alkanol having the formula ROH, wherein R is a linear or branched
chain alkyl moiety having greater than 11 carbon atoms, into a
reaction zone to form a reaction mixture; maintaining a flow rate
through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer; and
(c) up to about 99 percent by weight based on the total weight of
the composition, disregarding the water, of an adjunct.
18. The water-based composition of claim 17, wherein the adjunct is
selected from the group consisting of an emulsion polymer, a
coalescing solvent, a plasticizer, a cross-linking agent, a
defoamer, a pigment, a tackifier, a conventional surfactant, a
starch, a wax, a slip aid, a wetting agent, a surface modifier, an
inert filler, an inert extender, and mixtures thereof.
19. The water-based composition according to claim 17, wherein the
total adjunct is present in an amount ranging from about 10 to
about 99 percent by weight based on the total weight of the
composition disregarding the water.
20. The water-based composition according to claim 18, wherein the
water-based composition is selected from the group consisting of an
overprint varnish, an ink, a barrier coating material, a coil
coating material, a paper coating material, a foil coating
material, an adhesive, a floor polish, a paint, a primer, and a
paper sizing agent.
21. A polymeric surfactant, comprising: (a) at least one
ethylenically unsaturated acid-functional monomer which has been
radically incorporated into the polymeric surfactant; and (b) at
least one ester of the incorporated ethylenically unsaturated
acid-functional monomer having an R alkyl group, wherein R is a
linear or branched chain alkyl moiety having greater than 11 carbon
atoms; wherein the molar critical micelle concentration of the
polymeric surfactant is less than 1.0.times.10.sup.-2
moles/liter.
22. The polymeric surfactant according to claim 21, wherein the
surface area per molecule of the polymeric surfactant is less than
36 .ANG..sup.2.
23. The polymeric surfactant according to claim 22, wherein the
surface area per molecule of the polymeric surfactant is less than
20 .ANG..sup.2.
24. The polymeric surfactant according to claim 21, wherein R is a
linear or branched chain alkyl radical having from 12 to 50 carbon
atoms.
25. The polymeric surfactant according to claim 21, wherein R is a
linear or branched chain alkyl radical having from 12 to 22 carbon
atoms.
26. The polymeric surfactant according to claim 21, wherein R is a
linear or branched chain alkyl radical having 14 carbon atoms.
27. The polymeric surfactant according to claim 21, wherein R is a
linear alkyl radical having 14 carbon atoms.
28. The polymeric surfactant according to claim 21, wherein the
molar critical micelle concentration is less than
8.2.times.10.sup.-3 moles/liter.
29. The polymeric surfactant according to claim 21, wherein the
molar critical micelle concentration is less than
1.0.times.10.sup.-3 moles/liter.
30. The polymeric surfactant according to claim 21, further
comprising at least one vinyl aromatic monomer incorporated into
the polymeric surfactant.
31. The polymeric surfactant according to claim 21, further
comprising at least one non-aromatic monomer incorporated into the
polymeric surfactant.
32. The polymeric surfactant according to claim 31, wherein the
ethylenically unsaturated acid-functional monomer is acrylic
acid.
33. The polymeric surfactant according to claim 32, wherein the
polymeric surfactant comprises styrene and .alpha.-methylstyrene
incorporated into the polymeric surfactant.
34. A polymeric surfactant, comprising: (a) at least one
ethylenically unsaturated acid-functional monomer which has been
radically incorporated into the polymeric surfactant; and (b) at
least one ester of the incorporated ethylenically unsaturated
acid-functional monomer having an R alkyl group, wherein R is a
linear or branched chain alkyl radical having greater than 11
carbon atoms; wherein a 2 percent by weight neutralized aqueous
solution of the polymeric surfactant has a surface tension of less
than 45 mN/m at 30.degree. C. and undergoes a decrease in surface
tension of at least 5 mN/m as the temperature warms from 30.degree.
C. to 50.degree. C.
35. The polymeric surfactant according to claim 34, wherein the
molar critical micelle concentration of the polymeric surfactant is
less than 1.times.10.sup.-2 moles/liter.
36. The polymeric surfactant according to claim 34, wherein the
molar critical micelle concentration of the polymeric surfactant is
less than 8.2.times.10.sup.-3 moles/liter.
37. The polymeric surfactant according to claim 34, wherein the
molar critical micelle concentration of the polymeric surfactant is
less than 1.0.times.10.sup.-3 moles liter.
38. The polymeric surfactant according to claim 34, wherein R is a
linear or branched chain alkyl radical having from 12 to 50 carbon
atoms.
39. The polymeric surfactant according to claim 34, wherein R is a
linear or branched chain alkyl radical having from 12 to 22 carbon
atoms.
40. The polymeric surfactant according to claim 34, further
comprising at least one vinyl aromatic monomer incorporated into
the polymeric surfactant.
41. The polymeric surfactant according to claim 34, further
comprising at least one vinyl non-aromatic monomer incorporated
into the polymeric surfactant.
42. The polymeric surfactant according to claim 41, wherein the
ethylenically unsaturated acid-functional monomer is acrylic
acid.
43. The polymeric surfactant according to claim 42, wherein the
polymeric surfactant comprises styrene and .alpha.-methylstyrene
incorporated into the polymeric surfactant.
44. A process for preparing an emulsion of a polyolefin resin,
comprising: (a) mixing together a polyolefin resin and a polymeric
product, the polymeric product produced by a bulk polymerization
and esterification process comprising: continuously charging at
least one ethylenically unsaturated acid-functional monomer and at
least one alkanol having the formula ROH, wherein R is a linear or
branched chain alkyl moiety having greater than 11 carbon atoms,
into a reaction zone to form a reaction mixture; maintaining a flow
rate through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer; (b)
mixing a base with the combination of (a); and (c) mixing the
combined base, resin and polymeric product with water.
45. The process for preparing an emulsion of a polyolefin resin
according to claim 44, further comprising adding a conventional
surfactant to the combination of (a).
46. The process for preparing an emulsion of a polyolefin resin
according to claim 45, wherein the conventional surfactant is
selected from the group consisting of an anionic surfactant and a
non-ionic surfactant, and further wherein the conventional
surfactant is present in an amount up to about 10 percent by weight
based on the total weight of the solids.
47. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polymeric product has an acid
number from 20 to 740.
48. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the base is selected from the group
consisting of ammonia, diethylaminoethanol, morpholine, sodium
hydroxide, potassium hydroxide, and mixtures thereof.
49. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin has a number
average molecular weight ranging from about 500 to about
20,000.
50. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin has an acid
number of about 0 to about 150 and a melting point of about
40.degree. C. to about 250.degree. C.
51. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin, the polymeric
product, and the base are melted together to produce a molten
mixture and the molten mixture is added to the water.
52. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin and the
polymeric product are heated to produce a molten mixture, the base
is added to the molten mixture, and the water is subsequently added
to the base and molten mixture.
53. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin and the
polymeric product are heated to produce a molten mixture, the base
is added to the molten mixture, and the base and molten mixture are
subsequently added to the water.
54. The process for preparing an emulsion of a polyolefin resin
according to claim 44, wherein the polyolefin resin and the
polymeric product are heated to produce a molten mixture, the base
is added to the molten mixture, and the water is subsequently added
to the base and molten mixture.
55. An emulsion prepared according to claim 44.
56. An emulsion prepared according to claim 46.
57. An emulsion prepared according to claim 50.
58. An emulsion of a polyolefin resin, comprising: (a) a polyolefin
resin and a polymeric product consisting of (i) about 3 to 97
percent by weight of at least one ethylenically unsaturated
acid-functional monomer which has been polymerized into the
polymeric product, (ii) about 3 to 97 percent by weight at least
one alkyl ester of the ethylenically unsaturated acid-functional
monomers, wherein the alkyl group is a linear or branched chain
alkyl radical having greater than 11 carbon atoms which has been
polymerized into the polymeric product, (iii) about 0 to about 85
percent by weight of at least one aromatic ethylenically
unsaturated monomer which has been polymerized into the polymeric
product; and (iv) about 0 to about 85 percent by weight of at least
one non-aromatic ethylenically unsaturated vinyl monomer which has
been polymerized into the polymeric product, wherein an aqueous
resin cut at a solids content of 30.5%, a pH of from 7.7 to 8.2,
and a temperature of 25C., of the polymeric product has a solution
viscosity which is less than about 50 percent of the solution
viscosity of an aqueous resin cut at a solids content of 30.5%, a
pH of 7.8, and a temperature of 25C., of a second polymeric product
identical to the polymeric product except that it does not contain
any of the alkyl ester of the ethylenically unsaturated
acid-functional monomers of (ii), and wherein the weight percent of
(i), (ii), (iii) and (iv) is base on the total weight of the
polymeric product; (b) a base; and (c) water.
59. The emulsion of the polyolefin resin according to claim 58,
further comprising a conventional surfactant.
60. The emulsion of the polyolefin resin according to claim 59,
wherein the conventional surfactant is selected from the group
consisting of an anionic surfactant and a non-ionic surfactant, and
further wherein the conventional surfactant is present in an amount
up to about 10 percent by weight based on the total weight of the
solids.
61. The emulsion of the polyolefin resin according to claim 58,
wherein the polymeric product has an acid number from 20 to
740.
62. The emulsion of the polyolefin resin according to claim 58,
wherein the base is selected from the group consisting of ammonia,
diethylaminoethanol, morpholine, sodium hydroxide, potassium
hydroxide, and mixtures thereof.
63. The emulsion of the polyolefin resin according to claim 58,
wherein the polyolefin resin has a number average molecular weight
ranging from about 500 to about 20,000.
64. The emulsion of the polyolefin resin according to claim 63,
wherein the polyolefin resin has an acid number of about 0 to about
150 and a melting point of about 40.degree. to about 250.degree.
C.
65. A process for preparing a wax dispersion, comprising mixing a
wax with an aqueous solution of a polymeric product, the polymeric
product produced by a bulk polymerization and esterification
process comprising: continuously charging at least one
ethylenically unsaturated acid-functional monomer and at least one
alkanol having the formula ROH, wherein R is a linear or branched
chain alkyl moiety having greater than 11 carbon atoms, into a
reaction zone to form a reaction mixture; maintaining a flow rate
through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer.
66. The process for preparing a wax dispersion according to claim
65, further comprising adding a conventional surfactant.
67. The process for preparing a wax dispersion according to claim
66, wherein the conventional surfactant is selected from the group
consisting of an anionic surfactant and a non-ionic surfactant, and
further wherein the conventional surfactant is present in an amount
up to about 10 percent by weight based on the total weight of the
solids.
68. A wax dispersion prepared according to claim 65.
69. A wax dispersion, comprising: (a) a wax; (b) the polymeric
product consisting of (i) about 3 to 97 percent by weight of at
least one ethylenically unsaturated acid-functional monomer which
has been polymerized into the polymeric product, (ii) about 3 to 97
percent by weight at least one alkyl ester of the ethylenically
unsaturated acid-functional monomers, wherein the alkyl group is a
linear or branched chain alkyl radical having greater than 11
carbon atoms which has been polymerized into the polymeric product,
(iii) about 0 to about 85 percent by weight of at least one
aromatic ethylenically unsaturated monomer which has been
polymerized into the polymeric product; and (iv) about 0 to about
85 percent by weight of at least one non-aromatic ethylenically
unsaturated vinyl monomer which has been polymerized into the
polymeric product, wherein an aqueous resin cut at a solids content
of 30.5%, a pH of from 7.7 to 8.2, and a temperature of 25C., of
the polymeric product has a solution viscosity which is less than
about 50 percent of the solution viscosity of an aqueous resin cut
at a solids content of 30.5%, a pH of 7.8, and a temperature of
25C., of a second polymeric product identical to the polymeric
product except that it does not contain any of the alkyl ester of
the ethylenically unsaturated acid-functional monomers of (ii), and
wherein the weight percent of (i), (ii), (iii) and (iv) is base on
the total weight of the polymeric product; (c) an aqueous
medium.
70. The wax dispersion according to claim 69, further comprising a
conventional surfactant.
71. The wax dispersion according to claim 70, wherein the
conventional surfactant is selected from the group consisting of an
anionic surfactant and a non-ionic surfactant, and further wherein
the conventional surfactant is present in an amount up to about 10
percent by weight based on the total weight of the solids.
72. The process for preparing an oil emulsion, comprising: (a)
heating a mixture of an oil and a polymeric product, the polymeric
product produced by a continuous bulk polymerization and
esterification process comprising: continuously charging at least
one ethylenically unsaturated acid-functional monomer and at least
one alkanol having the formula ROH, wherein R is a linear or
branched chain alkyl moiety having greater than 11 carbon atoms,
into a reaction zone to form a reaction mixture; maintaining a flow
rate through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer; (b)
mixing a base with the heated mixture of the oil and the polymeric
product; and (c) mixing water with the components of (b).
73. The process for preparing an oil emulsion according to claim
72, further comprising adding a conventional surfactant.
74. The process for preparing an oil emulsion according to claim
73, wherein the conventional surfactant is selected from the group
consisting of an anionic surfactant and a non-ionic surfactant, and
further wherein the conventional surfactant is present in an amount
up to about 10 percent by weight based on the total weight of the
solids.
75. The process for preparing an oil emulsion according to claim
72, wherein the base is selected from the group consisting of
ammonia, diethylaminoethanol, morpholine, sodium hydroxide,
potassium hydroxide, and mixtures thereof.
76. The process of claim 72, wherein the water is added to the
components of (b).
77. The process of claim 72, wherein the components of (b) are
added to the water.
78. An oil emulsion prepared according to the process of claim
72.
79. An oil emulsion, comprising: (a) an oil (b) a base (c) the
polymeric product consisting of (i) about 3 to 97 percent by weight
of at least one ethylenically unsaturated acid-functional monomer
which has been polymerized into the polymeric product, (ii) about 3
to 97 percent by weight at least one alkyl ester of the
ethylenically unsaturated acid-functional monomers, wherein the
alkyl group is a linear or branched chain alkyl radical having
greater than 11 carbon atoms which has been polymerized into the
polymeric product, (iii) about 0 to about 85 percent by weight of
at least one aromatic ethylenically unsaturated monomer which has
been polymerized into the polymeric product; and (iv) about 0 to
about 85 percent by weight of at least one non-aromatic
ethylenically unsaturated vinyl monomer which has been polymerized
into the polymeric product, wherein an aqueous resin cut at a
solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature
of 25C., of the polymeric product has a solution viscosity which is
less than about 50 percent of the solution viscosity of an aqueous
resin cut at a solids content of 30.5%, a pH of 7.8, and a
temperature of 25C., of a second polymeric product identical to the
polymeric product except that it does not contain any of the alkyl
ester of the ethylenically unsaturated acid-functional monomers of
(ii), and wherein the weight percent of (i), (ii), (iii) and (iv)
is base on the total weight of the polymeric product; (d)
water.
80. The oil emulsion according to claim 79, further comprising a
conventional surfactant.
81. The oil emulsion according to claim 80, wherein the
conventional surfactant is selected from the group consisting of an
anionic surfactant and a non-ionic surfactant, and further wherein
the conventional surfactant is present in an amount up to about 10
percent by weight based on the total weight of the solids.
82. The oil emulsion according to claim 79, wherein the base is
selected from the group consisting of ammonia, diethylaminoethanol,
morpholine, sodium hydroxide, potassium hydroxide, and mixtures
thereof.
83. A process for improving the viscosity profile of an aqueous
pigment dispersion, comprising adding a polymeric product to the
aqueous pigment dispersion, the polymeric product produced by a
continuous bulk polymerization and esterification process
comprising: continuously charging at least one ethylenically
unsaturated acid-functional monomer and at least one alkanol having
the formula ROH, wherein R is a linear or branched chain alkyl
moiety having greater than 11 carbon atoms, into a reaction zone to
form a reaction mixture; maintaining a flow rate through the
reaction zone sufficient to provide an average residence time of
the reaction mixture in the reaction zone of less than 60 minutes;
and maintaining an effective temperature in the reaction zone
sufficient to produce the polymeric product incorporating at least
some of the alkanol as an ester of the polymerized ethylenically
unsaturated acid-functional monomer.
84. An aqueous pigment dispersion with an improved viscosity
profile comprising: (a) an aqueous pigment dispersion; and (b) the
polymeric product consisting of (i) about 3 to 97 percent by weight
of at least one ethylenically unsaturated acid-functional monomer
which has been polymerized into the polymeric product, (ii) about 3
to 97 percent by weight at least one alkyl ester of the
ethylenically unsaturated acid-functional monomers, wherein the
alkyl group is a linear or branched chain alkyl radical having
greater than 11 carbon atoms which has been polymerized into the
polymeric product, (iii) about 0 to about 85 percent by weight of
at least one aromatic ethylenically unsaturated monomer which has
been polymerized into the polymeric product; and (iv) about 0 to
about 85 percent by weight of at least one non-aromatic
ethylenically unsaturated vinyl monomer which has been polymerized
into the polymeric product, wherein an aqueous resin cut at a
solids content of 30.5%, a pH of from 7.7 to 8.2, and a temperature
of 25C., of the polymeric product has a solution viscosity which is
less than about 50 percent of the solution viscosity of an aqueous
resin cut at a solids content of 30.5%, a pH of 7.8, and a
temperature of 25C., of a second polymeric product identical to the
polymeric product except that it does not contain any of the alkyl
ester of the ethylenically unsaturated acid-functional monomers of
(ii), and wherein the weight percent of (i), (ii), (iii) and (iv)
is base on the total weight of the polymeric product.
85. A process for increasing the total solids concentration of an
aqueous coating, comprising adding a polymeric product to the
aqueous coating, the polymeric product produced by a continuous
bulk polymerization and esterification process comprising:
continuously charging at least one ethylenically unsaturated
acid-functional monomer and at least one alkanol having the formula
ROH, wherein R is a linear or branched chain alkyl moiety having
greater than 11 carbon atoms, into a reaction zone to form a
reaction mixture; maintaining a flow rate through the reaction zone
sufficient to provide an average residence time of the reaction
mixture in the reaction zone of less than 60 minutes; and
maintaining an effective temperature in the reaction zone
sufficient to produce the polymeric product incorporating at least
some of the alkanol as an ester of the polymerized ethylenically
unsaturated acid-functional monomer.
86. An aqueous coating having an increase in total solids
comprising: (a) an aqueous coating; and (b) the polymeric product
consisting of (i) about 3 to 97 percent by weight of at least one
ethylenically unsaturated acid-functional monomer which has been
polymerized into the polymeric product, (ii) about 3 to 97 percent
by weight at least one alkyl ester of the ethylenically unsaturated
acid-functional monomers, wherein the alkyl group is a linear or
branched chain alkyl radical having greater than 11 carbon atoms
which has been polymerized into the polymeric product, (iii) about
0 to about 85 percent by weight of at least one aromatic
ethylenically unsaturated monomer which has been polymerized into
the polymeric product; and (iv) about 0 to about 85 percent by
weight of at least one non-aromatic ethylenically unsaturated vinyl
monomer which has been polymerized into the polymeric product,
wherein an aqueous resin cut at a solids content of 30.5%, a pH of
from 7.7 to 8.2, and a temperature of 25C., of the polymeric
product has a solution viscosity which is less than about 50
percent of the solution viscosity of an aqueous resin cut at a
solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of
a second polymeric product identical to the polymeric product
except that it does not contain any of the alkyl ester of the
ethylenically unsaturated acid-functional monomers of (ii), and
wherein the weight percent of (i), (ii), (iii) and (iv) is base on
the total weight of the polymeric product.
87. A process for stabilizing a compound in an aqueous medium,
comprising: (a) providing a resin melt of a polymeric product in a
reactor operating at or above atmospheric pressure, the polymeric
product produced by a continuous bulk polymerization and
esterification process comprising: continuously charging at least
one ethylenically unsaturated acid-functional monomer and at least
one alkanol having the formula ROH, wherein R is a linear or
branched chain alkyl moiety having greater than 11 carbon atoms,
into a reaction zone to form a reaction mixture; maintaining a flow
rate through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer; (b)
charging the reactor with a base and water; (c) dispersing a
compound selected from the group consisting of an oil and a wax
into the resin melt; and (d) charging additional water into the
reactor.
88. A stabilized compound prepared according to claim 83.
89. A barrier coating, comprising: (a) a polymeric product, the
polymeric product produced by a continuous bulk polymerization and
esterification process comprising: continuously charging at least
one ethylenically unsaturated acid-functional monomer and at least
one alkanol having the formula ROH, wherein R is a linear or
branched chain alkyl moiety having greater than 11 carbon atoms,
into a reaction zone to form a reaction mixture; maintaining a flow
rate through the reaction zone sufficient to provide an average
residence time of the reaction mixture in the reaction zone of less
than 60 minutes; and maintaining an effective temperature in the
reaction zone sufficient to produce the polymeric product
incorporating at least some of the alkanol as an ester of the
polymerized ethylenically unsaturated acid-functional monomer; (b)
an emulsion polymer; and (c) a paraffin wax emulsion.
90. The barrier coating according to claim 89, wherein the water
vapor transmission rate of a film with a thickness of 0.9 mils is
less than 6 grams per 100 square inches per 24 hours at 90 percent
relative humidity and 37.8.degree. C.
91. The barrier coating according to claim 90, wherein the water
vapor transmission rate of the film is less than 3 grams per 100
square inches per 24 hours at 90 percent relative humidity and
37.8.degree. C.
92. A barrier coating, comprising: (a) the polymeric product
consisting of (i) about 3 to 97 percent by weight of at least one
ethylenically unsaturated acid-functional monomer which has been
polymerized into the polymeric product, (ii) about 3 to 97 percent
by weight at least one alkyl ester of the ethylenically unsaturated
acid-functional monomers, wherein the alkyl group is a linear or
branched chain alkyl radical having greater than 11 carbon atoms
which has been polymerized into the polymeric product, (iii) about
0 to about 85 percent by weight of at least one aromatic
ethylenically unsaturated monomer which has been polymerized into
the polymeric product: and (iv) about 0 to about 85 percent by
weight of at least one non-aromatic ethylenically unsaturated vinyl
monomer which has been polymerized into the polymeric product,
wherein an aqueous resin cut at a solids content of 30.5%, a pH of
from 7.7 to 8.2, and a temperature of 25C., of the polymeric
product has a solution viscosity which is less than about 50
percent of the solution viscosity of an aqueous resin cut at a
solids content of 30.5%, a pH of 7.8, and a temperature of 25C., of
a second polymeric product identical to the polymeric product
except that it does not contain any of the alkyl ester of the
ethylenically unsaturated acid-functional monomers of (ii), and
wherein the weight percent of (i), (ii), (iii) and (iv) is base on
the total weight of the polymeric product; (b) an emulsion polymer;
and (c) a paraffin wax emulsion.
93. The barrier coating according to claim 92, wherein the water
vapor transmission rate of a film with a thickness of 0.9 mils is
less than 6 grams per 100 square inches per 24 hours at 90 percent
relative humidity and 37.8.degree. C.
94. The barrier coating according to claim 93, wherein the water
vapor transmission rate of the film is less than 3 grams per 100
square inches per 24 hours at 90 percent relative humidity and
37.8.degree. C.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of provisional patent
application No. 60/092,405, filed Jul. 10, 1998, the disclosure of
which is incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a bulk polymerization and
esterification process for maximizing the conversion of an
aliphatic alkanol to an ester in a radically-initiated
polymerization of an ethylenically unsaturated acid-functional
monomer, to the polymeric products produced by the process, to
polymeric products, to processes for preparing emulsions and
dispersions utilizing the polymeric products, and to overprint
varnishes (OPVs), inks, coatings, surfactants, adhesives, paints,
primers, and floor polishes containing the polymeric products.
BACKGROUND OF THE INVENTION
[0003] Conventional solvent-based industrial finishes and coatings
have presented many problems to date. Organic solvents can pollute
the workplace and environment. In addition, many organic solvents
are readily ignited, toxic, expensive, and lower the quality of
finishes, and they can add undesirable colors to an otherwise
colorless finish. As a replacement for these solvent-based
finishes, the trend in the polymer industry has been toward high
solids, liquid coatings and polymerization processes reducing or
eliminating solvent.
[0004] High solids coatings offer significant advantages over
conventional, solvent-thinned coatings. For example, high solids
coatings do not pollute the air, they reduce or eliminate exudation
of fumes in use, they reduce the energy requirements for their
preparation in terms of material, energy expended and labor, and
unlike solvent-based systems, they do not present significant fire
and toxicity problems. High solids coatings also provide
substantial advantages over other high solids liquids, such as
solventless, water-borne, powder and non-aqueous systems.
Additionally, they offer a better balance of properties.
[0005] One of the most enduring and difficult problems in preparing
and utilizing high solids coatings is the selection and control of
viscosity. Significant efforts have been made to improve processes
and polymeric products for use in high solids applications. For
example, various methods of characterizing polymers such as the
number average molecular weight (M.sub.n), weight average molecular
weight (M.sub.w), and the sedimentation average molecular weight
(M.sub.z) and ratios calculated using these characteristics such as
the polydispersity ratio (M.sub.w/M.sub.n) and the dispersion index
(M.sub.z/M.sub.n) have been investigated and adjusted to obtain
polymeric products with viscosities useful for high solids
applications. Although these efforts have produced vast
improvements in polymers for use in high solids applications,
improved processes are required to produce polymers with
characteristics maximized for high solids applications.
[0006] U.S. Pat. No. 4,414,370 discloses a continuous bulk
polymerization process for polymerizing vinylic monomers to prepare
low molecular weight polymers employing thermal initiation at
reaction temperatures from 235.degree. C. to 310.degree. C. and
residence times of at least 2 minutes in a continuous stirred
reactor zone. The vinylic monomers of the disclosed process include
styrenic monomers such as styrene and .alpha.-methylstyrene;
acrylic monomers such as acrylic acid, methacrylic acid, acrylates,
methacrylates; and other non-acrylic ethylenic monomers such as
vinyl acetate.
[0007] U.S. Pat. No. 4,529,787 discloses a continuous bulk
polymerization process including an initiator for preparing low
molecular weight, uniform polymers from vinylic monomers at short
residence times and moderate reaction temperatures to provide high
yields of a product suitable for high solids applications. The
disclosed vinyl monomers include styrenic monomers such as styrene
and .alpha.-methylstyrene; acrylic monomers such as acrylic acid,
methacrylic acid, acrylates, methacrylates, and functional acrylic
monomers; and non-acrylic ethylenic monomers such as maleic
anhydride and vinyl pyrrolidone.
[0008] U.S. Pat. No. 4,546,160 discloses a continuous bulk
polymerization process for polymerizing acrylic monomers to prepare
low molecular weight, uniform, polymers for use in high solids
applications which uses a minor amount of initiator at short
residence times and moderate temperatures.
[0009] U.S. Pat. No. 5,130,369 discloses a batch process for
preparing functionalized polymeric compositions. The functionalized
polymeric compositions are prepared by polymerizing an
ethylenically unsaturated functional monomer in a solvent including
a reactive compound. The polymeric compositions prepared according
to the process can be used as builders in detergent compositions,
as pigments, dispersants in coating compositions, as tanning agents
for leather, as associative thickeners and as rheology modifiers in
coating compositions.
[0010] U.S. Pat. No. 5,521,267 discloses a batch process for
preparing polymers from ethylenically unsaturated compounds
containing acid groups with further ethylenically unsaturated
compounds and monohydroxy compounds
[0011] The polymer industry has long known that continuous
polymerization processes are best for obtaining large quantities of
polymeric product. Furthermore, optimized continuous processes
provide economic advantages over batch polymerization processes and
may provide more uniform polymeric products. While continuous
processes have been disclosed for the preparation of certain
polymeric products for use in high solids coatings applications, a
continuous process is needed for preparing polymeric products with
improved viscosity characteristics in aqueous media for use in high
solids applications. Furthermore, a need remains for a
polymerization process which incorporates an esterification
reaction in which an alcohol with desirable viscosity-modifying
behavior is incorporated into a polymeric chain with a high degree
of conversion.
SUMMARY OF THE INVENTION
[0012] It would be highly desirable to be able to produce a
polymeric product exhibiting low viscosity in aqueous solution
using a continuous polymerization process where an alkanol is
incorporated with high conversion into the polymer via an
esterification reaction with an ethylenically unsaturated
acid-functional monomer or a residue of such a monomer already
present in the polymer.
[0013] One object of the invention is to provide a continuous bulk
polymerization and esterification process including charging
continuously into a reaction zone at least one ethylenically
unsaturated acid-functional monomer and at least one alkanol having
the formula ROH, where R is a linear or branched chain alkyl
moiety, or combinations thereof, having greater than 11 carbon
atoms. The process also includes maintaining a flow rate through
the reaction zone sufficient to provide an average residence time
of the monomers in the reaction zone of less than 60 minutes and
maintaining a temperature in the reaction zone sufficient to
produce a polymeric product. Preferably, the polymeric product of
the continuous bulk polymerization and esterification process
incorporates at least 80 percent of the alkanol as an ester of the
ethylenically unsaturated acid-functional monomer when the alkanol
is present in the reaction zone in an average amount of at least up
to 25 mole percent of the total moles of the ethylenically
unsaturated monomers. More preferably, the polymeric product of the
continuous bulk polymerization and esterification process
incorporates at least 85 percent of the alkanol as an ester of the
ethylenically unsaturated acid-functional monomer when the alkanol
is present in the reaction zone in an average amount of at least up
to 20 mole percent of the total moles of the ethylenically
unsaturated monomers. Most preferably, the polymeric product of the
continuous bulk polymerization and esterification process
incorporates at least 90 percent of the alkanol as an ester of the
ethylenically unsaturated acid-functional monomer when the alkanol
is present in the reaction zone in an average amount of at least up
to 15 mole percent of the total moles of the ethylenically
unsaturated monomers.
[0014] In preferred processes, the ethylenically unsaturated
acid-functional monomer is acrylic acid, methacrylic acid, or
crotonic acid while in other preferred processes, the R group of
the alkanol has 12 to 50 carbon atoms and all combinations and
subcombinations and ranges contained therein. More preferably, the
R group of the alkanol has 12 to 36 carbon atoms, or 12 to 22
carbon atoms. In especially preferred processes, the alkanol has 16
to 18 carbon atoms, and in other especially preferred processes a
mixture of alkanols, particularly those having 16 to 18 carbon
atoms is used. In some preferred processes and products, the
polymeric product has an aqueous solution viscosity which is less
than about 50 percent of the aqueous solution viscosity of the
equivalent unmodified polymeric product.
[0015] In still other preferred processes, the polymeric product
has an acid number ranging from about 10 to about 740.
[0016] Other preferred processes further include adding a
polymerization initiator, preferably di-t-butyl peroxide, into the
reaction zone, preferably in an amount to provide a molar ratio of
the initiator to the combined monomers of from about 0.0005:1 to
0.04:1. In other preferred processes, the polymerization and
esterification process incorporates at least 95 percent of the
alkanol as an ester of the polymerized ethylenically unsaturated
acid-functional monomer when the alkanol is present in the reaction
zone in an average amount of at least up to 15 mole percent of the
total moles of the ethylenically unsaturated acid-functional
monomers.
[0017] In preferred processes, the average residence time in the
reaction zone is less than 30 minutes while in other preferred
processes the temperature in the reaction zone ranges from
180.degree. to 270.degree. C.
[0018] Preferred processes include continuously charging into the
reaction zone at least one aromatic ethylenically unsaturated
monomer, a C.sub.1 to C.sub.8 alkyl acrylate monomer, a C.sub.1 to
C.sub.8 alkyl methacrylate monomer, or a non-aromatic ethylenically
unsaturated vinyl monomer, while in other preferred processes at
least two different aromatic ethylenically unsaturated monomers are
continuously charged into the reaction zone.
[0019] In still another preferred process, at least two different
alkanols are continuously charged into the reaction zone.
[0020] Another object of the present invention is to provide a
continuous bulk polymerization and esterification process including
continuously charging into a reaction zone at least one
ethylenically unsaturated acid-functional monomer and at least one
alkanol having the formula ROH, where R is a linear or branched
chain alkyl moiety having from 12 to 50 carbon atoms and all
combinations and subcombinations and ranges contained therein. The
process also includes maintaining a flow rate through the reaction
zone sufficient to provide an average residence time in the
reaction zone of less than 60 minutes and maintaining a temperature
in the reaction zone sufficient to produce a polymeric product. The
polymeric product of the continuous bulk polymerization and
esterification process has a number average molecular weight
ranging from 600 to 20,000. Furthermore, an aqueous resin cut of
the polymeric product has a solution viscosity which is less than
about 50 percent of the solution viscosity of the equivalent
unmodified polymeric product.
[0021] Another object of the invention is to provide a polymeric
product consisting essentially of about 3 to about 97 percent by
weight of a residue of at least one ethylenically unsaturated
acid-functional monomer; about 3 to about 97 percent by weight at
least one ester of the ethylenically unsaturated acid-functional
monomers having an --OR group, where R is a linear or branched
chain alkyl moiety having greater than 11 carbon atoms; about 0 to
about 85 percent by weight of a residue of at least one aromatic
ethylenically unsaturated monomer; and about 0 to about 85 percent
by weight of a residue of at least one non-aromatic ethylenically
unsaturated vinyl monomer.
[0022] A further object of the invention is to provide water-based
compositions including water; from about 0.1 to about 100 percent
by weight based on the total weight of the composition of the
polymeric product of the invention or the polymeric product
produced by the continuous bulk polymerization and esterification
process; and up to about 99 percent by weight based on the total
weight of the composition of an adjunct.
[0023] Preferred water-based compositions contain about 10 to about
99 percent by weight of the adjunct while other preferred
water-based compositions are overprint varnishes, inks, coating
materials, adhesives, floor polishes, paints, primers, and paper
sizing agents.
[0024] A further object of the invention is to provide a process
for preparing an emulsion of a polyolefin resin which includes
mixing together a polyolefin resin and the polymeric product of the
bulk polymerization and esterification process; mixing a base with
the combination; and mixing the combined base, resin and polymeric
product with water.
[0025] Another object of the invention is to provide the emulsion
prepared by the above emulsion preparation process.
[0026] Still another object of the invention is to provide an
emulsion of a polyolefin resin which includes a polyolefin resin,
the polymeric product of the invention, a base, and water. In
preferred processes and compositions containing a polyolefin resin,
the polyolefin resin has a number average molecular weight ranging
from about 500 to about 20,000, an acid number of about 0 to about
150, or a melting point of about 40.degree. to about 250.degree.
C.
[0027] Yet another object of the invention is to provide a process
for preparing a wax dispersion which includes mixing a wax in an
aqueous medium with the polymeric product of the continuous bulk
polymerization and esterification process.
[0028] Yet another object of the invention is to provide a wax
dispersion prepared according to the above process for preparing a
wax dispersion.
[0029] Yet another object of the invention is to provide a wax
dispersion which includes a wax; the polymeric product of the
invention; and an aqueous medium.
[0030] A still further object of the invention is to provide a
process for preparing an oil emulsion which includes heating a
mixture of an oil and the polymeric product of the continuous bulk
polymerization and esterification process; mixing a base with the
heated mixture of the oil and the polymeric product; and mixing
water with the combined components.
[0031] Still another object of the invention is to provide an oil
emulsion prepared according to the above process for preparing an
oil emulsion.
[0032] Yet another object of the invention is to provide an oil
emulsion which includes an oil; a base; the polymeric product; and
water.
[0033] Preferred processes for preparing emulsions, emulsion
compositions, processes for preparing dispersions, and dispersion
compositions optionally include a conventional surfactant,
preferably an anionic or non-ionic surfactant, in an amount up to
about 10 percent by weight based on the total weight of solids.
[0034] Still another object of the invention is to provide a
process for improving the viscosity profile of an aqueous pigment
dispersion which includes adding the polymeric product of the
continuous bulk polymerization and esterification process to an
aqueous pigment dispersion.
[0035] A still further object of the invention is to provide an
aqueous pigment dispersion with an improved viscosity profile that
includes an aqueous pigment dispersion; and the polymeric
product.
[0036] Yet another object of the invention is to provide a process
for increasing the total solids concentration of an aqueous coating
which includes adding the polymeric product of the continuous bulk
polymerization and esterification process to an aqueous
coating.
[0037] A still further object of the invention is to provide an
aqueous coating having an increase in total solids which includes
an aqueous coating; and the polymeric product.
[0038] Another object of the invention is to provide a process for
stabilizing a compound in an aqueous medium which includes
providing a resin melt of the polymeric product of the continuous
bulk polymerization and esterification process in a reactor
operating at or above atmospheric pressure; charging the reactor
with a base and water; dispersing an oil or a wax into the resin
melt; and charging additional water into the reactor.
[0039] In preferred processes and compositions, the base is
ammonia, diethylaminoethanol, morpholine, sodium hydroxide,
potassium hydroxide or mixtures of these.
[0040] Another object of the invention is to provide a stabilized
compound prepared according to the above process.
[0041] Another object of the invention is to provide a polymeric
surfactant which includes at least one ethylenically unsaturated
acid-functional monomer which has been radically incorporated into
the polymeric surfactant and at least one ester of the incorporated
ethylenically unsaturated acid-functional monomer having an R alkyl
group. The R group is a linear or branched chain alkyl moiety
having greater than 11 carbon atoms, and the molar critical micelle
concentration of the neutralized aqueous polymeric surfactant is
less than 1.0.times.10.sup.-2 moles/liter.
[0042] Another object of the invention is to provide a polymeric
surfactant which includes at least one ethylenically unsaturated
acid-functional monomer which has been radically incorporated into
the polymeric surfactant and at least one ester of the incorporated
ethylenically unsaturated acid-functional monomer having an R alkyl
group. The R group is a linear or branched chain alkyl moiety
having greater than 11 carbon atoms, and a 2 percent neutralized
aqueous solution of the polymeric surfactant has a surface tension
of less than 45 mN/m at 30.degree. C. and undergoes a decrease in
surface tension of at least 5 mN/m as the temperature of the
solution warms from 30.degree. C. to 50.degree. C.
[0043] In preferred embodiments, the surface area per molecule of
the polymeric surfactant is less than 36 .ANG..sup.2. In other
preferred embodiments, the molar critical micelle concentration of
the polymeric surfactant is less than 8.2.times.10.sup.-3
moles/liter, and in even more preferred embodiments, the molar
critical micelle concentration is less than 1.0.times.10.sup.-3
moles/liter. In still other preferred embodiments, the polymeric
surfactant further includes at least one vinyl aromatic monomer
incorporated into the polymeric surfactant, and in more preferred
embodiments at least two vinyl aromatic monomers are incorporated
into the polymeric surfactant.
[0044] Still another object of the invention is to provide a
barrier coating that includes a polymeric product according to the
invention, an emulsion polymer, and a paraffin wax emulsion. In
preferred embodiments, the barrier coating has a water vapor
transmission of less than 6, more preferably less than 3, grams per
100 square inches per 24 hours at 90 percent relative humidity and
37.8.degree. C.
[0045] Still further objects, features, and advantages of the
invention will be apparent from the following detailed description
when taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0046] The preferred exemplary embodiment of the invention will
hereinafter be described in conjunction with the appended drawings,
wherein like numerals denote like elements and:
[0047] FIG. 1 is a schematic diagram of a portion of a polymer
production line of the present invention;
[0048] FIG. 2 is a graph of resin type versus cut viscosity at
25.degree. C. for conventional and exemplary resins with pH ranging
from 8.0 to 8.5;
[0049] FIG. 3 is a graph of resin type versus cut viscosity at
25.degree. C. for conventional and exemplary resins at
approximately equal M.sub.w and acid number with pH ranging from
8.3 to 8.8;
[0050] FIG. 4 is a graph comparing the conversion rates of
aliphatic alkanols (1-tetradecanol and 1-docosanol) and diethylene
glycol monoethyl ether to the corresponding esters in a
radically-initiated polymerization of a monomer having an
ethylenically unsaturated acid-functional group to obtain a
modified polymers exhibiting low solution viscosity in an aqueous
medium;
[0051] FIG. 5 is a graph illustrating the viscosity of various
aqueous resin cuts at 25.degree. C. and 48.3% solids content and
the relationship between viscosity and the number of carbons in the
alkanol;
[0052] FIG. 6 is a graph illustrating the viscosity of various
aqueous resin cuts at 25.degree. C. and 30.5% solids content and
the relationship between viscosity and the number of carbons in the
alkanol;
[0053] FIG. 7 is a graph illustrating the relative incorporation of
various linear and branched chain alkanols at a constant
temperature into a polymer formed by polymerizing an ethylenically
unsaturated acid-functional monomer using the process of the
present invention;
[0054] FIG. 8 is a graph comparing the surface tensions of aqueous
solutions of Exemplary Resins 39 and 40 with Conventional Resin 6
and FC-120, a brand of fluorosurfactant available from 3M
Corporation (Minneapolis, Minn.), at various concentrations;
[0055] FIG. 9 is a graph comparing the surface tensions of 2%
aqueous solutions of Exemplary Resins 2, 3, and 43; Conventional
Resins 4-6, and 16; and sodium lauryl sulfate with that of water at
various temperatures;
[0056] FIG. 10 is a graph comparing the surface tensions of 2%
aqueous solutions of Exemplary Resins 2, 3, and 43; Conventional
Resins 4-6 and 16; and sodium lauryl sulfate at various
temperatures; and
[0057] FIG. 11 is a graph comparing the surface pressure (surface
tension of water --surface tension of the solution) of 2% aqueous
solutions of Exemplary Resins 2, 3, and 43; Conventional Resins 4-6
and 16; and sodium lauryl sulfate at various temperatures.
DETAILED DESCRIPTION OF THE INVENTION
[0058] The process of the present invention combines polymerization
and esterification reactions in a reaction zone. The continuous
polymerization and esterification process includes continuously
charging into a reaction zone at least one ethylenically
unsaturated acid-functional monomer and at least one alkanol;
maintaining a flow rate through the reaction zone sufficient to
provide an average residence time of the monomers in the reaction
zone of less than 60 minutes; and maintaining a temperature in the
reaction zone sufficient to provide a polymeric product.
[0059] The term "low viscosity" is hereby defined as a polymeric
product which exhibits an aqueous solution viscosity which is less
than about 50 percent of the aqueous solution viscosity of the
equivalent unmodified polymeric product at identical
concentrations. The term "equivalent unmodified polymeric product"
is hereby defined as a composition having about the same M.sub.n
and acid number which is prepared in an identical fashion as the
polymeric product except that no alkanol is incorporated into the
composition. The term "continuous" is herein defined as a process
wherein a reactant, such as an alkanol and/or an ethylenically
unsaturated acid-functional monomer, is fed into a reactor while a
polymeric product is removed simultaneously during at least part of
the reaction process.
[0060] The continuous bulk polymerization and esterification
process includes continuously charging into a reaction zone at
least one ethylenically unsaturated acid-functional monomer
although a mixture of one or more ethylenically unsaturated
acid-functional monomers may be used in the process. The
ethylenically unsaturated acid-functional monomer is an
.alpha.,.beta.-unsaturated carboxylic acid such as, but not limited
to, acrylic acid, methacrylic acid, and crotonic acid.
[0061] The continuous bulk polymerization and esterification
process also includes continuously charging at least one alkanol
into the reaction zone although a mixture of one or more alkanols
may be used in the process. The terms "alkanol" or "ROH" as used
herein refer to both saturated and unsaturated alcohols, and the
term "R" refers to both unsaturated and saturated alkyl groups. The
alkanol used in the process may be represented by the formula ROH
where R is a linear or branched chain, or combinations thereof,
alkyl moiety having greater than 11 carbon atoms. Preferably, the
alkanol contains from 12 to 50 carbon atoms and all combinations
and subcombinations and ranges contained therein. More preferably,
the alkanol contains from 12 to 36 carbon atoms. In an even more
preferred embodiment, the alkanol contains from 12 to 22 carbon
atoms. In most preferred processes, the alkanol has 16 to 18 carbon
atoms. Examples of primary alkanols for use in the process include,
but are not limited to, 1-dodecanol, 1-tridecanol, 1-tetradecanol,
1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol,
1-nonadecanol, 1-eicosanol, 1-docosanol, 1-tetracosanol,
1-hexacosanol, 1-octacosanol, 1-triacontanol, 1-tetracontanol,
1-pentacontanol, and other similar primary alkanols. Longer chain
alcohols such as those sold under the trademark Unilin.TM. 350,
425, 550, and 700 available from Baker-Petrolite, Inc. (Tulsa,
Okla.), may also be used in the present invention as may alkanols
containing sites of unsaturation such as, but not limited to oleyl
alcohol, a C18 alcohol available from Jarchem Industries (Newark,
N.J.). Among others, commercial manufacturers of alcohols for use
in the present invention include Condea Vista (Houston, Tex.),
Ashland Chemical, Inc. (Columbus, Ohio), Witco Corp. (Greenwich,
Conn.), and Henkel Corp. (Cincinnati, Ohio). Moreover, in preferred
processes, a mixture of two, three or more alcohols may be
continuously charged into the reaction zone according to the
present invention. A preferred mixture of alcohols have linear or
branched chain R groups of from 16 to 18 carbon atoms.
[0062] Other monomers are preferably used in the current process.
For example additional monomers such as aromatic ethylenically
unsaturated monomers, which include, but are not limited to, alkyl
acrylates and alkyl methacrylates, and non-aromatic ethylenically
unsaturated vinyl monomers may be charged into the reaction zone in
the continuous bulk polymerization and esterification process.
Additionally, mixtures of these monomers may be used.
[0063] Aromatic ethylenically unsaturated monomers that may be used
in the process are styrenic monomers that include, but are not
limited to, styrene, .alpha.-methylstyrene, vinyl toluene,
p-methylstyrene, t-butylstyrene, o-chlorostyrene, vinyl pyridine,
and mixtures of these species. Preferred ethylenically unsaturated
monomers for use in the process include styrene and
.alpha.-methyl-styrene. In preferred embodiments, at least two
different aromatic ethylenically unsaturated monomers are
continuously charged into the reaction zone in addition to the
ethylenically unsaturated acid-functional monomer and alkanol.
Preferably, the two different aromatic ethylenically unsaturated
monomers added to the reaction zone include styrene and
.alpha.-methylstyrene, preferably in a ratio of from 1:2 to 2:1,
such that a polymeric product is formed which includes residues of
styrene, .alpha.-methylstyrene, and an ethylenically unsaturated
acid-functional monomer such as acrylic acid, methacrylic acid, or
crotonic acid where the residues of the ethylenically unsaturated
acid-functional monomer are present either as the carboxylic acid
or the ester formed during the polymerization and esterification
process. A preferred monomer charge in the polymerization and
esterification process employs from about 60-80 percent by weight
of an aromatic ethylenically unsaturated monomer and 40-20 percent
by weight of an ethylenically unsaturated acid-functional monomer,
such as acrylic acid. Other preferred processes wherein at least
one aromatic ethylenically unsaturated monomer is charged into the
reaction zone produce a polymeric product having an M.sub.n from
700 to 5000 and an acid number from 140 to 300.
[0064] In addition to the ethylenically unsaturated acid-functional
monomer and the alkanol, other preferred polymerization and
esterification processes include charging into the reaction zone at
least one aromatic ethylenically unsaturated monomer and at least
one acrylate or methacrylate monomer.
[0065] Another type of monomer that may be added to the reaction
zone in the process is an alkyl acrylate or alkyl methacrylate
monomer. Monomers of this type include typical alkyl acrylates and
methacrylates and functional acrylates and methacrylates.
Functional acrylates and methacrylates include at least one
functional group in addition to the ester and alkene
functionalities. A non-exhaustive list of exemplary alkyl acrylates
and methacrylates includes methyl acrylate, ethyl acrylate,
n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl
acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate,
i-amyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate,
cyclopentyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl
acrylate, cinnamyl acrylate, 2-phenylethyl acrylate, allyl
acrylate, methallyl acrylate, propargyl acrylate, crotyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl
acrylate, 6-hydroxyhexyl acrylate, 5,6-dihydroxyhexyl acrylate,
2-methoxybutyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl
acrylate, 2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, glycidyl
acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate,
tetrahydropyryl acrylate, N,N-dimethylaminoethyl acrylate,
N,N-diethylaminoethyl acrylate, N-butylaminoethyl acrylate,
2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl acrylate,
trifluoroethyl acrylate, hexafluoroisopropyl acrylate,
2-nitro-2-methylpropyl acrylate, 2-sulfoethyl acrylate, methyl
.alpha.-chloroacrylate, methyl .alpha.-cyanoacrylate, and the
corresponding methacrylates.
[0066] Preferred alkyl acrylates and methacrylates for use in the
continuous bulk polymerization and esterification process include
alkyl groups having from 1 to 8 carbon atoms in the alkyl group
attached to the non-carbonyl oxygen atom of the alkyl acrylate or
methacrylates. Examples of such compounds include methyl, ethyl,
propyl, butyl, i-butyl, i-amyl, 2-ethylhexyl, and octyl acrylates
and methacrylates. Other preferred alkyl acrylates and
methacrylates for use in the polymerization and esterification
process include acrylates and methacrylates having an OR group
where R has the same characteristics as it does in the alkanol of
the present invention, i.e., R is a linear or branched alkyl moiety
having greater than 11 carbon atoms, preferably 12 to 50, more
preferably 12 to 36, even more preferably 12 to 22, and most
preferably 16 to 18 carbon atoms.
[0067] Monomers that contain functional groups such as, but not
limited to, amino, isocyanate, and epoxy groups, which are capable
of reacting with either the alkanol or the ethylenically
unsaturated acid-functional monomer of the invention should
preferably not be used in the process.
[0068] Non-aromatic ethylenically unsaturated monomers may also be
added to the reaction zone in the continuous bulk polymerization
and esterification process. Examples of such monomers include vinyl
esters and also vinyl acetate, maleic acid, vinyl pyrrolidone, and
maleic anhydride. Other non-aromatic ethylenically unsaturated
monomers that may be added to the reaction zone are related to the
above-described esters of acrylic and methacrylic acid. These
include amides of acrylic and methacrylic acid, nitriles, and
aldehydes. Examples of suitable amides include acrylamide, N-ethyl
acrylamide, N,N-diethyl acrylamide, N-methyl acrylamide,
N,N-dimethyl acrylamide, N-phenyl acrylamide, and the corresponding
methacrylamides. Examples of suitable nitriles and aldehydes
include acrylonitrile, acrolein, methacrylonitrile, and
methacrolein.
[0069] Preferred monomer charges in the continuous bulk
polymerization and esterification process include comonomers,
termonomers, and tetramonomers. Examples of preferred comonomers
include styrene and acrylic acid; styrene and methacrylic acid;
vinyltoluene and acrylic acid; and 2-ethylhexyl acrylate and
acrylic acid. Examples of preferred termonomers include styrene,
.alpha.-methylstyrene, and acrylic acid; styrene, n-butyl acrylate
and acrylic acid; styrene, n-butyl methacrylate and acrylic acid;
and styrene, methyl methacrylate and acrylic acid. Examples of
preferred tetramonomers include styrene, butyl acrylate, methyl
methacrylate, and methacrylic acid; styrene, n-butyl acrylate,
ethylacrylate and acrylic acid; and styrene, .alpha.-methyl
styrene, n-butyl acrylate and acrylic acid.
[0070] In preferred processes where both an aromatic ethylenically
unsaturated monomer and an alkyl acrylate or methacrylate are
charged into the reaction zone, the weight ratio of the aromatic
ethylenically unsaturated monomer to the alkyl acrylate or
methacrylate preferably ranges from 2:1 to 1:2.
[0071] Although no initiator is required in the radically-initiated
continuous bulk polymerization and esterification process, an
initiator may be added to the reaction zone. The initiators
suitable for carrying out the continuous bulk polymerization and
esterification process are compounds which decompose thermally into
radicals in a first order reaction. Suitable initiators preferably
have half-life periods in the radical decomposition process of
about 1 hour at 90.degree. C. and more preferably 10 hours at
100.degree. C. Others with about 10 hour half-lives at temperatures
significantly lower than 100.degree. C. may also be used. Suitable
initiators include, for example, aliphatic azo compounds,
peroxides, peresters, and hydroperoxides such as
1-t-amylazo-1-cyanocyclohexane, azo-bis-isobutyronitrile,
1-t-butylazo-1-cyanocyclohexane, t-butylperoctoate, t-butyl
perbenzoate, dicumyl peroxide, di-t-butyl peroxide, cumene
hydroperoxide, t-butyl hydroperoxide and the like. The particular
initiator is not critical so long as the initiator will generate
free radicals. However, di-t-butyl peroxide is a preferred
initiator in the polymerization and esterification process.
[0072] It has been found that when the molar ratio of initiator to
monomer charge is at least about 0.0005:1, it is possible to reduce
reaction temperature to improve purity, color, conversion and ease
processing conditions, while maintaining or improving low molecular
weight and molecular weight distribution.
[0073] Use of excess initiator is costly and does not significantly
improve either the properties of the resulting polymer nor the
reaction conditions sufficiently, to normally justify its use.
Accordingly, in general, a mole ratio no greater than about 0.04:1
of initiator to total monomers charged need be employed. If
desired, a somewhat higher ratio may be employed, under certain
circumstances, usually up to about 0.06:1, to provide another means
to reduce the molecular weight and improve distribution of the
resulting product. However, best conversion and weight distribution
is usually achieved with the mole ratio at 0.0005:1 to 0.04:1. It
is believed that the present reaction is primarily thermally
initiated, with the minor amounts of initiator utilized cooperating
to permit reduced reaction temperatures and improving conversion
and distribution characteristics. Therefore, sufficient amounts of
initiator are employed for this purpose. For industrial purposes a
molar ratio of about 0.005:1 to 0.015:1 of initiator to monomers is
most preferably used.
[0074] The initiator is preferably added simultaneously with the
monomer or monomers. Thus, if an initiator is employed, it is
either mixed with the monomer feed or added to the reaction zone as
a separate feed. Initiator levels are an important consideration in
the process of this invention.
[0075] The temperature in the reaction zone of the continuous bulk
esterification and polymerization process is generally maintained
at greater than about 150.degree. C. or a temperature sufficient to
produce a polymeric product such that the polymeric product of the
bulk polymerization and esterification process incorporates at
least 80 percent of the alkanol as an ester of the ethylenically
unsaturated acid-functional monomer when the alkanol is present in
the reaction zone in an average amount of at least up to 25 mole
percent of the total moles of the ethylenically unsaturated
monomers. More preferably, the polymeric product of the continuous
bulk polymerization and esterification process incorporates at
least 85 percent of the alkanol as an ester of the ethylenically
unsaturated acid-functional monomer when the alkanol is present in
the reaction zone in an average amount of at least up to 20 mole
percent of the total moles of the ethylenically unsaturated
monomers. Most preferably, the polymeric product of the continuous
bulk polymerization and esterification process incorporates at
least 90 percent of the alkanol as an ester of the ethylenically
unsaturated acid-functional monomer when the alkanol is present in
the reaction zone in an average amount of at least up to 15 mole
percent of the total moles of the ethylenically unsaturated
monomers.
[0076] In general, for these and other purposes, the reaction
temperature is preferably maintained at from about 180.degree. C.
to about 275.degree. C. and to all combinations and subcombinations
within this range. At temperatures below about 180.degree. C., the
polymer product tends to exhibit a higher molecular weight and
broader molecular weight distribution than is generally acceptable
for high solids applications, unless excessive solvent addition is
employed. The reaction conversion rate is reduced and higher
molecular weight fractions are also increased. The product tends to
become unduly viscous for efficient processing and high solids
products cannot be obtained readily. At reaction temperatures from
about 180.degree. C. to about 215.degree. C., it is often useful to
employ a solvent to increase the uniformity of the product, obtain
fewer chromophores, and reduce viscosity. If desired, the amount of
initiator employed may be increased in accordance with the
invention to improve reaction parameters and enhance product
properties. In more preferred processes, reaction temperatures are
maintained from about 215.degree. C. to about 275.degree. C. and to
all combinations and subcombinations within this range such as from
about 215.degree. C. to about 270.degree. C. or from about
230.degree. C. to about 275.degree. C.
[0077] Although higher reaction temperatures may be employed, at
temperatures above about 310.degree. C., the temperature can have
adverse effects on the product of the continuous polymerization and
esterification process, such as excessive chromophore production.
Excess temperature may also result in excessive equipment
maintenance.
[0078] In general, the reaction time or residence time in the
reaction zone is controlled by the rate of flow of constituents
through the reaction system. The residence time is inversely
proportional to flow rate. It has been found that at a given
temperature, the molecular weight of the polymer product decreases
as the residence time increases.
[0079] In accordance with these factors, it is therefore preferred
to utilize reaction average residence times of at least 1 minute to
provide satisfactory reaction completion in the bulk polymerization
and esterification process. Often this lower limit is controlled by
polymerization heat removal or the difficulty in achieving
steady-state reaction conditions. While the residence time in the
reaction zone may be longer than 1 hour at lower reaction
temperatures, normally discoloring reactions and other side
reactions will dictate that residence times shorter than 1 hour be
employed. For most cases, preferred average residence times of from
about 1 to 30 minutes and, more preferably, from 1 to 20 minutes
are employed.
[0080] In general, longer residence times may increase the yield of
product, but the rate of increase of product yield is generally
very slow after about 30 minutes of reaction. More importantly,
after about 30 minutes, depolymerization tends to occur with
formation of undesired chromophores and by-products. However, the
particular flow rate selected will depend upon the reaction
temperature, constituents, and desired molecular weight of product.
Thus, for best results, to produce a given resin with a desired
M.sub.n and M.sub.w with low residual monomer, the reaction
temperature and residence times are mutually manipulated.
[0081] Other processes to produce these product include multiple
reactor configurations in which one or more subsequent reactors are
utilized in series. In particular, any situation in which it is
desired to raise the conversion of the alkanol or the monomer, it
is appropriate to configure a subsequent reactor (as the primary)
in the process. Any appropriate reactor(s) could be used subsequent
to the primary reactor such as a tube reactor (usually fitted with
a static mixer), a CSTR, an extruder reactor, a loop reactor, or
any reactor type in which the reaction can proceed in a continuous
manner. Additionally, although less preferred, the subsequent
reactor(s) could be a batch reactor whereby the product from the
continuous reactor is fed into a batch reactor where the mixture is
held for further reaction to occur. The temperature of the
subsequent reactor(s) would be maintained at about 180.degree. C.
to about 270.degree. C. (not necessarily the same reactor) with a
residence time of 1-60 minutes, however, longer residence times can
be used.
[0082] Although no solvent is required in the continuous bulk
polymerization and esterification process, a solvent may be added
to the reaction zone. If desired, from about 0 to about 25 percent
and preferably from 0 to about 15 percent of reaction solvent is
employed based on the weight of monomers. The solvent, when
employed, is added to the reaction zone with the monomer feed or is
added to the reaction as a separate feed. The selection of a
particular solvent and its level of addition is made based on the
monomers selected, solubility considerations, suitability to
reaction conditions, and the desired applications for the polymer
produced. In general, it is preferred to use as little solvent as
possible to reduce separation and recovery requirements and
minimize formation of contaminants.
[0083] In general, the use of a solvent permits a lower reaction
temperature to be employed, reduces the solution viscosity of the
molten polymer product, acts as a heat sink to prevent run-away
reactions and reduce cooling requirements, assists in plasticizing
the polymer product, may reduce the acid number if the solvent
esterifies with the resin, and may reduce the molecular weight of
the resulting polymeric product.
[0084] Most conventional polymerization or reaction solvents may be
utilized in the continuous bulk polymerization process to prepare
lower molecular weight polymers. The higher boiling solvents are
preferred due to their low pressure at high temperatures. In
general, preferred solvents have a boiling point above 100.degree.
C., more preferably above 150.degree. C. Examples of higher boiling
solvents include the aromatic alcohols, such as benzyl alcohol, the
toluene alcohols and the like; the alcohol and glycol ethers,
esters and mixed ethers and esters, such as diethylene glycol,
Cellosolve.TM. (a brand of solvent available from the Union Carbide
Corporation (Danbury, Conn.)), butyl Cellosolve, Cellosolve
acetate, the Carbitols.TM. (a brand of solvent available from the
Union Carbide Corporation (Danbury, Conn.)), the (poly) alkylene
glycol dialkyl ethers and the like. However, lower boiling point
solvents including, but not limited to, isopropyl alcohol and
acetone may be used in the process.
[0085] In addition, if there is minimal reaction, some glycols may
also be utilized as the reaction solvent including ethylene,
propylene and butylene glycols and their various polyether analogs.
The aliphatic alcohols, such as hexanol and decanol, can also be
used. Although other alcohols may be used as solvents, care should
be taken to avoid choosing solvents which react more readily with
the ethylenically unsaturated acid-functional monomer than does the
alkanol of the process or the desired level of alkanol
incorporation into the polymer may not be obtained due to the
competing reaction between the solvent and the ethylenically
unsaturated acid-functional monomer. Further, various hydrocarbon
fractions may be utilized, the most preferred being Aromatic 150,
Aromatic 100, or Isopar solvents all available from the Exxon
Chemical Company (Houston, Tex.). Aromatic solvents can also be
employed, for example, toluene, xylene, cumene, and ethyl
benzene.
[0086] Although no catalyst is required in the continuous bulk
polymerization and esterification process, optionally, a catalyst
is added to the reaction components in the reaction zone. In
preferred processes, however, no catalyst is used. When a catalyst
is employed, the catalyst is selected from the group consisting of
an esterification catalyst and a transesterification catalyst. For
example, a catalyst such as p-toluenesulfonic acid may be added to
the reaction zone to increase the rate of reaction between the
alkanol and carboxylic acid functionality on the ethylenically
unsaturated acid-functional monomer or the residue of the monomer
in the polymeric chain during the polymerization reaction.
[0087] It is not necessary to add a chain transfer agent to the
continuous bulk polymerization and esterification process. However,
if desired, any standard chain transfer agent known to those
skilled in the art may be added to the reaction zone. Examples of
some typical chain transfer agents include, but are not limited to,
bromotrichloromethane and isooctyl .beta.-mercaptopropionate.
Benzyl alcohols and secondary alcohols such as, but not limited to
isopropyl alcohol, are also good chain transfer agents. If added, a
chain transfer agent is preferably used in an amount up to about 2
mole percent.
[0088] Continuous polymerization methodologies are well known in
the art. The radical polymerization processes described in U.S.
Pat. No. 4,414,370, U.S. Pat. No. 4,529,787, and U.S. Pat. No.
4,546,160 may be used in conjunction with the reactants described
herein. These patents describe continuous polymerization processes
for polymerizing vinylic monomers including acrylic monomers and
mixtures of acrylic monomers with aromatic ethylenically
unsaturated monomers. Thus, U.S. Pat. No. 4,414,370, U.S. Pat. No.
4,529,787, and U.S. Pat. No. 4,546,160 are herein expressly
incorporated by reference in their entirety.
[0089] The process of the present invention may be conducted using
any type of reactor well-known in the art, preferably in a
continuous configuration. Such reactors include, but are not
limited to, continuous stirred tank reactors ("CSTRs"), tube
reactors, loop reactors, extruder reactors, or any reactor suitable
for continuous operation. Additionally, one or more reactors, in
any combination such as in parallel, in series, or both, may be
used in the current process.
[0090] In one preferred embodiment, the reaction zone of the
continuous bulk polymerization and esterification process generally
comprises a CSTR of any type adapted for variable fillage operation
of from as low as 10% to as much as 100% of the usable volume
thereof for the production of esterified polymers. The CSTR
generally used in the process may be either horizontal or vertical
and should have provision for close control of the temperature
therein by any desired means, including control by a cooling
jacket, internal cooling coils or by withdrawal of vaporized
monomer and alkanol followed by condensation thereof and return of
the condensed reactants to the reaction zone.
[0091] A preferred form of CSTR which has been found suitable for
carrying out the process is a tank reactor provided with cooling
coils sufficient to remove any heat of polymerization not taken up
by raising the temperature of the continuously charged monomer
composition so as to maintain a preselected temperature for
polymerization therein. Preferably such a CSTR will be provided
with at least one and usually more, vane agitators to provide a
well-mixed reaction zone.
[0092] In operating the present continuous bulk, polymerization
process, flexibility and range of choice may be realized in the
types of polymer produced and the production rate of the polymer by
proper choice of polymerization reaction conditions. In operation,
at least one ethylenically unsaturated acid-functional monomer and
at least one alkanol are continuously charged to the reactor and
maintained at the desired temperature. The reactor is generally
charged from a stirred feed tank which contains the mixed
reactants. However, the monomer or monomers and alkanol may also be
individually charged into the reactor.
[0093] After initially filling the reactor to the desired level and
initiating the polymerization and esterification of the charged
reactants, the volume of reactant composition charged into the
reactor is adjusted to maintain a desired level of reactant and
polymeric product mixture in the reactor. Thereafter, the liquid
mixture of polymer and unreacted monomer or monomers and alkanol is
withdrawn from the reactor at a rate to maintain the desired level
in the reaction zone. Polymerization conditions are maintained in
the reactor to produce a polymer of selected molecular weight
percent solids of polymer in such liquid mixture.
[0094] As noted, the level that the reactor is filled can vary from
as low as 10% to as high as 100% of the usable volume and may be
controlled by any desired means, for example, a level controller
associated with a valve or pump in the transfer line from the
reactor.
[0095] Any desired means of controlling the temperature within the
reactor may be employed. It is preferred that the temperature be
controlled by circulation of a cooling fluid, such as oil, through
internal cooling coils in reactors so equipped. Generally, the
entry of relatively cool reactants serves to remove the greatest
proportion of the heat of polymerization released, and the internal
cooling coils serve to remove the remainder so as to maintain the
temperature of the reaction mixture at a preselected value. Thus, a
polymer is produced that has the desired degree of alkanol
incorporation and molecular weight distribution.
[0096] After reaction, the resulting mixture is typically subjected
to separation and product recovery. Unreacted monomer and alkanol
is preferably recycled to the reaction zone or the monomer feed.
During the separation step, volatile components, such as solvent
and other by-products are vaporized and recycled, where
appropriate. For this step, conventional equipment is readily
available, such as a thin film evaporator, falling strand
evaporator or any appropriate devolatization equipment.
[0097] One non-limiting methodology of conducting the present
process according to the present invention will be described with
respect to FIG. 1. FIG. 1 is a schematic diagram of a portion of an
exemplary polymer process line 1 using a CSTR. Fresh monomer feed 2
conveys the monomer or monomers of the present invention into CSTR
4 having agitator 6. CSTR 4 provides the proper choice of reaction
conditions for obtaining the desired types of polymers. The
polymeric product of the reaction is then fed from CSTR 4 to
devolatizer 16 for devolatization. The polymer product is fed by
way of conduit 15 for additional processing, or as a final product
as desired. Condensed distillate is fed by way of conduits 14 and
10 to recycle feed 8 back into CSTR 4 and/or purged by way of purge
12 as desired. Preferably, a separate feed 18 of molten alkanol is
provided into CSTR 4. In this preferred embodiment, a separate tank
20 preheats the alkanol to a molten state. Between condenser 22 and
devolatizer 16 is optional partial condensing unit 24, that may be
a heated unit. Condenser 24 splits out the higher boiling fractions
of the distillate stream and optionally recycles it to CSTR 4 a
portion of which can be purged via 25. Optionally, the condensate
from 22 may be returned to CSTR 4 or purged via 12 from the reactor
system. Optionally, condenser 24 may be replaced by an apparatus or
system such as, but not limited to, membrane separation systems,
distillation, and centrifugation.
[0098] Although CSTR 4 is depicted as a CSTR, reactor 4 also
includes reactors capable of continuous, semi-batch, and batch
processes although reactors capable of continuous polymerizations
are highly preferred. Thus, reactor 4 may also be a tube reactor, a
loop reactor, extruder, or any reactor capable of continuous
operation.
[0099] As illustrated in FIGS. 2 and 3, the continuous
polymerization and esterification process produces modified
polymers that can be used in processes such as in preparing high
solids, water-based compositions. As demonstrated in FIGS. 2 and 3,
the polymeric products, also referred to as "resins", produced by
the bulk polymerization and esterification process have a
significantly lower viscosity than do conventional resins at the
same percentages of solids in basic aqueous solution. The
viscosities of various resins were compared using "resin cuts"
which are defined as an aqueous solution or dispersion of a resin
in an alkaline aqueous medium. The preparation of resin cuts is
described in the following Examples. The unique low viscosity
properties of the polymers produced by the continuous
polymerization and esterification process, and the high degree of
alkanol incorporation into the polymeric product allow production
of unique compositions with improved characteristics. For example,
the low viscosities of aqueous resin cuts of the polymer product
allows for the production of compositions with higher quantities of
the polymeric product as compared to conventional polymers because
the increased viscosity associated with increasing the solids
content is comparatively lower when the polymeric product of the
present invention is employed.
[0100] FIG. 4 illustrates the unexpectedly high rates obtained in
the conversion of an alkanol to an ester using the continuous
process of the present invention utilizing 1-tetradecanol and
1-docosanol as alkanols. The esterified polymer also exhibits the
low solution viscosity in an aqueous medium exhibited by the
polymeric product of the invention. Conventional Resin 7 was
prepared using approximately 33.6 percent acrylic acid; 23 percent
styrene; 27.1 percent .alpha.-methylstyrene; 7.5 percent xylene;
0.2 percent di-t-butyl peroxide; and 8.7 percent diethylene glycol
monoethyl ether in a reactor at 216.degree. C. Conventional Resin 8
was prepared using approximately 33.6 percent acrylic acid; 24.4
percent styrene; 28.7 percent .alpha.-methylstyrene; 7.5 percent
xylene; 0.2 percent di-t-butyl peroxide; and 5.7 percent diethylene
glycol monoethyl ether in a reactor at 216.degree. C. Conventional
Resin 1 was prepared using approximately 28.2 percent acrylic acid;
27.4 percent styrene; 30.5 percent .alpha.-methylstyrene; 0.2
percent di-t-butyl peroxide; and 13.8 percent diethylene glycol
monoethyl ether in a reactor at 228.degree. C. Exemplary Resin 13
was prepared using approximately 33.6 percent acrylic acid; 20.6
percent styrene; 24.3 percent .alpha.-methylstyrene; 7.5 percent
xylene; 0.2 percent di-t-butyl peroxide; and 13.8 percent
1-tetradecanol in a reactor at 216.degree. C. Exemplary Resin 14
was prepared using approximately 33.6 acrylic acid; 20.6 percent
styrene; 24.3 percent .alpha.-methylstyrene; 7.5 percent xylene;
0.2 percent di-t-butyl peroxide; and 13.8 percent 1-docosanol in a
reactor at 217.degree. C. Exemplary Resin 8 was prepared using
approximately 33.6 percent acrylic acid; 14.3 percent styrene; 16.8
percent .alpha.-methylstyrene; 7.5 percent xylene; 0.2 percent
di-t-butyl peroxide; and 27.7 percent 1-docosanol in a reactor at
216.degree. C. The continuous bulk esterification and
polymerization process of the current invention produced
unexpectedly high incorporation of the alkanol when compared to
conventional systems in the relative weight percent conversion of
acrylic acid monomer to acrylate in the polymeric composition.
[0101] The number of the carbon atoms in the alkanol influences the
viscosity of aqueous resin cuts prepared from polymeric products
containing the alkanol as illustrated in FIGS. 5 and 6. The degree
that the alkanol is incorporated into a polymer through
esterification with the carboxylic acid functionality is also
dependent upon the number of carbon atoms in the alkanol and the
mixture of monomers as illustrated in FIG. 7 which shows the
percent of alkanol incorporation occurring under similar reaction
conditions.
[0102] As noted, the continuous bulk polymerization and
esterification process produces a polymeric product with a high
percentage of the alkanol incorporated into the polymer as an ester
of the polymerized ethylenically unsaturated acid-functional
monomer. Preferably, the polymeric product of the continuous bulk
polymerization and esterification process incorporates at least 80
percent of the alkanol as an ester of the ethylenically unsaturated
acid-functional monomer when the alkanol is present in the reaction
zone in an average amount of at least up to 25 mole percent of the
total moles of the ethylenically unsaturated monomers. More
preferably, the polymeric product of the continuous bulk
polymerization and esterification process incorporates at least 85
percent of the alkanol as an ester of the ethylenically unsaturated
acid-functional monomer when the alkanol is present in the reaction
zone in an average amount of at least up to 20 mole percent of the
total moles of the ethylenically unsaturated monomers. Most
preferably, the polymeric product of the continuous bulk
polymerization and esterification process incorporates at least 90
percent of the alkanol as an ester of the ethylenically unsaturated
acid-functional monomer when the alkanol is present in the reaction
zone in an average amount of at least up to 15 mole percent of the
total moles of the ethylenically unsaturated monomers.
[0103] The polymeric product of the polymerization and
esterification reaction generally has an acid number ranging from
about 10 to about 740, but preferably has an acid number from about
35 to about 400. Even more preferably, the polymeric product has an
acid number ranging from about 65 to about 300. Generally, the
polymeric product has a number average molecular weight ranging
from 600 to 20,000 daltons.
[0104] Preferred polymeric products consist essentially of about 3
to about 97 percent, preferably 10 to 95 percent and all
combinations and subcombinations contained therein, by weight of at
least one incorporated ethylenically unsaturated acid-functional
monomer, about 3 to about 97 percent, preferably 5 to 90- percent
and all combinations and subcombinations contained therein, by
weight of at least one ester of the incorporated ethylenically
unsaturated acid-functional monomer having an --OR group, wherein
the R group is a linear or branched chain alkyl moiety having
greater than 11 carbon atoms; about 0 to about 85 percent by
weight, or up to 85 percent by weight, of at least one incorporated
aromatic ethylenically unsaturated monomer; and about 0 to about 85
percent by weight, or up to 85 percent by weight, of at least one
incorporated non-aromatic ethylenically unsaturated vinyl monomer.
In more preferred polymeric products, the R group of the ester of
the incorporated acid-functional monomer has from 12 to 50, 12 to
36, 12 to 22, 16 to 18 carbon atoms, or mixtures of from 16 to 18
carbon atoms. Other preferred polymeric products contain at least
one incorporated aromatic ethylenically unsaturated monomer or
non-aromatic ethylenically unsaturated vinyl monomer and other
preferred polymeric products include at least two aromatic
ethylenically unsaturated monomers. Additionally, preferred
polymeric products will comprise at least two different R alkyl
groups.
[0105] As noted, aqueous resin cuts of preferred polymeric products
of the continuous bulk polymerization and esterification process
exhibit low viscosities in aqueous basic solution. For example,
aqueous resin cuts of preferred polymeric products have a solution
viscosity which is less than about 50 percent of the solution
viscosity of the equivalent unmodified polymeric products.
[0106] The polymeric products of the bulk polymerization and
esterification process can be used in a number of processes to
produce compositions having excellent performance characteristics.
For example, water-based compositions prepared using the polymeric
product have a higher total solids concentration, higher dry film
thickness, and better gloss than comparable formulations not using
the polymeric product of the present invention.
[0107] Numerous types of water-based compositions can utilize the
esterified polymeric product. The preparation of a number of
compositions is described in greater detail under the Examples
section. Exemplary water-based compositions include overprint
varnishes, inks, coatings, adhesives, floor polishes, paints,
barrier coatings, primers, coil coatings, wax dispersions, oil
dispersions, wax emulsions, oil emulsions, functional paper
coatings, foil coatings, paper sizing agents, and pigment
dispersions. These water-based compositions comprise in the range
of about 0.1 to about 100 percent by weight based on the total
weight of the composition, disregarding water, of the polymeric
product of the bulk polymerization and esterification process. The
water-based composition also includes up to about 99.9 percent,
preferably from about 10 to about 99 percent, by weight based on
the total weight of the composition, disregarding the water, of an
adjunct such as, but not limited to, an emulsion polymer, a
coalescing solvent, a plasticizer, a cross-linking agent, a
defoamer, a pigment, a tackifier, a conventional surfactant, a
starch, a wax, a slip aid, a wetting agent, a surface modifier, an
inert filler, an inert extender, and mixtures of these in addition
to other formulating aids known to those skilled in the art.
Preferably the emulsion polymers are free of any additional
cross-linking agent.
[0108] Other processes that utilize the polymeric product of the
continuous bulk polymerization and esterification process include a
process for increasing the total solids concentration of an aqueous
coating which includes adding the polymeric product to an aqueous
coating; and processes that enhance the viscosity profile or
increase the total solids concentration of an aqueous pigment
dispersion which includes adding the polymeric product to an
aqueous pigment dispersion.
[0109] The polymeric product, including that made by the
polymerization and esterification process, is also beneficially
employed in processes for preparing stable emulsions of polyolefin
resins. It has been surprisingly and unexpectedly discovered that
when preparing an oil or wax emulsion, the addition of the
polymeric product according to the present invention to the
emulsion will enhance emulsion formation and furthermore, will
enhance the stability of the resulting emulsion, i.e., separation
of the emulsion will be reduced as compared to emulsions which are
identical except that they lack the polymeric product and instead
include only conventional resins. An exemplary process for
preparing a stable emulsion of a polyolefin resin includes the
steps of mixing the polyolefin resin, the polymeric product, and
optionally a conventional surfactant, preferably with heating
sufficient to melt the components to obtain a molten mixture;
adding a base to the molten mixture or alternatively adding the
molten mixture to the base; and thereafter adding the molten
mixture to water or alternatively adding water to the molten
mixture.
[0110] An alternative process for preparing an emulsion of a
polyolefin resin includes mixing the polyolefin resin, the
polymeric product, the base and, optionally, a conventional
surfactant, preferably with heating sufficient to melt the
components to obtain a molten mixture; and, adding the molten
mixture to water, or adding water to the molten mixture.
[0111] In preferred processes the base is added to the molten
mixture and then, after waiting for an effective time period of
about 5 minutes, water is added to the resulting mixture.
Generally, the effective period of time is determined empirically
based on the particular materials used. The base becomes
incorporated into the molten mixture during the effective time
period. The polymeric product used in the processes for preparing
an emulsion of a polyolefin resin preferably has an acid number
ranging from 20 to 740.
[0112] The polyolefin resin used in the invented processes and
compositions preferably has a number average molecular weight of
about 500 to about 20,000 daltons, an acid number of 0 to about
150, and a melting point of about 40.degree. C. to about
250.degree. C. The polyolefin resin may be a crystalline polyolefin
resin, a modified polyolefin resin, a natural wax, a synthetic wax,
or mixtures of these materials. Exemplary polyolefin resin material
include paraffin, beeswax, carnauba, oxidized polyethylene,
oxidized polypropylene, ethylene acrylic acid copolymers, vegetable
waxes, wax derived form animals, synthetic waxes, mineral waxes,
candelilla wax, Fischer-Tropsch wax, microcrystalline wax, lanolin,
cottonseed wax, stearin wax, Japan wax, bayberry wax, myrtle wax,
mace wax, palm kernel wax, spermaceti wax, Chinese insect wax,
mutton tallow wax, polyethylene wax, polypropylene wax, copolymers
of ethylene and acrylic acid waxes, a wax obtained by the
hydrogenation of coconut oil, a wax obtained by hydrogenation of
soybean oil, ozokerite wax, a montan wax, a lignite wax, a ceresin
wax, a utah wax, a peat wax, a fir wax, an ouricury wax, a rice-oil
wax, a sugar cane wax, an ucuhuba wax, a cocoa butter wax, a
shellac wax, a wool wax, a chlorinated wax, a duroxon wax, a
synthetic beeswax, a modified spermaceti wax, a modified lanolin
wax, an oxazoline wax, and a metallic soap wax.
[0113] A wax dispersion may be prepared with the polymeric product
of the polymerization and esterification process. The wax
dispersion preparation process includes mixing a wax with an
aqueous solution of the polymeric product. A conventional
surfactant is optionally added to the other components in the
process, but addition of a conventional surfactant is not required.
Preferably, the wax is in the form of a wax powder.
[0114] The wax powder that is used in this method includes a powder
of paraffin and beeswax, a carnauba wax, oxidized polyethylene wax,
oxidized polypropylene wax, ethylene acrylic acid copolymers,
vegetable waxes, waxes derived from animals, synthetic waxes,
mineral waxes, candelilla wax, Fischer-Tropsch waxes,
microcrystalline waxes, lanolin wax, cottonseed wax, stearin wax,
Japan wax, bayberry wax, myrtle wax, mace wax, palm kernel wax,
spermaceti wax, Chinese insect wax, mutton tallow wax, polyethylene
wax, polypropylene wax, copolymers of ethylene and acrylic acid
wax, wax obtained by the hydrogenation of coconut oil, wax obtained
by hydrogenation of soybean oil, ozokerite, montan wax, lignite
wax, ceresin wax, utah wax, peat wax, fir wax, ouricury wax,
rice-oil wax, sugar cane wax, ucuhuba wax, cocoa butter wax,
shellac wax, wool wax, chlorinated wax, duroxon wax, synthetic
beeswax, modified spermaceti wax, modified lanolin wax, oxazoline
wax, metallic soap wax, and combinations and derivatives of
these.
[0115] A stable oil emulsion containing the polymeric product of
the continuous bulk polymerization and esterification process may
be prepared by heating the oil, the polymeric product, and
optionally a conventional surfactant, to a temperature sufficient
to melt the components. A base and then water are then added to the
heated mixture or alternatively the heated mixture is added to the
base and then the water. Alternatively, the oil, the polymeric
product, the base and optionally the conventional surfactant may be
heated to a temperature sufficient to melt the components. The
melted components may then be added to water or alternatively,
water may be added to the melted components.
[0116] An oil or a wax may be stabilized in an aqueous medium by
providing a resin melt of the polymeric product of the continuous
bulk polymerization and esterification process in a reactor at or
above atmospheric pressure; charging the reactor with a base and
water; dispersing a wax or an oil into the resin melt; and charging
additional water into the reactor. The process for stabilizing an
oil or a wax in an aqueous medium may be conducted by heating the
resin melt with the base prior to or subsequent to dispersing the
wax or oil in the mixture.
[0117] A base is added in various compositions of the present
invention and is present in the resulting compositions. Although
various bases known to those skilled in the art may be used in
conjunction with the various processes or included in the various
compositions, preferred bases of the present invention include
ammonia, diethylaminoethanol, morpholine, sodium hydroxide,
potassium hydroxide, or mixtures of these.
[0118] Similarly, a conventional surfactant is optionally added in
various processes and present in various compositions of the
present invention. Although varying quantities of surfactants known
to those skilled in the art may be used in conjunction with the
various processes and compositions, the preferred conventional
surfactants are anionic or non-ionic surfactants that are
preferably present or used in an amount up to about 10 percent
based on the total weight of the solids in the water-based
compositions.
[0119] It is appreciated that all processes for wax and oil
emulsions or dispersions can be carried out at or above atmospheric
pressure, and that the temperature of the processes may be varied
according to the particular materials present in the
compositions.
[0120] Surfactants are surface active agents which, when dissolved
in a solvent such as water, adsorb preferentially at the water/air
interface at the surface of the solution. This causes a reduction
in the surface energy or surface tension of the solution's surface.
The tendency of surfactant molecules to reduce surface tension
results from the attempt to satisfy the opposing affinities of the
hydrophobic and hydrophilic portions of the molecule. It is this
particular behavior of surfactants that forms the basis for their
activity as detergents, wetting agents, and emulsifiers. A careful
balance exists between the hydrophobic and hydrophilic moieties to
obtain highly efficient surfactants. Although there are several
classes of simple non-polymeric surfactants which are very
effective in reducing the surface tensions of liquids, it is very
difficult to design polymeric surfactants, due to their structural
complexity. Most surfactant solutions show a gradual reduction in
surface tension with increase in temperature. In most cases, this
temperature induced reduction in surface tension results mostly
from the lowering surface tension of water that occurs as the
temperature is increased. A polymeric surfactant which displays
abrupt changes in surface tension with a change in the temperature
of a solution containing the surfactant is highly useful in
industrial applications. For example, this property can be used to
control wetting and dewetting behavior of products such as floor
cleaners and inks by changing the temperature by a few degrees.
Such systems exhibit low enough surface tensions to wet low surface
tension substrates at elevated temperatures, but have high enough
surface energy when cooled to accept a second coating. Such
properties are highly useful in coatings and printing applications,
especially those involving multiple coatings.
[0121] It has been discovered that certain polymers may be obtained
which have excellent surfactant properties. The polymeric products
of the present invention were evaluated as neutralized aqueous
solutions and were shown to have excellent surfactant properties.
The preferred neutralizing agents include bases well-known in the
art as previously described. For example, the surfactants exhibit
an abrupt change in surface tension which varies greatly over a
small temperature range. Importantly, this surface tension change
is exhibited at mild temperatures, ranging from 20 to 70.degree.
C., allowing the polymeric products to be useful for printing or
coating on low surface tension substrates such as polyethylene
film, plastics in general, and foil.
[0122] The polymeric surfactants include at least one ethylenically
unsaturated acid-functional monomer which has been radically
incorporated into the polymer surfactant. They also include at
least one ester of the incorporated ethylenically unsaturated
acid-functional monomer which has an R alkyl group having the same
properties as the alkanol used in the process of the invention.
Thus, the R group is a linear or branched chain alkyl moiety having
more than 11 carbon atoms. The R group of the polymeric surfactant
preferably has from 12 to 50, more preferably has 12 to 36, and
even more preferably has 12 to 22 carbon atoms. Most preferably,
the R group has 14 carbon atoms.
[0123] Preferred polymeric surfactants also include at least one
vinyl aromatic monomer, preferably styrene or
.alpha.-methylstyrene, incorporated into the polymeric surfactant.
Other preferred monomers include vinyl non-aromatic monomers
including, but not limited to, acrylates, either alone or in
combination with vinyl aromatic monomers. In more preferred
polymeric surfactants, the ethylenically unsaturated
acid-functional monomer is acrylic acid, and in most preferred
polymeric surfactants, both styrene and .alpha.-methylstyrene are
incorporated into the polymeric surfactant.
[0124] The molar critical micelle concentration of the polymeric
surfactants is preferably less than 1.0.times.10.sup.-2
moles/liter, is more preferably less than 8.2.times.10.sup.-3
moles/liter, and is most preferably less than 1.0.times.10.sup.-3
moles/liter. In more preferred surfactants, the surface area per
surfactant molecule is less than 36 .ANG..sup.2, and more
preferably less than 20 .ANG..sup.2. Other preferred polymeric
surfactants include those in which 2 percent (w/w) neutralized
aqueous solutions of the surfactant have a surface tension of less
than 45 mN/m at 30.degree. C. These preferred surfactant solutions
also undergo a decrease in surface tension of at least about 5 mN/m
as the temperature warms from 30.degree. C. to 50.degree. C. Other
preferred 2% neutralized aqueous surfactant solutions also undergo
a decrease in surface tension of at least about 10 mN/m as the
temperature warms from 30.degree. C. to 50.degree. C.
[0125] FIGS. 8 through 11 demonstrate the remarkable surfactant
properties of the exemplary resins according to the present
invention. FIG. 8 illustrates the significantly lower surface
tensions of Exemplary Resins 39 and 40 containing the tetradecyl
group as compared to Conventional Resin 6 and FC 120, a
fluorosurfactant with excellent surfactant properties, as a
function of concentration. On the other hand, FIG. 9 demonstrates
the surface tension as a function of temperature for 2% aqueous
solutions of Exemplary Resins 2, 3 and 43; Conventional Resins 4-6
and 16; water; and sodium lauryl sulfate, a surfactant well-known
to those skilled in the art. Exemplary Resins 2 and 43 each contain
the hexadecyl group while Exemplary Resin 3 contains a docosyl
group. As illustrated in FIG. 9, the surface tensions of each of
Exemplary Resins 2, 3, and 43 drop considerably as the temperature
is increased from 30.degree. C. to 50.degree. C. whereas the
surface tensions of the conventional resins and sodium lauryl
sulfate change little with the increase in temperature. The change
in the surface tension of the exemplary resins is even more
dramatically illustrated in FIG. 10 which is an enlargement of FIG.
9 which does not show the surface tension of the water. Because the
surface tension of water changes with changes in temperature, this
is an important factor that influences the surface tensions of
aqueous solutions containing surfactants. Thus, the surface
pressure of the exemplary and conventional resins and that of
sodium lauryl sulfate are plotted as a function of temperature in
FIG. 11. The surface pressure is equal to the surface tension of
water at a given temperature minus the surface tension of the
surfactant solution at the same temperature. Thus, FIG. 11 allows
the various materials to be compared based on their ability to
lower surface tension without the interference of the surface
tension of water. The positive slopes observed in the surface
pressures of the exemplary resins, particularly Exemplary Resin 3,
demonstrate that the surface tensions of aqueous solutions of the
polymeric surfactants of the present invention decrease at a much
faster rate than does the surface tension of water. This property
allows the polymeric surfactants of the invention to be used in a
wide variety of applications as described above.
[0126] The present invention is further described in the following
non-limiting examples.
EXAMPLES
Preparation of Exemplary and Conventional Resins
[0127] Exemplary resins created by the invention described above
are described below in the various examples. The materials and
products described in the examples are characterized by a number of
standard techniques. The molecular weight of each polymer was
determined via gel permeation chromatography ("GPC") techniques
using tetrahydrofuran ("THF") as eluent and poly(styrene)
standards. The poly(styrene) standards employed are presently
available from Polymer Laboratories Limited (Church Stretton, Great
Britain) and are further characterized as having number average
molecular weights of 2,250,000; 1,030,000; 570,000; 156,000;
66,000; 28,500; 9,200; 3,250; and 1,250. Acid numbers were
determined by titration with a standardized base and are defined as
the number of milligrams of potassium hydroxide needed to
neutralize one gram of polymer. Viscosity was measured using a
Brookfield viscometer available from Brookfield Engineering
Laboratories (Stoughton, Mass.) with the appropriate LV spindle at
an appropriate speed.
[0128] Exemplary Resin 1
[0129] Exemplary Resin 1 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 1. The
polymerization reaction conditions included about 15 minute reactor
residence time and a reaction temperature of about 254.degree. C.
The resultant resin had a molecular weight (M.sub.w) of about 1,800
daltons and an acid number of 237. Analysis of the polymeric
product and process indicated that about 95.2 percent of the
alkanol had been incorporated into the polymer.
1TABLE 1 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.20
16.70 17.7 Acrylic Acid 35.50 36.60 35.4 .alpha.-Methylstyrene
35.30 36.39 33.7 1-Hexadecanol 10.00 10.31 Hexadecyl acrylate 13.2
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0130] Exemplary Resin 2
[0131] Exemplary Resin 2 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 2. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,800 daltons and an acid number of 155. Analysis of the
polymeric product and process indicated that about 84.6 percent of
the alkanol had been incorporated into the polymer.
2TABLE 2 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 19.09
19.68 23.1 Acrylic Acid 21.32 21.98 20.0 .alpha.-Methylstyrene
41.59 42.88 36.6 1-Hexadecanol 15.00 15.46 Hexadecyl acrylate 20.3
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0132] Exemplary Resin 3
[0133] Exemplary Resin 3 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 3. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,100 daltons and an acid number of 233. Analysis of the
polymeric product and process indicated that about 95.1 percent of
the alkanol had been incorporated into the polymer.
3TABLE 3 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.56
16.04 17.5 Acrylic Acid 34.07 35.12 30.1 .alpha.-Methylstyrene
33.87 34.92 34.8 1-Docosanol 13.50 13.92 Docosyl acrylate 17.6
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0134] Exemplary Resin 4
[0135] Exemplary Resin 4 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 4. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
210.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 6,300 daltons and an acid number of 159. Analysis of the
polymeric product and process indicated that about 57.2 percent of
the alkanol had been incorporated into the polymer.
4TABLE 4 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 32.38
32.99 35.9 Acrylic Acid 21.05 21.45 20.9 .alpha.-Methylstyrene
38.10 38.82 38.6 1-Docosanol 6.62 6.74 Docosyl acrylate 4.6
Di-t-butyl peroxide 1.85 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0136] Exemplary Resin 5
[0137] Exemplary Resin 5 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 5. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
216.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 9,100 daltons and an acid number of 221. Analysis of the
polymeric product and process indicated that about 95.5 percent of
the alkanol had been incorporated into the polymer.
5TABLE 5 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 25.78
25.91 26.7 Acrylic Acid 33.39 33.56 30.7 .alpha.-Methylstyrene
30.33 30.48 29.7 1-Hexadecanol 10.00 10.10 Hexadecyl acrylate 12.9
Di-t-butyl peroxide 0.50 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0138] Exemplary Resin 6
[0139] Exemplary Resin 6 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 6. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
230.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 6,000 daltons and an acid number of 223. Analysis of the
polymeric product and process indicated that about 93.0 percent of
the alkanol had been incorporated into the polymer.
6TABLE 6 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 25.78
25.91 26.8 Acrylic Acid 33.39 33.56 31.4 .alpha.-Methylstyrene
30.33 30.48 28.6 1-Hexadecanol 10.00 10.10 Hexadecyl acrylate 13.2
Di-t-butyl peroxide 0.50 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0140] Exemplary Resin 7
[0141] Exemplary Resin 7 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 7. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
244.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 4,300 daltons and an acid number of 223. Analysis of the
polymeric product and process indicated that about 95.5 percent of
the alkanol had been incorporated into the polymer.
7TABLE 7 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 25.78
25.91 26.5 Acrylic Acid 33.39 33.56 31.4 .alpha.-Methylstyrene
30.33 30.48 29.1 1-Hexadecanol 10.00 10.10 Hexadecyl acrylate 13.0
Di-t-butyl peroxide 0.50 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0142] Exemplary Resin 8
[0143] Exemplary Resin 8 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 8. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 13,700 daltons and an acid number of 208.
Analysis of the polymeric product and process indicated that about
99.4 percent of the alkanol had been incorporated into the
polymer.
8TABLE 8 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 14.27
15.46 15.4 Acrylic Acid 33.57 36.36 29.0 .alpha.-Methylstyrene
16.79 18.18 17.6 1-Docosanol 27.70 30.00 Docosyl acrylate 38.2
Xylene 7.50 -- -- Di-t-butyl peroxide 0.18 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0144] Exemplary Resin 9
[0145] Exemplary Resin 9 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 9. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,800 daltons and an acid number of 223.
Analysis of the polymeric product and process indicated that about
96.3 percent of the 1-hexadecanol and 97.9 percent of the
1-octadecanol had been incorporated into the polymer.
9TABLE 9 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.61
17.60 17.7 Acrylic Acid 28.50 32.14 31.7 .alpha.-Methylstyrene
34.69 39.12 36.5 1-Hexadecanol 2.74 3.09 3.9 Hexadecyl acrylate
1-Octadecanol 7.13 8.04 Octadecyl acrylate 10.2 Xylene 10.0 -- --
Di-t-butyl peroxide 1.32 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0146] Exemplary Resin 10
[0147] Exemplary Resin 10 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 10. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 232.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,000 daltons and an acid number of 188.
Analysis of the polymeric product and process indicated that about
93.1 percent of the 1-tetradecanol and about 95.2 percent of the
1-docosanol had been incorporated into the polymer.
10TABLE 10 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 19.40
21.02 20.8 Acrylic Acid 29.32 31.76 27.4 .alpha.-Methylstyrene
22.82 24.72 23.4 1-Tetradecanol 8.23 8.92 11.6 Tetradecyl acrylate
1-Docosanol 12.54 13.58 Docosyl acrylate 16.8 Xylene 7.50 -- --
Di-t-butyl peroxide 0.19 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0148] Exemplary Resin 11
[0149] Exemplary Resin 11 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 11. The
polymerization reaction conditions included an about 12 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,100 daltons and an acid number of 248. Analysis of the
polymeric product and process indicated that about 97.0 percent of
the alkanol had been incorporated into the polymer.
11TABLE 11 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.20
16.70 17.5 Acrylic Acid 35.50 36.60 35.0 .alpha.-Methylstyrene
35.30 36.39 34.3 1-Hexadecanol 10.0 10.31 Hexadecyl acrylate 13.2
Di-t-butyl peroxide 3.0 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0150] Exemplary Resin 12
[0151] Exemplary Resin 12 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 12. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 207.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,500 daltons and an acid number of 167.
Analysis of the polymeric product and process indicated that about
96.1 percent of the 1-tetradecanol and about 98.9 percent of the
1-docosanol had been incorporated into the polymer.
12TABLE 12 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Acrylic Acid
22.20 24.74 22.6 Methyl Methacrylate 34.32 38.24 37.4 Butyl
Acrylate 20.60 22.95 22.5 1-Tetradecanol 5.06 5.64 7.2 Tetradecyl
acrylate 1-Docosanol 7.57 8.43 Docosyl acrylate 10.3 Xylene 10.00
-- -- Di-t-butyl peroxide 0.25 -- -- .sup.aNormalized reactor feed
was calculated by assuming that initiator and solvent were not
present in the feed.
[0152] Exemplary Resin 13
[0153] Exemplary Resin 13 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 13. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 215.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 11,480 daltons and an acid number of 226.
Analysis of the polymeric product and process indicated that about
96.9 percent of the alkanol had been incorporated into the
polymer.
13TABLE 13 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 20.63
22.35 22.6 Acrylic Acid 33.56 36.36 31.3 .alpha.-Methylstyrene
24.26 26.29 26.0 1-Tetradecanol 13.84 15.00 Tetradecyl acrylate
20.1 Xylene 7.50 -- -- Di-t-butyl peroxide 0.21 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator was not present in the feed.
[0154] Exemplary Resin 14
[0155] Exemplary Resin 14 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 14. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 214.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 13,000 daltons and an acid number of 236.
Analysis of the polymeric product and process indicated that about
99.4 percent of the alkanol had been incorporated into the
polymer.
14TABLE 14 Reactor Normalized Resin Reaction Feed Reactor Feed
Composition Components (% w/w) (% w/w).sup.a (% w/w) Styrene 20.63
22.35 22.3 Acrylic Acid 33.56 36.36 33.2 .alpha.-Methylstyrene
24.26 26.29 26.4 1-Docosanol 13.84 15.00 Docosyl acrylate 18.1
Xylene 7.50 -- -- Di-t-butyl peroxide 0.21 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator was not
present in the feed.
[0156] Exemplary Resin 15
[0157] Exemplary Resin 15 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 15. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,800 daltons and an acid number of 223. Analysis of the
polymeric product and process indicated that about 95.6 percent of
the alkanol had been incorporated into the polymer.
15TABLE 15 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 18.39
18.98 20.2 Acrylic Acid 31.14 32.13 31.4 .alpha.-Methylstyrene
40.86 42.15 38.8 1-Decanol 6.51 6.72 Decyl acrylate 9.6 Di-t-butyl
peroxide 3.10 -- -- .sup.aNormalized reactor feed was calculated by
assuming that initiator was not present in the feed.
[0158] Exemplary Resin 16
[0159] Exemplary Resin 16 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 16. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,000 daltons and an acid number of 219. Analysis of the
polymeric product and process indicated that about 97.6 percent of
the alkanol had been incorporated into the polymer.
16TABLE 16 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 18.03
18.60 19.6 Acrylic Acid 31.15 32.14 31.1 .alpha.-Methylstyrene
40.07 41.34 38.3 1-Dodecanol 7.68 7.92 Dodecyl acrylate 11.0
Di-t-butyl peroxide 3.07 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0160] Exemplary Resin 17
[0161] Exemplary Resin 17 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 17. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,900 daltons and an acid number of 223. Analysis of the
polymeric product and process indicated that about 97.9 percent of
the alkanol had been incorporated into the polymer.
17TABLE 17 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.68
18.23 19.1 Acrylic Acid 31.16 32.14 30.9 .alpha.-Methylstyrene
39.29 40.52 37.7 1-Tetradecanol 8.83 9.11 Tetradecyl acrylate 12.3
Di-t-butyl peroxide 3.03 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0162] Exemplary Resin 18
[0163] Exemplary Resin 18 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 18. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,900 daltons and an acid number of 221. Analysis of the
polymeric product and process indicated that about 98.0 percent of
the alkanol had been incorporated into the polymer.
18TABLE 18 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.33
17.87 18.9 Acrylic Acid 31.18 32.14 31.2 .alpha.-Methylstyrene
38.50 39.69 36.2 1-Hexadecanol 9.99 10.30 Hexadecyl acrylate 13.7
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0164] Exemplary Resin 19
[0165] Exemplary Resin 19 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 19. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,000 daltons and an acid number of 221. Analysis of the
polymeric product and process indicated that about 98.4 percent of
the 1-hexadecanol and about 94.2 percent of the 1-octadecanol had
been incorporated into the polymer.
19TABLE 19 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.22
17.75 18.4 Acrylic Acid 31.18 32.14 31.5 .alpha.-Methylstyrene
38.27 39.45 36.5 1-Hexadecanol 6.99 7.21 9.4 Hexadecyl acrylate
1-Octadecanol 3.34 3.44 Octadecyl acrylate 4.2 Di-t-butyl peroxide
2.99 -- -- .sup.aNormalized reactor feed was calculated by assuming
that initiator was not present in the feed.
[0166] Exemplary Resin 20
[0167] Exemplary Resin 20 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 20. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,900 daltons and an acid number of 220. Analysis of the
polymeric product and process indicated that about 98.7 percent of
the 1-hexadecanol and about 97.5 percent of the 1-octadecanol had
been incorporated into the polymer.
20TABLE 20 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.08
17.61 18.0 Acrylic Acid 31.18 32.14 32.3 .alpha.-Methylstyrene
37.95 39.12 35.7 1-Hexadecanol 3.00 3.09 4.0 Hexadecyl acrylate
1-Octadecanol 7.80 8.04 Octadecyl acrylate 10.0 Di-t-butyl peroxide
2.98 -- -- .sup.aNormalized reactor feed was calculated by assuming
that initiator was not present in the feed.
[0168] Exemplary Resin 21
[0169] Exemplary Resin 21 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 21. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,000 daltons and an acid number of 222. Analysis of the
polymeric product and process indicated that about 97.3 percent of
the alkanol had been incorporated into the polymer.
21TABLE 21 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.98
17.50 18.9 Acrylic Acid 31.19 32.14 29.1 .alpha.-Methylstyrene
37.72 38.87 36.7 1-Octadecanol 11.15 11.49 Octadecyl acrylate 15.3
Di-t-butyl peroxide 2.97 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0170] Exemplary Resin 22
[0171] Exemplary Resin 22 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 22. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,100 daltons and an acid number of 211.
22 TABLE 22 Reactor Normalized Feed Reactor Feed Reaction
Components (% w/w) (% w/w).sup.a Styrene 15.45 15.92 Acrylic Acid
29.65 30.55 .alpha.-Methylstyrene 34.34 25.39 1-Docosanol 12.80
13.19 Docosyl acrylate Xylene 5.00 -- Di-t-butyl peroxide 2.76 --
.sup.aNormalized reactor feed was calculated by assuming that
initiator was not present in the feed.
[0172] Exemplary Resin 23
[0173] Exemplary Resin 23 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 23. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,800 daltons and an acid number of 224. Analysis of the
polymeric product and process indicated that about 96.2 percent of
the alkanol had been incorporated into the polymer.
23TABLE 23 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 18.03
18.60 19.8 Acrylic Acid 31.15 32.14 31.4 .alpha.-Methylstyrene
40.07 41.34 37.9 Isododecanol 7.68 7.92 Isododecyl acrylate 11.0
Di-t-butyl peroxide 3.07 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0174] Exemplary Resin 24
[0175] Exemplary Resin 24 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 24. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,900 daltons and an acid number of 222. Analysis of the
polymeric product and process indicated that about 97.8 percent of
the alkanol had been incorporated into the polymer.
24TABLE 24 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.33
17.87 18.3 Acrylic Acid 31.18 32.14 35.3 .alpha.-Methylstyrene
38.50 39.69 30.2 Isohexadecanol 9.99 10.30 Isohexadecyl acrylate
16.2 Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed
was calculated by assuming that initiator was not present in the
feed.
[0176] Exemplary Resin 25
[0177] Exemplary Resin 25 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 25. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,900 daltons and an acid number of 222. Analysis of the
polymeric product and process indicated that about 99.3 percent of
the alkanol had been incorporated into the polymer.
25TABLE 25 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.88
17.39 18.3 Acrylic Acid 31.19 32.14 31.1 .alpha.-Methylstyrene
37.50 38.64 35.3 Isoeicosanol 11.47 11.82 Isoeicosyl acrylate 15.3
Di-t-butyl peroxide 2.96 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0178] Exemplary Resin 26
[0179] Exemplary Resin 26 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 26. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 2,400 daltons and an acid number of 208.
26 TABLE 26 Reactor Normalized Feed Reactor Feed Reaction
Components (% w/w) (% w/w).sup.a Styrene 13.79 14.17 Acrylic Acid
31.28 32.14 .alpha.-Methylstyrene 30.57 31.41 Isohexatriacontanol
21.68 Isohexatriacosyl acrylate 22.28 Di-t-butyl peroxide 2.68 --
.sup.aNormalized reactor feed was calculated by assuming that
initiator was not present in the feed.
[0180] Exemplary Resin 27
[0181] Exemplary Resin 27 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 27. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,100 daltons and an acid number of 235.
Analysis of the polymeric product and process indicated that about
71.2 percent of the alkanol had been incorporated into the
polymer.
27TABLE 27 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.82
18.98 19.9 Acrylic Acid 28.48 32.13 31.8 .alpha.-Methylstyrene
37.37 42.16 41.1 1-Decanol 5.96 6.72 Decyl acrylate 7.2 Xylene
10.00 -- -- Di-t-butyl peroxide 1.46 -- -- .sup.aNormalized reactor
feed was calculated by assuming that initiator and solvent were not
present in the feed.
[0182] Exemplary Resin 28
[0183] Exemplary Resin 28 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 28. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,200 daltons and an acid number of 229.
Analysis of the polymeric product and process indicated that about
88.1 percent of the alkanol had been incorporated into the
polymer.
28TABLE 28 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.49
18.60 19.4 Acrylic Acid 28.49 32.14 31.1 .alpha.-Methylstyrene
36.64 41.34 39.4 1-Dodecananol 7.02 7.92 Dodecyl acrylate 10.1
Xylene 10.00 -- -- Di-t-butyl peroxide 1.36 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0184] Exemplary Resin 29
[0185] Exemplary Resin 29 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 29. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,400 daltons and an acid number of 227.
Analysis of the polymeric product and process indicated that about
93.3 percent of the alkanol had been incorporated into the
polymer.
29TABLE 29 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.16
18.23 18.8 Acrylic Acid 28.49 32.14 30.4 .alpha.-Methylstyrene
35.92 40.52 39.0 1-Tetradecanol 8.08 9.11 Tetradecyl acrylate 11.8
Xylene 10.00 -- -- Di-t-butyl peroxide 1.35 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0186] Exemplary Resin 30
[0187] Exemplary Resin 30 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 30. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,400 daltons and an acid number of 223.
Analysis of the polymeric product and process indicated that about
96.6 percent of the alkanol had been incorporated into the
polymer.
30TABLE 30 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.84
17.86 18.4 Acrylic Acid 28.50 32.14 30.3 .alpha.-Methylstyrene
35.20 39.70 37.8 1-Hexadecanol 9.13 10.30 Hexadecyl acrylate 13.5
Xylene 10.00 -- -- Di-t-butyl peroxide 1.34 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0188] Exemplary Resin 31
[0189] Exemplary Resin 31 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 31. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,500 daltons and an acid number of 224.
Analysis of the polymeric product and process indicated that about
96.4 percent of the 1-hexadecanol and about 96.6 percent of the
1-octadecanol had been incorporated into the polymer.
31TABLE 31 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.74
17.75 18.2 Acrylic Acid 28.50 32.14 31.0 .alpha.-Methylstyrene
34.98 39.45 37.1 1-Hexadecanol 6.39 7.21 Hexadecyl acrylate 9.4
1-Octadecanol 3.06 3.45 Octadecyl acrylate 4.4 Xylene 10.00 -- --
Di-t-butyl peroxide 1.33 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0190] Exemplary Resin 32
[0191] Exemplary Resin 32 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 32. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,800 daltons and an acid number of 223.
Analysis of the polymeric product and process indicated that about
96.3 percent of the 1-hexadecanol and about 97.9 percent of the
1-octadecanol had been incorporated into the polymer.
32TABLE 32 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.61
17.60 17.7 Acrylic Acid 28.50 32.14 31.7 .alpha.-Methylstyrene
34.69 39.12 36.5 1-Hexadecanol 2.74 3.09 3.9 Hexadecyl acrylate
1-Octadecanol 7.13 8.04 Octadecyl acrylate 10.2 Xylene 10.00 -- --
Di-t-butyl peroxide 1.32 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0192] Exemplary Resin 33
[0193] Exemplary Resin 33 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 33. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,700 daltons and an acid number of 224.
Analysis of the polymeric product and process indicated that about
97.8 percent of the alkanol had been incorporated into the
polymer.
33TABLE 33 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.51
17.49 18.0 Acrylic Acid 28.50 32.14 30.1 .alpha.-Methylstyrene
34.37 38.87 37.0 1-Octadecanol 10.19 11.49 Octadecyl acrylate 14.9
Xylene 10.00 -- -- Di-t-butyl peroxide 1.32 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0194] Exemplary Resin 34
[0195] Exemplary Resin 34 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 34. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,600 daltons and an acid number of 218.
34 TABLE 34 Reactor Normalized Feed Reactor Feed Reaction
Components (% w/w) (% w/w).sup.a Styrene 14.04 16.76 Acrylic Acid
26.93 32.14 .alpha.-Methylstyrene 31.19 37.22 1-Docosanol 11.63
Docosyl acrylate 13.88 Xylene 15.00 -- Di-t-butyl peroxide 1.22 --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0196] Exemplary Resin 35
[0197] Exemplary Resin 35 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 35. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,200 daltons and an acid number of 236.
Analysis of the polymeric product and process indicated that about
77.4 percent of the alkanol had been incorporated into the
polymer.
35TABLE 35 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.49
18.60 19.5 Acrylic Acid 28.49 32.14 31.3 .alpha.-Methylstyrene
36.64 41.34 40.3 Isododecanol 7.02 7.92 Isododecyl acrylate 8.9
Xylene 10.00 -- -- Di-t-butyl peroxide 1.36 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0198] Exemplary Resin 36
[0199] Exemplary Resin 36 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 36. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,300 daltons and an acid number of 225.
Analysis of the polymeric product and process indicated that about
94.8 percent of the alkanol had been incorporated into the
polymer.
36TABLE 36 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.84
17.86 18.5 Acrylic Acid 28.50 32.14 30.4 .alpha.-Methylstyrene
35.20 39.70 37.9 Isohexadecanol 9.13 10.30 Isohexadecyl acrylate
13.2 Xylene 10.00 -- -- Di-t-butyl peroxide 1.34 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0200] Exemplary Resin 37
[0201] Exemplary Resin 37 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 37. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 211.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,500 daltons and an acid number of 225.
Analysis of the polymeric product and process indicated that about
97.2 percent of the alkanol had been incorporated into the
polymer.
37TABLE 37 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.42
17.39 17.9 Acrylic Acid 28.50 32.14 30.3 .alpha.-Methylstyrene
34.27 39.65 36.8 Isoeicosanol 10.48 11.82 Isoeicosyl acrylate 15.0
Xylene 10.00 -- -- Di-t-butyl peroxide 1.32 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0202] Exemplary Resin 38
[0203] Exemplary Resin 38 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 38. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,700 daltons and an acid number of 212.
38 TABLE 38 Reactor Normalized Feed Reactor Feed Reaction
Components (% w/w) (% w/w).sup.a Styrene 12.58 14.17 Acrylic Acid
28.54 32.14 .alpha.-Methylstyrene 27.95 31.48 Isohexatriacontanol
19.73 Isohexatriacosyl acrylate 22.22 Xylene 10.00 -- Di-t-butyl
peroxide 1.19 -- .sup.aNormalized reactor feed was calculated by
assuming that initiator and solvent were not present in the
feed.
[0204] Exemplary Resin 39
[0205] Exemplary Resin 39 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 39. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 215.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 6,600 daltons and an acid number of 149.
Analysis of the polymeric product and process indicated that about
71.3 percent of the alkanol had been incorporated into the
polymer.
39TABLE 39 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 19.05
22.56 25.9 Acrylic Acid 15.62 18.49 19.9 .alpha.-Methylstyrene
42.32 50.11 42.7 1-Tetradecanol 7.47 8.84 Tetradecyl acrylate 11.5
Xylene 15.00 -- -- Di-t-butyl peroxide 0.54 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0206] Exemplary Resin 40
[0207] Exemplary Resin 40 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 40. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 215.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 3,800 daltons and an acid number of 150.
Analysis of the polymeric product and process indicated that about
66.7 percent of the alkanol had been incorporated into the
polymer.
40TABLE 40 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 18.69
22.55 26.0 Acrylic Acid 15.33 18.50 20.3 .alpha.-Methylstyrene
41.53 50.11 43.9 1-Tetradecanol 7.33 8.84 Tetradecyl acrylate 9.8
Xylene 15.00 -- -- Di-t-butyl peroxide 2.13 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0208] Exemplary Resin 41
[0209] Exemplary Resin 41 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 41. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 215.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,200 daltons and an acid number of 205.
Analysis of the polymeric product and process indicated that about
87.3 percent of the alkanol had been incorporated into the
polymer.
41TABLE 41 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.42
19.45 16.8 Acrylic Acid 24.05 28.49 28.8 .alpha.-Methylstyrene
36.49 43.22 42.1 1-Tetradecanol 7.46 8.84 Tetradecyl acrylate 12.3
Xylene 15.00 -- -- Di-t-butyl peroxide 0.57 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0210] Exemplary Resin 42
[0211] Exemplary Resin 42 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 42. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 212.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 18,200 daltons and an acid number of 187.
Analysis of the polymeric product and process indicated that about
84.4 percent of the alkanol had been incorporated into the
polymer.
[0212] Exemplary Resin 43
[0213] Exemplary Resin 43 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 43. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 254.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 1,900 daltons and an acid number of 212.
Analysis of the polymeric product and process indicated that about
95.4 percent of the alkanol had been incorporated into the
polymer.
42TABLE 43 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.81
16.30 17.4 Acrylic Acid 31.73 32.71 32.5 .alpha.-Methylstyrene
34.46 35.53 30.0 1-Hexadecanol 15.00 15.46 Hexadecyl acrylate 20.1
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0214] Exemplary Resin 44
[0215] Exemplary Resin 44 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 44. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 5,100 daltons and an acid number of 169.
Analysis of the polymeric product and process indicated that about
84.1 percent of the alkanol had been incorporated into the
polymer.
[0216] Exemplary Resin 45
[0217] Exemplary Resin 45 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 45. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 207.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 8,000 daltons and an acid number of 167.
Analysis of the polymeric product and process indicated that about
93.1 percent of 1-tetradecanol and about 90.9 percent of
1-docosanol had been incorporated into the polymer.
43TABLE 45 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Acrylic Acid
22.20 24.74 22.9 Methyl methacrylate 34.32 38.24 37.9 Butyl
acrylate 20.59 22.94 22.7 1-Tetradecanol 5.06 5.64 Tetradecyl
acrylate 7.0 1-Docosanol 7.57 8.44 Docosyl acrylate 9.6 Xylene
10.00 -- -- Di-t-butyl peroxide 0.25 -- -- .sup.aNormalized reactor
feed was calculated by assuming that initiator and solvent were not
present in the feed.
[0218] Exemplary Resin 46
[0219] Exemplary Resin 46 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 46. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 11,300 daltons and an acid number of 192.
Analysis of the polymeric product and process indicated that about
95.3 percent of the alkanol had been incorporated into the
polymer.
44TABLE 46 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 14.27
15.46 15.7 Acrylic Acid 33.57 36.36 26.0 .alpha.-Methylstyrene
16.79 18.18 17.9 1-Tetradecanol 27.70 30.00 Tetradecyl acrylate
40.4 Xylene 7.50 -- -- Di-t-butyl peroxide 0.18 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0220] Exemplary Resin 47
[0221] Exemplary Resin 47 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 47. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,400 daltons and an acid number of 144.
45 TABLE 47 Reactor Normalized Feed Reactor Feed Reaction
Components (% w/w) (% w/w).sup.a Styrene 17.84 21.11 Acrylic Acid
15.63 18.50 .alpha.-Methylstyrene 39.64 46.92 1-Docosanol 11.38
Docosyl acrylate 13.47 Xylene 15.00 -- Di-t-butyl peroxide 0.52 --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0222] Exemplary Resin 48
[0223] Exemplary Resin 48 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 48. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 3,700 daltons and an acid number of 145.
Analysis of the polymeric product and process indicated that about
67.6 percent of the alkanol had been incorporated into the
polymer.
46TABLE 48 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.52
21.12 24.3 Acrylic Acid 15.35 18.50 19.8 .alpha.-Methylstyrene
38.91 46.90 41.8 1-Docosanol 11.18 13.48 Docosyl acrylate 14.1
Xylene 15.00 -- -- Di-t-butyl peroxide 2.04 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0224] Exemplary Resin 49
[0225] Exemplary Resin 49 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 49. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 4,200 daltons and an acid number of 198.
Analysis of the polymeric product and process indicated that about
88.6 percent of the alkanol had been incorporated into the
polymer.
[0226] Exemplary Resin 50
[0227] Exemplary Resin 50 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 50. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 7,800 daltons and an acid number of 202.
Analysis of the polymeric product and process indicated that about
91.6 percent of the alkanol had been incorporated into the
polymer.
47TABLE 50 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 15.21
18.01 18.7 Acrylic Acid 24.06 28.49 27.1 .alpha.-Methylstyrene
33.81 40.03 37.0 1-Docosanol 11.38 13.47 Docosyl acrylate 17.2
Xylene 15.00 -- -- Di-t-butyl peroxide 0.55 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0228] Exemplary Resin 51
[0229] Exemplary Resin 51 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 51. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 4,400 daltons and an acid number of 201.
Analysis of the polymeric product and process indicated that about
94.0 percent of the alkanol had been incorporated into the
polymer.
48TABLE 51 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 14.92
18.01 18.8 Acrylic Acid 23.60 28.49 27.1 .alpha.-Methylstyrene
33.16 40.03 37.5 1-Docosanol 11.16 13.47 Docosyl acrylate 16.6
Xylene 15.00 -- -- Di-t-butyl peroxide 2.15 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0230] Exemplary Resin 52
[0231] Exemplary Resin 52 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized, reactor feeds and resin composition are summarized in
Table 52. The polymerization reaction conditions included an about
15 minute reactor residence time and a reaction temperature of
about 216.degree. C. The resultant resin had a molecular weight
(M.sub.w) of about 5,000 daltons and an acid number of 178.
Analysis of the polymeric product and process indicated that about
87.2 percent of the alkanol had been incorporated into the
polymer.
49TABLE 52 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 16.96
20.27 21.6 Acrylic Acid 19.65 23.49 23.5 .alpha.-Methylstyrene
37.70 45.07 40.8 1-Octadecanol 9.34 11.17 Octadecyl acrylate 14.1
Xylene 15.00 -- -- Di-t-butyl peroxide 1.35 -- -- .sup.aNormalized
reactor feed was calculated by assuming that initiator and solvent
were not present in the feed.
[0232] Exemplary Resin 53
[0233] Exemplary Resin 53 was prepared by the bulk polymerization
and esterification process. The reaction components utilized,
reactor feeds and resin composition are summarized in Table 53. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
255.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,200 daltons and an acid number of 201. Analysis of the
polymeric product and process indicated that about 97.6 percent of
the alkanol had been incorporated into the polymer.
50TABLE 53 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 45.59
46.52 49.5 Methacrylic Acid 42.41 43.28 36.4 1-Hexadecanol 10.00
10.20 Hexadecyl acrylate 14.1 Di-t-butyl peroxide 2.00 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator was not present in the feed.
[0234] Exemplary Resin 54
[0235] Exemplary Resin 54 was prepared by the bulk polymerization
and esterification process using an unsaturated C18 alkanol. The
reaction components utilized, reactor feeds and resin composition
are summarized in Table 54. The polymerization reaction conditions
included an about 15 minute reactor residence time and a reaction
temperature of about 254.degree. C. The resultant resin had a
molecular weight (M.sub.w) of about 4,200 daltons and an acid
number of 242. Analysis of the polymeric product and process
indicated that about 94.0 percent of the unsaturated alkanol had
been incorporated into the polymer.
51TABLE 54 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 14.32
14.76 15.2 Acrylic Acid 36.49 37.62 38.4 .alpha.-Methylstyrene
31.19 32.15 30.9 Oleyl alcohol 15.00 15.46 Oleyl acrylate 15.5
Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator was not present in the
feed.
[0236] Conventional Resin 1
[0237] A series of conventional resins were also prepared. These
conventional resins were prepared by a similar process as the
exemplary resins of the present invention, but were prepared
without the presence of the R--OH alkanol of the present invention,
with R being a linear or branched chain alkyl moiety having greater
than 11 carbon atoms. These conventional resins were then compared
to the exemplary resins of the present invention in a number of
applications.
[0238] Conventional Resin 1 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 55. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 228.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 9,000
daltons and an acid number of 220.
52 TABLE 55 Reactor Feed Reaction Components (% w/w) Styrene 27.35
Acrylic Acid 28.19 .alpha.-Methylstyrene 30.49 Diethylene Glycol
13.79 Monoethyl Ether Di-t-butyl peroxide 0.18
[0239] Conventional Resin 2
[0240] Conventional Resin 2 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 56. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 240.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 6,500
daltons and an acid number of 201.
53 TABLE 56 Reactor Feed Reaction Components (% w/w) Styrene 42.39
Acrylic Acid 31.00 .alpha.-Methylstyrene 18.50 Diethylene Glycol
7.94 Monoethyl Ether Di-t-butyl peroxide 0.16
[0241] Conventional Resin 3
[0242] Conventional Resin 3 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 57. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 250.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 4,700
daltons and an acid number of 219.
54 TABLE 57 Reactor Feed Reaction Components (% w/w) Styrene 40.56
Acrylic Acid 33.25 .alpha.-Methylstyrene 18.16 Diethylene Glycol
7.87 Monoethyl Ether Di-t-butyl peroxide 0.16
[0243] Conventional Resin 4
[0244] Conventional Resin 4 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 58. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 278.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 1,800
daltons and an acid number of 244.
55 TABLE 58 Reactor Feed Reaction Components (% w/w) Styrene 32.28
Acrylic Acid 33.78 .alpha.-Methylstyrene 33.94
[0245] Conventional Resin 5
[0246] Conventional Resin 5 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 59. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 254.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 1,800
daltons and an acid number of 244.
56 TABLE 59 Reactor Feed Reaction Components (% w/w) Styrene 20.67
Acrylic Acid 31.04 .alpha.-Methylstyrene 45.29 Di-t-butyl peroxide
3.00
[0247] Conventional Resin 6
[0248] Conventional Resin 6 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 60. The polymerization
reaction conditions included an about 12 minute reactor residence
time and a reaction temperature of about 254.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 1,800
daltons and an acid number of 243.
57 TABLE 60 Reactor Feed Reaction Components (% w/w) Styrene 17.82
Acrylic Acid 32.33 .alpha.-Methylstyrene 39.57 2-Ethylhexyl
Acrylate 7.27 Di-t-butyl peroxide 3.00
[0249] Conventional Resin 7
[0250] Conventional Resin 7 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized and reactor feeds are summarized in Table 61. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
216.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 11,300 daltons and an acid number of 250. Analysis
indicated that 68.9 percent of the ethylene glycol monoethyl ether
was incorporated into the polymeric product.
58TABLE 61 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 23.00
24.93 25.9 Acrylic Acid 33.56 36.37 33.9 .alpha.-Methylstyrene
27.05 29.32 29.7 Diethylene Glycol 8.66 9.39 Monoethyl Ether
Diethylene Glycol 10.5 Monoethyl Ether Acrylate Xylene 7.50 -- --
Di-t-butyl peroxide 0.22 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0251] Conventional Resin 8
[0252] Conventional Resin 8 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized and reactor feeds are summarized in Table 62. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
216.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 11,100 daltons and an acid number of 254. Analysis of the
polymeric product and process indicated that 67 percent of the
ethylene glycol monoethyl ether was incorporated into the polymeric
product.
59TABLE 62 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 24.37
26.41 27.3 Acrylic Acid 33.56 36.36 34.9 .alpha.-Methylstyrene
28.67 31.07 31.2 Diethylene Glycol 5.69 6.17 Monoethyl Ether
Diethylene Glycol 6.6 Monoethyl Ether Acrylate Xylene 7.50 -- --
Di-t-butyl peroxide 0.21 -- -- .sup.aNormalized reactor feed was
calculated by assuming that initiator and solvent were not present
in the feed.
[0253] Conventional Resin 9
[0254] Conventional Resin 9 was prepared by the bulk polymerization
and esterification process. The reaction components utilized and
reactor feeds are summarized in Table 63. The polymerization
reaction conditions included an about 90 minute reactor residence
time and a reaction temperature of about 160.degree. C. The
resultant resin had a molecular weight (M.sub.w) of about 8,200
daltons and an acid number of 162.
60 TABLE 63 Reactor Feed Reaction Components (% w/w) Styrene 23.35
Acrylic Acid 15.51 .alpha.-Methylstyrene 23.19 Diethylene Glycol
36.03 Monoethyl Ether Di-t-butyl peroxide 1.92
[0255] Conventional Resin 10
[0256] Conventional Resin 10 was prepared by the bulk
polymerization and esterification process. The reaction components
utilized and reactor feeds are summarized in Table 64. The
polymerization reaction conditions included an about 12 minute
reactor residence time and a reaction temperature of about
209.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 16,200 daltons and an acid number of 212.
61 TABLE 64 Reactor Feed Reaction Components (% w/w) Styrene 36.56
Acrylic Acid 29.00 .alpha.-Methylstyrene 26.70 Diethylene Glycol
3.20 Monoethyl Ether Butyl acrylate 4.40 Di-t-butyl peroxide
0.14
[0257] Conventional Resin 11
[0258] Conventional Resin 11 was prepared by the bulk
polymerization and esterification process. The reaction components
utilized and reactor feeds are summarized in Table 65. The
polymerization reaction conditions included an about 90 minute
reactor residence time and a reaction temperature of about
161.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 9,400 daltons and an acid number of 200.
62 TABLE 65 Reactor Feed Reaction Components (% w/w) Styrene 17.80
Acrylic Acid 18.52 .alpha.-Methylstyrene 22.82 Diethylene Glycol
39.07 Monoethyl Ether Di-t-butyl peroxide 1.79
[0259] Conventional Resin 12
[0260] Conventional Resin 12 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized and reactor feeds are summarized in Table 66. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,600 daltons and an acid number of 224.
63TABLE 66 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 19.57
22.49 25.3 Acrylic Acid 23.95 27.53 31.9 .alpha.-Methylstyrene
43.48 49.98 42.8 Xylene 10.00 -- -- Di-t-butyl peroxide 3.00 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0261] Conventional Resin 13
[0262] Conventional Resin 13 was prepared by the bulk
polymerization and esterification process. The reaction components
utilized and reactor feeds are summarized in Table 67. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
254.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 1,600 daltons and an acid number of 221.
64TABLE 67 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.03
19.57 21.0 Acrylic Acid 25.30 29.08 31.7 .alpha.-Methylstyrene
37.85 43.51 38.7 2-Ethylhexyl Acrylate 6.82 7.84 8.6 Xylene 10.00
-- -- Di-t-butyl peroxide 3.00 -- -- .sup.aNormalized reactor feed
was calculated by assuming that initiator and solvent were not
present in the feed.
[0263] Conventional Resin 14
[0264] Conventional Resin 14 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized and reactor feeds are summarized in Table 68. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
211.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 6,300 daltons and an acid number of 220.
65TABLE 68 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 19.93
22.49 23.8 Acrylic Acid 44.28 49.98 46.5 .alpha.-Methylstyrene
24.39 27.53 29.8 Xylene 10.00 -- -- Di-t-butyl peroxide 1.40 -- --
.sup.aNormalized reactor feed was calculated by assuming that
initiator and solvent were not present in the feed.
[0265] Conventional Resin 15
[0266] Conventional Resin 15 was prepared by the polymerization and
esterification process with added solvent. The reaction components
utilized and reactor feeds are summarized in Table 69. The
polymerization reaction conditions included an about 15 minute
reactor residence time and a reaction temperature of about
211.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 6,500 daltons and an acid number of 217.
66TABLE 69 Reactor Normalized Resin Feed Reactor Feed Composition
Reaction Components (% w/w) (% w/w).sup.a (% w/w) Styrene 17.35
19.58 20.2 Acrylic Acid 38.54 43.50 30.3 .alpha.-Methylstyrene
25.76 29.07 41.3 2-Ethylhexyl acrylate 6.95 7.84 8.2 Xylene 10.00
-- -- Di-t-butyl peroxide 1.40 -- -- .sup.aNormalized reactor feed
was calculated by assuming that initiator and solvent were not
present in the feed.
[0267] Conventional Resin 16
[0268] Conventional Resin 16 was prepared by the bulk
polymerization and esterification process. The reaction components
utilized and reactor feeds are summarized in Table 70. The
polymerization reaction conditions included an about 12 minute
reactor residence time and a reaction temperature of about
204.degree. C. The resultant resin had a molecular weight (M.sub.w)
of about 8,500 daltons and an acid number of 205;
67 TABLE 70 Reactor Feed Reaction Components (% w/w) Styrene 28.83
Acrylic Acid 27.56 .alpha.-Methylstyrene 34.03 Diethylene Glycol
8.40 Monoethyl Ether Di-t-butyl peroxide 1.18
Preparation of Resin Cuts
[0269] The term "resin cut" or "resin solution" denotes an aqueous
mixture of a resin, water, and a base. Exemplary resin cuts are
described herein. An aqueous cut of an acid-functional acrylic or
styrene/acrylic resin can be prepared by mixing the resin, water,
and a base. The mixture is stirred from about 25.degree. C. to
about 90.degree. C. until the resin is completely dissipated. The
acid functional resin comprises about 5 to about 70 weight percent
of the final resin cut. A sufficient amount of a base is added to
neutralize about 50 to 150 percent of the acid in the acid
functional resin. Typical bases used for neutralization of the acid
functional resin are ammonia, hydroxides of group I elements,
primary amines, secondary amines, and tertiary amines. The
remainder of the resin cut is comprised of water, and optionally, a
water-miscible solvent. The amount of water used in a resin cut is
dependent on the acid value of the resin and its molecular weight.
Typically, water is added at a level, such that the cut viscosity
is below about 10,000 cps. Water-miscible solvents, such as lower
alkyl alcohols, glycol ethers, tetrahydrofuran, and
tetrahydrofurfuryl alcohol, can be added up to about 10 weight
percent of the resin cut.
[0270] Resin Cut A: Preparation of an Aqueous Resin Cut of
Exemplary Resin 1
[0271] The aqueous resin cut of Exemplary Resin 1 was prepared by
the method described above. The cut was prepared from 488 grams of
Exemplary Resin 1, 125.17 grams of 28 percent ammonia, and 386.83
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 1,350 cps at a pH of 48.8 percent solids.
[0272] Resin Cut B: Preparation of an Aqueous Resin Cut of
Exemplary Resin 5
[0273] The aqueous resin cut of Exemplary Resin 5 was prepared by
the method described above. The cut was prepared from 340 grams of
Exemplary Resin 5, 81.69 grams of 28 percent ammonia, and 428.47
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 41,500 cps at a pH of 8.9 at 40 percent solids. After
dilution to 34 percent solids, the cut had a viscosity of 520
cps.
[0274] Resin Cut C: Preparation of an Aqueous Resin Cut of
Exemplary Resin 6
[0275] The aqueous cut of Exemplary Resin 6 was prepared by the
method described above. The cut was prepared from 400 grams of
Exemplary Resin 6, 96.10 grams of 28 percent ammonia, and 503.90
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 3,680 cps at a pH of 8.5 at 40 percent solids. After
dilution to 33 percent solids, the cut had a viscosity of 120
cps.
[0276] Resin Cut D: Preparation of an Aqueous Resin Cut of
Exemplary Resin 7
[0277] The aqueous cut of Exemplary Resin 7 was prepared by the
method described above. The cut was prepared from 450 grams of
Exemplary Resin 7, 108.12 grams of 28 percent ammonia, and 441.88
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 7,500 cps at a pH of 8.5 at 45 percent solids. After
dilution to 37 percent solids, the cut had a viscosity of 280
cps.
[0278] Conventional Resin Cut A: Preparation of an Aqueous Resin
Cut of Conventional Resin 1
[0279] The aqueous cut of Conventional Resin 1 was prepared by the
method described above. The cut was prepared from 330 grams of
Conventional Resin 1, 75.0 grams of 28 percent ammonia, and 585.0
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 5,350 cps at a pH of 8.5 at 34 percent solids.
[0280] Conventional Resin Cut B: Preparation of an Aqueous Resin
Cut of Conventional Resin 2
[0281] The aqueous cut of Conventional Resin 2 was prepared by the
method described above. The cut was prepared from 330 grams of
Conventional Resin 2, 71.0 grams of 28 percent ammonia, and 599.0
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 4,500 cps at a pH of 8.5 at 33 percent solids.
[0282] Conventional Resin Cut C: Preparation of an Aqueous Resin
Cut of Conventional Resin 3
[0283] The aqueous cut of Conventional Resin 3 was prepared by the
method described above. The cut was prepared from 370 grams of
Conventional Resin 3, 86.0 grams of 28 percent ammonia, and 543.0
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 5,000 cps at a pH of 8.4 at 37 percent solids.
[0284] Conventional Resin Cut D: Preparation of an Aqueous Resin
Cut of Conventional Resin 4
[0285] The aqueous cut of Conventional Resin 4 was prepared by the
method described above. The cut was prepared from 488 grams of
Conventional Resin 4, 125.70 grams of 28 percent ammonia, and 386.3
grams of water. The resultant clear, amber resin cut exhibited a
viscosity of 4,900 cps at a pH of 8.5 at 48.8 percent solids.
[0286] Conventional Resin Cut E: Preparation of an Aqueous Resin
Cut of Conventional Resin 5
[0287] The aqueous cut of Conventional Resin 5 was prepared by the
method described above. The cut was prepared from 488 grams of
Conventional Resin 5, 129.39 grams of 28 percent ammonia, and
382.61 grams of water. The resultant clear, amber resin cut
exhibited a viscosity of 7,400 cps at a pH of 8.9 at 48.8 percent
solids.
Tabulated Viscosity Measurements and Other Polymer Properties
[0288] Tables 71 through 77 present various data regarding the
viscosity of resin cuts at various pH and concentrations for
exemplary and conventional resins. The comparative data presented
in Tables 71 through 77 are respectively illustrated in FIGS. 2-7
for convenience. These tables demonstrate the surprising and
unexpected discovery that aqueous basic solutions containing the
polymeric products of the invention exhibit remarkably low
viscosities.
68TABLE 71 Aqueous Solution Resin Viscosity Acid Resin Solution
Solution Resin (cps) Number M.sub.w % Solids pH Conventional 5,500
220 9,000 34 8.4 Resin 1 Exemplary 520 221 9,100 34 8.0 Resin 5
Conventional 4,500 201 6,500 33 8.5 Resin 2 Exemplary 120 223 6,000
33 8.1 Resin 6 Exemplary 3,680 223 6,000 40 8.1 Resin 6
Conventional 5,000 219 4,700 37 8.4 Resin 3 Exemplary 280 223 4,300
37 8.0 Resin 7 Exemplary 7,500 223 4,300 45 8.0 Resin 7
[0289]
69TABLE 72 Aqueous Solution Resin Viscosity Acid Resin Solution
Solution Resin (cps) Number M.sub.w % Solids pH Conventional 4,900
244 1,800 48.8 8.4 Resin 4 Conventional 7,400 244 1,800 48.8 8.8
Resin 5 Exemplary 1,350 237 1,800 48.8 8.3 Resin 1 Exemplary 1,600
233 2,100 48.8 8.5 Resin 3
[0290]
70TABLE 73 Weight % Moles in % Alcohol Alcohol in Alcohol to Ester
Reactor in Reactor Resin Conversion Feed Feed Alcohol Type
Conventional 69.9 9.39 0.0700 diethylene glycol Resin 7 monoethyl
ether Exemplary 96.9 15.00 0.0700 1-tetradecanol Resin 13
Conventional 67.0 6.17 0.0460 diethylene glycol Resin 8 monoethyl
ether Exemplary 99.4 15.00 0.0460 1-docosanol Resin 14 Conventional
27.0 13.80 0.1029 diethylene glycol Resin 1 monoethyl ether
Exemplary 99.4 30.00 0.0919 1-docosanol Resin 8
[0291]
71TABLE 74 48.3% Number of Solids Resin Carbons in Viscosity
Solution Acid Alkanol Exemplary Resin (cps) pH Number M.sub.w C0
Conventional 6,300 9.3 224 1,600 Resin 12 C8 Conventional 4,200 9.1
221 1,600 Resin 13 C10 Exemplary Resin 15 3,700 8.9 223 1,800 C12
Exemplary Resin 16 4,000 8.4 219 2,000 C14 Exemplary Resin 17 3,500
9.5 223 1,900 C16 Exemplary Resin 18 2,900 9.4 221 1,900 C16/18
Exemplary Resin 19 2,400 9.1 221 2,000 C18/16 Exemplary Resin 20
2,600 8.3 220 1,900 C18 Exemplary Resin 21 2,900 9.1 222 2,000 C22
Exemplary Resin 22 5,200 9.3 211 2,100 Iso-C12 Exemplary Resin 23
3,500 9.3 224 1,800 Iso-C16 Exemplary Resin 24 3,500 9.4 222 1,900
Iso-C20 Exemplary Resin 25 3,200 8.8 222 1,900 Iso-C36 Exemplary
Resin 26 6,400 9.1 208 2,400
[0292]
72TABLE 75 Resin 30.5% (Number of Solids Resin Carbons in Viscosity
Solution Acid Alkanol) Exemplary Resin (cps) pH Number M.sub.w
Conventional Conventional 394 8.1 201 6,500 Resin 2 Resin 2 C0
Conventional 395 7.8 220 6,300 Resin 14 C8 Conventional 160 7.5 217
6,500 Resin 15 C10 Exemplary Resin 27 55 8.0 235 6,100 C12
Exemplary Resin 28 40 8.0 229 6,200 C14 Exemplary Resin 29 35 8.0
227 6,400 C16 Exemplary Resin 30 30 7.9 223 6,400 C16/18 Exemplary
Resin 31 20 8.0 224 6,500 C18/16 Exemplary Resin 32 35 8.0 223
6,800 C18 Exemplary Resin 33 35 8.1 224 6,700 C22 Exemplary Resin
34 55 8.2 218 6,600 Iso-C12 Exemplary Resin 35 40 8.0 236 6,200
Iso-C16 Exemplary Resin 36 40 8.1 225 6,300 Iso-C20 Exemplary Resin
37 40 8.1 225 6,500 Iso-C36 Exemplary Resin 38 270 7.7 212
7,700
[0293]
73TABLE 76 Fatty Alcohol Fatty Alcohol Number of Modified Resin %
ROH Modified Resin % ROH Carbons in Prepared at Conversion Prepared
at Conversion Alkanol 254.degree. C. of RCOOR 212.degree. C. of
RCOOR C10 Exemplary 95.6 Exemplary 71.2 Resin 15 Resin 27 C12
Exemplary 97.6 Exemplary 88.1 Resin 16 Resin 28 C14 Exemplary 97.9
Exemplary 93.3 Resin 17 Resin 29 C16 Exemplary 98.0 Exemplary 96.6
Resin 18 Resin 30 C16/C18 Exemplary 96.3 Exemplary 96.5 Resin 19
Resin 31 C18/C16 Exemplary 98.1 Exemplary 97.1 Resin 20 Resin 32
C18 Exemplary 97.3 Exemplary 97.8 Resin 21 Resin 33 Iso-C12
Exemplary 96.2 Exemplary 77.4 Resin 23 Resin 35 Iso-C16 Exemplary
97.8 Exemplary 94.8 Resin 24 Resin 36 Iso-C20 Exemplary 99.3
Exemplary 97.2 Resin 25 Resin 37
Preparation of Exemplary Coatings, Pigment Dispersions, Paints,
Inks, and Paper-Sizing Agents
[0294] The high solids polymers have many applications. They are
readily formulated into enamel appliance coatings, overprint
varnishes, adhesives, and auto, truck, or airplane exterior
finishes, coatings, and the like. They are also readily formulated
into floor finishes, ink dispersants, water-based clear overprint
varnishes, impregnants, binders, plasticizers, leveling agents,
melt flow improvers and the like. Formulations containing the
polymeric products of the present invention surprisingly and
unexpectedly demonstrate performance characteristics over similar
formulations that differ only in that the formulation incorporates
a conventional resin in place of the resins of the present
invention.
[0295] It was surprisingly and unexpectedly discovered that by
employing the polymeric products of the invention, essentially
solvent-free coatings systems may be obtained having usable
viscosities at room temperature. Such systems are applicable in
standard industrial coating processes, including spray coating,
roll coating and the like. The products prepared from the process
of the invention are formulated into such coating systems by
addition of solvents, fillers, pigments, flow control agents and
the like. Such coatings can be applied, with the addition of
conventional adjuvants, to cans, coils, fabrics, vinyl, paper,
metal, furniture, wire, metal parts, wood paneling and the like.
Additionally, the polymeric products can also be formulated into
excellent paper-sizing agents.
[0296] The alkali soluble resins may be formulated into resin cuts
employing available aqueous bases, to provide exceptional leveling
properties when incorporated into a floor polish composition with a
suitable metallized acrylic, methacrylic or copolymer emulsion, a
wax emulsion, and adjuvants such as plasticizers, conventional
surfactants, and anti-foaming agents for organic solvents and/or
organic bases.
[0297] It is contemplated that the esterification of the polymeric
product in the continuous bulk polymerization and esterification
process dramatically modifies the solubility of the resins in
various solvents as compared to resins without the ester alkyl
groups, and hence provides utility of the resins of the present
invention in solvent-based inks. The incorporation of the ester
groups in the resins of the present invention also dramatically
enhances the ability of the resin to stabilize various materials,
such as pigments, oils, waxes, other resins, solvents, monomers, or
polymer colloids, in an aqueous environment. Furthermore, the
resins of the present invention are contemplated to be useful in
water-based air dry coatings systems, high gloss systems
applications, and OPV applications. The resins are also
contemplated to be useful components in moisture vapor transmission
rate (MVTR) applications, and self-stratifying systems
applications.
[0298] Preparation of Exemplary and Conventional Coatings from
Exemplary Resin 1 and Conventional Resins 4 and 5
[0299] Coatings were formulated using the resins of the invention
and a series of emulsion polymers. The emulsion polymers were
prepared using the same processes as described below, but with
varying polymer compositions.
[0300] The emulsion polymers were prepared by first preparing a
resin solution. The resin solutions was prepared by mixing 20.2
grams of Polyglycol.TM. P1200, 314.6 grams of deionized water, and
825.7 grams of a solution of an acid functional styrene/acrylic
resin in aqueous ammonia at 28.5 percent solids in a round bottom
flask. The acid functional styrene/acrylic resin had a 34
.alpha.-methylstyrene/33 styrene/33 acrylic acid composition with
an M.sub.w of about 9,500 daltons and an acid number of about 226.
Polyglycol.TM. P1200 is a polypropylene glycol manufactured by The
Dow Chemical Company of Midland, Mich. This mixture was heated to
82.degree. C. under nitrogen.
[0301] A mixture of 14.8 grams of Tergitol.TM. 15-S-9, a linear
alcohol ethoxylate available from Union Carbide (Danbury, Conn.),
and a total of 668.3 grams of a hard non film-forming polymer, a
hard film-forming polymer or a soft film-forming polymer was
prepared. Ten percent of the Tergitol.TM.-containing mixture was
charged to the flask containing the hot resin solution and mixed
for 3 minutes. A solution containing 4.4 grams of ammonium
persulfate in 17.6 grams of water was then added and the resulting
mixture was mixed for 5 minutes. The remainder of the
Tergitol.TM.-containing mixture was then added over 70 minutes.
With 10 minutes remaining in the addition, the temperature was
raised to 85.degree. C. After the addition was complete, 112.0
grams of water and a second ammonium persulfate solution (2.6 grams
in 10.4 grams of water) were added and the reaction mixture was
heated at 85.degree. C. for 1 hour. The emulsion polymer was then
cooled and 3.0 grams of 28 percent ammonia was added.
[0302] Three polymer compositions were used to prepare the emulsion
polymer. These included: a 100 percent styrene homopolymer, a hard
non film-forming composition; a 50 percent methyl methacrylate/10
percent butyl acrylate/40 percent 2-ethylhexyl acrylate terpolymer
composition, a hard film-forming composition; and a 20 percent
methyl methacrylate/40 percent butyl acarylate/40 percent
2-ethylhexyl acrylate terpolymer composition, a soft film-forming
polymer.
[0303] Coatings were prepared by mixing 10.7 parts of emulsion
polymer, 45 parts of a resin as specified below, 11.6 parts of 28
percent ammonia, and 32.7 parts of water in a blender for 6 minutes
at a medium speed. The resulting mixture was cooled and diluted to
105 cps with an appropriate amount of water to produce a coating.
The coating was applied on a N2C Leneta.TM. card obtained from
Leneta.TM. Company (Mahwah, N.J.), with a 165Q anilox handproofer.
Exemplary Resin 1 and Conventional Resins 4 and 5 were used as the
resin component of these coatings. Gloss (60.degree.) was measured
over the black and the white portions of Leneta.TM. cards with a
gloss meter. Wetting, leveling, holdout, and distinctness of image
(DOI) were assessed visually and compared. The results of these
tests are presented in Tables 77 through 79. In Tables 77-79,
"Std." denotes reference standard for visual assessments; "="
denotes performance equal to the standard; ">" denotes
performance better than the standard; and ">>" denotes
performance much better than the standard.
74TABLE 77 Coatings Containing Poly(styrene) Emulsion Polymer
Gloss/ Gloss/ Wet- Level- Hold- Resin Black White ting ing out DOI
Exemp. Resin 1 88 81 = > >> >> Conv. Resin 4 84 78
Std. Std. Std. Std.
[0304]
75TABLE 78 Coatings Containing Hard, Film-Forming Emulsion Polymer.
Gloss/ Gloss/ Wet- Level- Hold- Resin Black White ting ing out DOI
Exemp. Resin 1 86 79 = > >> >> Conv. Resin 4 84 75
Std. Std. Std. Std. Conv. Resin 5 81 74 = = = =
[0305]
76TABLE 79 Coatings Containing Soft, Film-Forming Emulsion Polymer.
Gloss/ Gloss/ Wet- Level- Hold- Resin Black White ting ing out DOI
Exemp. Resin 1 85 79 = > >> >> Conv. Resin 4 81 73
Std. Std. Std. Std. Conv. Resin 5 81 74 = = = =
[0306] Preparation of Exemplary and Conventional Coatings from
Exemplary Resins 39 and 40 and Conventional Resin 9
[0307] Clear coatings were formulated from emulsion polymers
containing resin cuts of Exemplary Resins 39 and 40. A control
emulsion polymer was prepared using Conventional Resin 9. A monomer
mixture of 41 percent styrene, 28 percent methyl methacrylate, and
31 percent 2-ethylhexyl acrylate was used in each of the emulsion
polymers. The final emulsion polymers had a solids content of about
43 percent.
[0308] Each of the three emulsion polymers was formulated into a
clear coating. The coating formulation consisted of: 30 parts
polymer solids; 9 parts of Dowanol.TM. EB, an ethylene glycol butyl
ether product of the Dow Chemical Company of Midland, Mich.; 0.02
parts Zonyl.TM. FSJ solids, a wetting agent and product of E. I.
duPont de Nemours, of Wilmington, Del.; and water added to produce
a total of 100 parts.
[0309] The clear coatings were drawn down on variety of substrates
for testing. A paddle blade and electric mixing motor was used to
make the coatings. A series of properties were evaluated and the
results are reported in the following table. It was surprisingly
and unexpectedly discovered that the clear coatings incorporating
the polymeric products of the present invention showed a greatly
enhanced early water resistance as compared to clear coatings
incorporating conventional resins.
77TABLE 80 Coating with Coating with Coating with Conventional
Exemplary Exemplary Test Substrate Resin 9 Resin 40 Resin 39 Early
Water Leneta .TM. 1B 5.8/7.3 9.8/10 9.9/10 Resistance- (black
sealed part) 4 hour dry Early Water Leneta .TM. 1B 9.3/8.7 9.7/10
9.8/9.5 Resistance- (black sealed part) 24 hour dry Chemical Leneta
.TM. 1B 8.8/8.6 9.2/9.2 10/10 Resistance- (black sealed part) 50%
Ethanol Chemical Leneta .TM. 1B 7.8/9.3 7.8/9.0 6.3/8.2 Resistance-
(black sealed part) 5% NaOH Corrosion Bonderite .TM. 1000 5.5 5.5
5.5 Resistance- cold rolled steel; Face rust 3 mil Bird Bar
Corrosion Bonderite .TM. 1000 3/32" 3/32" 3/32" Resistance- cold
rolled steel; Undercut 3 mil Bird Bar Corrosion Bonderite .TM. 1000
None #4 few (10%) None Resistance- cold rolled steel Blisters Konig
Hardness, Bonderite .TM. 1000 136 109 129 rocks cold rolled steel
Pencil Hardness Bonderite .TM. 1000 H B H cold rolled steel Gloss,
Leneta 1B 50 45 47 20 degrees white sealed part 1{grave over (
)}Gloss, Leneta .TM. 1B 93 90 92 60 degree white sealed part Cross
Hatch Bonderite .TM. 1000 5 4 4.5 Tape adhesion treated CRS
[0310] The following test protocols were followed for each test
shown in Table 80:
[0311] Early Water Resistance: The coating was applied to the
substrate with a #50 wire wound draw bar and allowed to air dry for
the indicated amount of time. At the end of the indicated time, a
filter paper disk saturated with deionized water was placed on the
coating for one hour. A watch glass was placed over the filter
paper disk to reduce water evaporation. The test panel was flushed
with tap water and the panels were inspected for damage to the
coating. Six responses were gathered for each coating and rated on
a 0-10 scale with 10 being the best. An average of the six
responses for each coating is shown in the table. The first number
corresponds to the average rating immediately after the test, and
the second number is the average rating after the coating has fully
recovered.
[0312] Chemical Resistance: The coating was applied to the
substrate, initially dried in an oven at 35.degree. C. overnight,
and then allowed to air dry for 7 days. The procedure from the
early water resistance test was followed for each of the indicated
chemicals.
[0313] Corrosion Resistance: The clear coating was applied with a 3
mil Bird drawbar to Bonderite.TM. 1000, a cold rolled steel product
of ACT Labs, Inc. of Hillsdale, Mich. The coating was allowed to
dry for 47 days. The coating was scribed and subjected to 83 hours
in a salt spray cabinet. Face rust was evaluated using ASTM B117
method. Undercut is the distance from the scribe to the edge of the
corrosion about the scribe. Blistering was evaluated using ASTM
D714.
[0314] Hardness: Hardness was measured using a Pendulum Hardness
Tester, Konig from the Byk Gardner Company of Rivers Park, Md. The
coating was air dried for 21 days. An average of 3 readings for
each coating is reported in the table above. Pencil hardness
measurements used Eagle Turquoise Pencils. The same drawdown
procedure used in the corrosion resistance test was used.
[0315] Gloss: Gloss was measured on the white sealed portion of a
Leneta 1B panel. The coating was applied to the panel with a #50
wire wound drawbar, and allowed to air dry for 2 days. A Micro-tri
Gloss meter from Byk Gardner, a product of the Byk Gardner Company
of Rivers Park, Md., was used to measure the gloss. The average
reported in the table was based on 6 to 9 measurements.
[0316] Cross Hatch Tape Adhesion (according to ASTM D3359-95): A
coating was applied to a panel of Bonderite.TM. 1000 cold rolled
steel with a 3 mil Bird Drawbar and allowed to air dry for 26 days.
The same drawdown procedure used in the corrosion resistance test
was used. The coating was scored in a cross hatch pattern with an
11 blade Paint Adhesion Tester with 1.5 mm spacings obtained from
Paul Gardner (Pompano Beach, Fla.). A piece of Scotch.TM. #610 tape
from 3M Company of St. Paul, Minn. was applied to the coating;
rubbed on with a pencil eraser; set in place for 60 to 120 seconds
and then pulled at a 180 degree angle. The removal of the coating
was evaluated with the 0-5 ("B") scale where a numerical value of 5
is equal to perfect adhesion.
[0317] Preparation of Exemplary and Conventional White Enamels from
Exemplary Resins 39 and 40 and Conventional Resin 9
[0318] White enamel paints were formulated from emulsion polymers
containing resin cuts of Exemplary Resin 39 and Exemplary Resin 40.
A control emulsion polymer was prepared using Conventional Resin 9.
A monomer mixture of 41 percent styrene, 28 percent methyl
methacrylate, and 31 percent 2-ethylhexyl acrylate was used in each
of the emulsion polymers. The final emulsion polymers had a solids
content of about 43 percent. Each of the three emulsion polymers
was formulated into a white enamel paint. It was surprisingly and
unexpectedly discovered that paints incorporating the polymeric
product of the present invention had a much higher gloss retention
than similar paints which differed only in that they incorporated
conventional resins rather than the polymeric products of the
present invention.
[0319] A grind base was prepared by mixing the following materials
shown in Table 81 in a high speed mixer for 15 minutes:
78 TABLE 81 Grind Base Components Quantity of Component Water 8.414
grams Surfynol .TM. CT-151 0.401 grams Surfynol .TM. 104DPM 0.161
grams Dehydran .TM. 1620 0.048 grams DSX .TM.-1550 0.040 grams
TiPure .TM. R-706 20.034 grams
[0320] Surfynol.TM. CT-151 and Surfynol.TM. 104DPM are brands of
surfactant available from Air Products and Chemicals, Inc.
(Allentown, Pa.). Dehydran.TM. 1620 is a brand of defoaming agent
available from Henkel Corporation (Ambler, Pa.), and DSX.TM.-1550
is a brand associative thickener manufactured by Henkel Corporation
(Ambler, Pa.). TiPure.TM. R-706 is a brand of titanium dioxide
pigment available from E. I. duPont de Nemours (Wilmington,
Del.).
[0321] Three white enamel paints were formulated by mixing the
materials in the table below. For each paint, a different emulsion
polymer was used.
79TABLE 82 Paint with Paint with Paint with Conventional Exemplary
Exemplary Materials Resin 9 Resin 40 Resin 39 Emulsion Polymer 58.1
58.8 58.1 Grind base (Table 81) 29.1 29.1 29.1 Deionized Water 67.5
67.5 67.5 Dehydran .TM. 1620 0.2 0.2 0.2 Dowanol .TM. EB 5.0 5.0
5.0 Dowanol .TM. DPnB 2.5 2.5 2.5 Raybo .TM. 60 0.3 0.3 0.3 RM825
.TM. 4.7 0.9 6.3
[0322] Dowanol.TM. EB and Dowanol.TM. DPnB, plasticizing solvent
brands of The Dow Chemical Company (Midland, Mich.), were mixed
together and added as a mixture to the paint formula. Raybo.TM. 60
a flash rust inhibitor is a product of the Raybo Corporation
(Huntington, W. Va.). RM825.TM. is an associative thickener
available from Rohm & Haas Company (Spring House, Pa.). The
associative thickener was added in various amounts to attain the
appropriate application viscosity for the paint.
[0323] The white enamel paints were drawn down on variety of
substrates for testing. A 0.003" Bird applicator was used to make
the coatings. A series of properties were evaluated coating and the
results are reported in the Table 83 below.
80TABLE 83 Paint with Paint with Paint with Conventional Exemplary
Exemplary Test Substrate Resin 9 Resin 40 Resin 39 Humidity Bare
rolled steel 6 none none Resistance- Rusting Humidity Bare rolled
steel #8D none none Resistance- Blistering Durability- 20 Aluminum
panels 13% 79% 41% Gloss retention Durability- 60 Aluminum panels
49% 97% 78% Gloss retention Scrub Resistance Leneta .TM. plastic
457 1140 500 scrub charts [#121-10N] Chemical Bonderite .TM. 1000
9.3 10 9.8 Resistance- cold rolled steel 10% Ethanol Chemical
Bonderite .TM. 1000 8 8.5 8 Resistance- cold rolled steel 10% NaOH
Corrosion Bare rolled steel 4 4 5 Resistance- Face rust Corrosion
Bare rolled steel 10/32" 7/32" 8/32" Resistance- Undercut Corrosion
Bare rolled steel #8MD #6D #4MD Resistance- Blisters Konig
Hardness, Bare rolled steel 76 85 73 rocks Gloss, 20 degrees Leneta
.TM. 1B 35/38 50/35 34/36 Gloss, 60 degree Leneta .TM. 1B 79/83
88/83 78/81 Cross Hatch Tape Bare rolled steel 5B 5B 5B
adhesion
[0324] The following test protocols were followed for each
test:
[0325] Humidity Resistance: Humidity resistance was tested by
placing panels in a QCT Cleveland Condensation cabinet, a product
of Q-Panel Lab Products of Cleveland, Ohio, for 200 hours. The face
rusting evaluation follows ASTM D-610. The blistering evaluation
follows ASTM D-714.
[0326] Durability: The coating is tested for QUV durability for
1000 hours with the A bulbs. The exposure is performed in a QUV
cabinet, a product of Q-Panel Lab Products of Cleveland, Ohio. The
gloss loss is presented as a measure of the effect of UV radiation
on these coatings. The gloss of the treated panel is presented as a
percentage of the sample's original gloss.
[0327] Scrub Resistance: The scrub resistance of the coatings was
evaluated using an Abrasion Tester, a product of Byk-Gardner
Company of Rivers Park, Md. Films were applied using a 0.007-inch
blade applicator to plastic scrub charts (Leneta.TM. #121-10N) and
allowed to dry 14 days. The coating was scrubbed with an abrasive
medium as per ASTM D-2486. The number of strokes needed to
completely penetrate the coating is reported.
[0328] Chemical Resistance: The coating was applied to the
substrate and allowed to air dry for at least 14 days. At the end
of the indicated time, a filter paper disk saturated with the
chemical was placed on the coating for one hour. A watch glass was
placed over the filter paper disk to reduce water evaporation. The
test panel was flushed with tap water and the panels were inspected
for damage to the coating. Six responses were gathered for each
coating and rated on a 0-10 scale with 10 being the best. An
average of the six responses for each coating is shown in the
table.
[0329] Corrosion Resistance: The clear coating was applied to bare
cold rolled steel obtained from ACT Labs, Inc. (Hillsdale, Mich.).
The coating was allowed to dry for at least 7 days. The coating was
scribed and subjected to 86 hours in a salt spray cabinet, a
product of Q-Panel Lab Products of Cleveland, Ohio. The tests were
run according to ASTM B-117-90. Face rust was evaluated using ASTM
D-610 method. Undercut was measured based on ASTM D-1654.
Blistering was evaluated using ASTM D714.
[0330] Hardness: Hardness was measured using a Pendulum Hardness
Tester, Konig from the Byk Gardner Company of Rivers Park, Md. An
average of 3 readings for each coating is reported in the table
above.
[0331] Gloss: Gloss was measured on the sealed portion of a
Leneta.TM. 1B panel. The coating was applied to the panel with a
3-mil (0.003-inch) Bird blade applicator, and allowed to air dry. A
Byk-Gardner micro tri-glossmeter, a product of the Byk Gardner
Company of Rivers Park, Md., was used to measure the gloss.
[0332] Cross Hatch Tape Adhesion: A coating was applied to a panel
of bare cold rolled steel and allowed to air dry for 14 days. The
coating was scored in a cross hatch pattern with 4 a multiple tip
cutter with eleven parallel blades spaced 1.5 mm apart, specified
in ASTM D-3359. A piece of Scotch.TM. #610 tape was applied to the
coating. The tape was pulled at a 90 degree angle and the removal
of the coating was evaluated. The number represents the extent of
adhesion loss, with 5 equal to no loss, 4 equal to very slight, and
so on, with 0 equal to greater than 65% loss.
[0333] Preparation of Exemplary Water-Based Coating with Improved
Barrier Properties and Preparation of Conventional Water-Based
Coating.
[0334] The barrier properties of clay coated carton stock was
evaluated after coating with a composition containing an acrylic
emulsion polymer, a conventional or exemplary styrene acrylic
resin, and a paraffin wax emulsion (Michelman 62330, Michelman
Corp. Cincinnati, Ohio). Barrier performance was determined by a
gravimetric method (TAPPI test method T 448 om-89 [TAPPI Press,
1992]), where the rate of water vapor passing through the coated
stock was measured. Table 84 summarizes the water vapor
transmission rate for a composition containing a standard styrene
acrylic resin, and for a composition containing a resin of the
present invention. The coating composition containing Exemplary
Resin 33 provided improved barrier properties (lower water vapor
transmission rate) compared to the coating composition containing
Conventional Resin 1 even though the film thickness of the coating
containing Exemplary Resin 33 was thinner than that containing
Conventional Resin 1. This indicates that the reins of the present
invention have important properties for use as MVTR
applications.
81TABLE 84 Water Coating Vapor Film Trans. Composition
Components.sup.a Thickness Rate.sup.b Conventional Acrylic Emulsion
56% 1.2 mils 6 Water-Barrier Polymer Coating Conventional Resin 1
24% Paraffin Wax 20% Emulsion Exemplary Water- Acrylic Emulsion 56%
0.9 mils 2 Barrier Coating Polymer Exemplary Resin 33 24% Paraffin
Wax 20% Emulsion .sup.aFormula represented as parts of solids of
each component. .sup.bExpressed as grams per 100 square inches per
24 hours at 90% relative humidity and 37.8.degree. C.
[0335] Preparation of Exemplary and Conventional High Solids
Pigment Dispersions, Inks, and Bleachouts
[0336] Various high solids pigment dispersions can be made
utilizing the polymers of the present invention. For example, a
higher solids yellow pigment dispersion was prepared by combining
220.86 grams of Roma Color 014-HS-1054 (a 48.9 percent solids
presscake from Roma Color of Fall River, Mass.), 67.5 grams of
Resin cut B, 9 grams of a polyalkylene glycol, 1.5 grams of Ultra
Additives PI-35 (a product of Ultra Additives, inc. of Paterson,
N.J.), and 1.14 grams of water in a 1 quart blending cup. This
mixture was stirred and then poured into an Eiger mill. This
mixture was processed for 40 minutes at 5,000 rpm using 70 mL of
1.0 to 1.5 mm glass beads as the grinding media. The cut had a
viscosity of 41.50 seconds in a #3 Zahn cup and a pH of about 8.5
after 24 hours. The viscosity was 41.50 seconds in a #3 Zahn cup
after 1 week.
[0337] A comparable yellow pigment dispersion was prepared using
220.86 grams of the Roma Color 014-HS-1054, 27 grams of powdered
resin (1:1 mixture of Joncryl.TM. HPD 671 and Joncryl.TM. 678, both
products of S. C. Johnson & Sons, Inc. of Racine, Wis.), 9
grams of polyalkylene glycol, 1.5 grams of Ultra Additives PI-35,
6.31 grams of 28 percent ammonia, and 35.33 grams of water. The
dispersion was processed using the procedure described above. The
resins had to be formulated into this system as powders because
resin solutions were too thick to handle at the appropriate solids
level. The dispersion had a viscosity of 50 seconds in a #3 Zahn
cup and a pH of about 8.5 after 24 hours. The viscosity was 50
seconds in a #3 Zahn cup after 1 week.
[0338] Inks were made using 50 grams of the yellow pigment
dispersion, 50 grams of Joncryl.TM. 624, and 5.25 grams of water. A
drawdown was made on a N2A Leneta.TM. card using a #4 wire wound
rod. Gloss measurements (60.degree.) were taken using a gloss
meter. The gloss of the ink containing resin dispersion B was 63
over the white portion of the card, while the gloss of the ink with
the commercial resins was 62. It was surprisingly and unexpectedly
discovered that inks that incorporated the polymeric products of
the present invention exhibited less bronzing as compared to
conventional inks which incorporated conventional resins.
[0339] Bleachouts were made with 95 grams of a bleaching white
formula (50 percent Flexiverse.TM. WFD-5006 and 50 percent
Joncryl.TM. 74), 4 grams of the yellow pigment dispersion, and 1
gram of Flexiverse.TM. BFD-1121. This formula was mixed thoroughly
by adding 25 mL of glass beads to the container and tumbling the
container on a roller mill. A drawdown was made on a N2A Leneta.TM.
card using a #6 wire wound rod. The bleachouts containing Resin
solution B exhibited better color development in comparison to the
dispersion based on the commercial resins.
[0340] Joncryl.TM. 624 and Joncryl.TM. 74 are film-forming
emulsions manufactured by S. C. Johnson & Sons, Inc. of Racine,
Wis. Flexiverse.TM. WFD-5006 and Flexiverse.TM. BFD-1121 are white
and blue pigment dispersions, respectively, manufactured by Sun
Chemical Corporation of Fort Lee, N.J.
[0341] Preparation of Exemplary and Conventional Pigment
Dispersions and Inks for Printing on Film and Foil
[0342] An ink based on Exemplary Resin 42 was prepared for printing
on film and foil. A conventional ink based on Conventional Resin 10
was prepared and used as a control. To prepare the inks, base
pigment dispersions were prepared with the components listed in
Table 85.
82TABLE 85 Conventional Pigment Dispersion Exemplary Pigment
Dispersion Component Quantity Component Quantity Cut of
Conventional 170.45 grams Cut of Exemplary 170.04 grams Resin 10
Resin 42 Water 140.80 grams Water 124.20 grams Surfynol .TM. 1.25
grams Surfynol .TM. 1.18 grams DF-58 DF-58 Sun 249-1282 .TM. 187.50
grams Sun 249-1282 .TM. 177.25 grams Blue Blue
[0343] The components of the pigment dispersion were combined and
stirred with a spatula to wet out the pigment. The pigment was
dispersed in the aqueous resin solution by milling the mixture in
an Eiger mill for 20 minutes at 5000 rpm using about 70 mL of 1.0
to 1.5 mm glass beads as the grinding medium. The pigment
dispersion formula contain 37.5 percent pigment and a 4 to 1
pigment to binder ratio. Surfynol.TM. DF-58 is a defoamer
manufactured by Air Products and Chemicals, Inc. of Allentown, Pa.
Sun 249-1282.TM. blue is a phthalo blue pigment manufactured by Sun
Chemical Corporation of Cincinnati, Ohio.
[0344] Inks were prepared by mixing the pigment dispersions,
emulsion polymers and water with an overhead stirring apparatus
according to the composition presented in Table 86. The emulsion
polymers were prepared in the presence of resin cuts of
Conventional Resin 11 and Exemplary Resin 41. A monomer mixture of
48 percent butyl acrylate, 21 percent methyl methacrylate, and 31
percent 2-ethylhexyl acrylate was used in each of the emulsion
polymers. The final emulsion polymers had a solids content of about
48 percent.
83TABLE 86 Conventional Ink Exemplary Ink Component Quantity
Component Quantity Conventional 43.00 grams Exemplary Pigment 43.00
grams Pigment Dispersion Dispersion Conventional 50.00 grams
Exemplary Emulsion 50.00 grams Emulsion Water 8.00 grams Water 3.00
grams
[0345] The water was used to adjust the ink viscosity to about 24
seconds on a #2 Zahn cup. Zahn cups can be purchased from Paul N.
Gardner Company of Pompano Beach, Fla.
[0346] Side by side drawdowns were made on Leneta.TM. N2A panels
with a #4 wire wound rod to test gloss and other ink appearance
properties. The results are presented in Table 87.
84 TABLE 87 Property Conventional Ink Exemplary Ink 60 gloss, black
portion 44.4 44.1 60 gloss, black portion 33.6 34.9 Transparency
Standard Slightly less Bronzing Yes No Color Strength Equal
Equal
[0347] Side by side drawdowns were made on paper backed aluminum
foil with a #4 wire wound rod to test gloss and other ink
appearance properties. The results are presented in Table 88.
85 TABLE 88 Property Conventional Ink Exemplary Ink 60 gloss 90.6
94.2 Color Strength Equal Equal Transparency Standard Slightly
less
[0348] The inks were coated, side by side, onto a white medium slip
LDPE (low density polyethylene) film, manufactured by the James
River Corporation of Orange, Tex., using a 200P line anilox
handproofer. The inked substrate was placed in a forced air oven at
50.degree. C. for 10 seconds.
86TABLE 89 Property Conventional Ink Exemplary Ink Gloss Standard
Slightly less Bronzing Yes No Ink Transfer Standard Slightly less
Immediate Wet Crinkle Standard- Much better- much ink loss little
ink loss 24 hour Wet Crinkle Standard- Equal- little ink loss
little ink loss Immediate Tape Adhesion Standard-little ink
Equal-little ink loss, slow pull loss, slow pull 24 hour Tape
Adhesion Standard- little ink Equal-little ink loss, slow pull
loss, slow pull Film Wetting Good Good
[0349] Gloss, bronzing, ink transfer, and film wetting were
evaluated by visual inspection and the results are presented in
Table 89. Tape adhesion was measured with 3M #610 tape, a product
of the 3M Company of St. Paul, Minn. The tape was applied with a
four pound roller. The tape was then pulled at an angle 180 degrees
from the plane of the inked film. Both a slow and a fast pull were
performed with the same tape. A visual assessment of the ink
removal was made. In the wet crinkle test, the inked substrate was
immersed in room temperature water for 1 minute. The substrate was
removed and crinkled between the thumb and forefinger of each hand
for 50 to 100 crinkles or until the ink began to come off. The ink
loss was evaluated visually. In the 24 hour wet crinkle test, the
inked substrate, which was dried under ambient conditions for 24
hours, was immersed in room temperature water for 4 hours. The
substrate was removed and crinkled between the thumb and forefinger
of each hand for 200 crinkles or until the ink begins to come off.
The ink loss was evaluated visually.
[0350] Preparation of Exemplary and Conventional Paper Surface
Sizing Agents
[0351] Surface sizing agents are applied to paper to improve the
ink receptivity and the surface properties of paper. The following
example illustrates the utility of the aforementioned resin
compositions as Surface Sizing Agents.
[0352] A 12% solids starch solution was prepared by charging 780
grams of deionized water and 120 grams of Penford 230, a starch
obtained from Penford Products (Cedar Rapids, Iowa), into a two
liter 4-necked round bottomed flask equipped with a thermometer,
heating mantle, condenser, and mechanical agitator. While
agitating, the temperature was raised to 95.degree. C. over
approximately 30 minutes, and an additional 30 minute conditioning
was implemented. After the additional conditioning, an additional
432 grams of deionized water was added and the temperature was
reduced to 65.degree. C. The resulting solution was an 8% solids
aqueous solution of Penford 230 starch.
[0353] Three equal 370 gram portions of the above starch solution
were transferred to beakers, and additional water and additive were
charged to complete the preparation of the surface size
compositions described in the Table 90.
87 TABLE 90 Example A Example B Example C 8% Starch Solution Used
370 grams 370 grams 370 grams Deionized Water 2.35 grams 2.46 grams
5.0 grams Conventional Resin 1 -- 2.54 grams -- Exemplary Resin 34
2.65 -- --
[0354] Tests were performed to determine the efficacy of the paper
sizing agents on paper stock. TAPPI (Technical Association of the
Pulp and Paper Industry) 530 pm-89 test method was employed to
determine the ink resistance of the coated paper stock. The method
utilized a Hercules Size Tester (Hercules, Wilmington, Del.), an
apparatus that provides a relative measure of the ink printability
of paper. A volume of ink was placed on the paper, and the time
needed to penetrate the liquid ink through the paper was measured.
In addition to printability derived from the Surface Size
Composition, the foaming attributes of the Size Composition are
critical for proper application of the Size Composition.
[0355] Table 91 summarizes the ink printability as measured by the
Hercules Size Tester and the foaming character of the corresponding
Size Compositions.
88TABLE 91 Ink Printability as Determined by Hercules Size Tester
(TAPPI T530) Paper Paper Paper Coated with Coated with Coated with
Example A Example B Example C Description Surface Size Surface Size
Control Composition of prepared from Example the Present
Conventional with no Invention Resin added resin HST
(Seconds).sup.8 56 seconds 47 seconds 2 seconds Foaming Minimal
Considerable None .sup.8Hercules Size Tester reading in seconds
[0356] As the above example illustrates, the resin composition of
the present invention provides improvement in ink printability as
well as reduced foaming in paper sizing applications.
Preparation of Exemplary Oil and Wax Emulsions
[0357] Various oil and wax emulsions were prepared using
conventional and exemplary resins. Three types of oil were used to
prepare oil emulsions including mineral oil, castor oil, and
silicone oil. Mineral oil was selected as a representative of a
common hydrocarbon oil, castor oil was chosen as a representative
natural oil, and silicone oil was chosen as an example of a
low-surface tension synthetic oil. All three oils formed emulsions
with the exemplary resins using sonication to agitate the mixture
and produce the emulsion.
[0358] Emulsions were prepared with paraffin wax, carnauba wax,
AC-629 polyethylene wax, a wax manufactured by Allied Signal
(Morristown, N.J.), and with Epolene E-15 wax, a product of Eastman
Chemical Company (Kingsport, Tenn.). In each of the following
preparations, parts were determined on the basis of weight.
[0359] Exemplary Oil Emulsion 1
[0360] A mixture of 43.72 parts of water and 33 parts of a 30.3%
solids aqueous resin cut of Exemplary Resin 44 (83.9% neutralized
with ammonia) was heated to 85.degree. C. Drakeol 7, a white
mineral oil available from Penreco Inc. (Karns City, Pa.) (20.00
parts), was separately heated to 85.degree. C. and then 1.28 parts
of diethylaminoethanol was blended into the heated oil. The aqueous
mixture containing the resin cut of Exemplary Resin 44 was mixed
with the oil/diethylaminoethanol mixture at 85.degree. C. using a
two inch, 3 blade propeller mixer increasing the speed from 200 to
620 rpm. After mixing the resulting emulsion for 15 minutes at
85.degree. C., mixing was stopped and the mixture was allowed to
stand for 3 minutes. The resulting mixture was then mixed for 10
minutes at 550 rpm and 85.degree. C. and then it was force-cooled.
An aliquot of the force-cooled product was removed and sonicated
for 45 seconds at a setting of 5 using a Vibra-Cell.TM. sonicator
available from Sonics & Materials (Bridgeport, Conn.). Without
sonication, an oil/water emulsion was obtained which was opaque and
unstable and phase separation began almost immediately. After
sonication, on the other hand, a highly opaque and stable oil/water
emulsion was obtained. No phase separation was detectable one hour
after sonication although a lower layer comprising 25% of the total
mixture occurred on standing overnight.
[0361] Exemplary Oil Emulsion 2
[0362] A mixture of 35.71 parts of water and 39.60 parts of a 30.3%
solids aqueous resin cut of Exemplary Resin 44 (83.9% neutralized
with ammonia) was mixed at 25.degree. C. Drakeol 7 (20.00 parts)
was separately blended with 0.68 parts of diethylaminoethanol. The
aqueous mixture containing the resin cut of Exemplary Resin 44 was
slowly added to the oil/diethylaminoethanol mixture at 25.degree.
C. while blended using a two inch, 3 blade propeller mixer
increasing the speed from 200 to 750 rpm. After the addition was
complete, the mixture was blended for an additional 5 minutes. The
mixture was then allowed to stand for 5 minutes. The resulting
mixture was then mixed for 20 minutes at 600 rpm and 25.degree. C.
While mixing was continued, the mixture was sonicated for 2 minutes
at a setting of 5 using a Vibra-Cell.TM. sonicator. The mixer speed
was decreased to 450 rpm as the emulsion thinned. Without
sonication, an opaque water/oil emulsion was obtained. The
water/oil emulsion was unstable and phase separation began almost
immediately. After sonication, on the other hand, a highly opaque,
low viscosity, and stable oil/water emulsion was obtained. Slight
creaming was observed several hours after sonication and mixing was
stopped, and lower layer comprising 5% of the total mixture was
observed.
[0363] Exemplary Oil Emulsions 3-12
[0364] Exemplary Oil Emulsions 3-12 were prepared using the
following procedure. At 25.degree. C., 20 parts of Drakeol 7 and
diethylaminoethanol (DEAE) were blended. The amount of
diethylaminoethanol added was sufficient to completely react with
any remaining carboxylic acid functionalities remaining on the
polymer after the resin cut had been added. Thus, the amount of
diethylaminoethanol used varied slightly from one oil emulsion to
another. An aqueous resin cut of about 30% solids prepared from an
exemplary resin was mixed with water, and warmed, if necessary, to
clarify the solution. The aqueous resin-containing solution was
then cooled to 30.degree. C. and then added to the
oil/diethylaminoethanol mixture over 5 minutes while increasing the
mixing speed from 200 to 600 rpm. After addition was complete, the
emulsion was mixed for 5 minutes at 750 rpm. While mixing was
continued, the emulsion was sonicated for 2 minutes using a
Vibra-Cell.TM. sonicator at a power setting of 5. The mixer speed
was decreased from 750 to 400 rpm as the emulsions thinned.
Generally, the emulsions were found to be viscous and opaque
water/oil emulsions if sonication was not performed. These inverted
to opaque low-viscosity oil/water emulsions with sonication. The
following table provides stability and composition data for
Exemplary Oil Emulsions 3-12.
89TABLE 92 Composition of Oil Emulsions 3-12.sup.a Shelf Stability
Resin Cut Characteristics of Oil Emulsions Exemplary Amount of
Water Exemplary Resin Used Resin Cut used DEAE Separation Days to
Oil to Prepare to Prepare Oil DN.sup.b added at 14 days Free Oil
Emulsion Resin Cut Emulsion (% w/w) (%) (% w/w) (%) Formation 3 39
32.57 83.4 0.51 51 >14 4 52 32.89 86.3 0.51 56 >14 5 48 34.01
93.1 0.21 53 >14 6 49 32.68 86.6 0.55 Broken 5 7 50 32.47 86.0
0.59 58 >14 8 47 33.33 87.7 0.37 53 >14 9 41 32.26 89.5 0.45
54 >14 10 51 32.79 87.8 0.51 56 >14 11 40 33.11 82.7 0.54
Broken 5 12 44 33.00 83.9 0.57 57 >14 .sup.aEach of the oil
emulsion formulations phase inverted on sonication to produce
oil/water emulsions. .sup.bDN (degree of neutralization) is the
percent that the exemplary resin is neutralized with ammonia prior
to adjustment with DEAE to 100% neutralization.
[0365] Exemplary Oil Emulsion 13
[0366] A mixture of 20 parts castor and 0.57 parts
diethylaminoethanol, an amount sufficient to neutralize all the
carboxylic acid groups on the exemplary resin, was prepared by
blending the two components together at 40.degree. C. A mixture of
33 parts of an aqueous resin cut with 30.3% solids of Exemplary
Resin 44 and 46.43 parts water was also prepared. The aqueous
mixture containing the resin cut of Exemplary Resin 44 was then
added to the oil/diethylaminoethanol mixture over 5 minutes at
40.degree. C. while the mixture was stirred at 200 to 350 rpm.
After addition was complete, the resulting mixture was stirred for
8 minutes at 350 rpm. While mixing at 350 rpm continued, the
mixture was sonicated at a power setting of 5 using a
Vibra-Cell.TM. sonicator for 2 minutes. Before sonication, the
mixture was a semi-opaque emulsion. After sonication, an opaque,
low viscosity oil/water emulsion was obtained. After 14 days, water
separation had occurred to an extent of 63%, but no free oil layer
was observed.
[0367] Exemplary Oil Emulsion 14
[0368] A mixture of 20 parts silicone oil and 0.57 parts
diethylaminoethanol, an amount sufficient to neutralize all the
carboxylic acid groups on the exemplary resin, was prepared by
blending the two components together at 25.degree. C. A mixture of
33 parts of an aqueous resin cut with 30.3% solids of Exemplary
Resin 44 and 46.43 parts water was also prepared. The aqueous
mixture containing the resin cut of Exemplary Resin 44 was then
added to the oil/diethylaminoethanol mixture over 6 minutes at
25.degree. C. while the mixture was stirred at 200 to 600 rpm.
After addition was complete, the resulting mixture was stirred for
10 minutes at 450 rpm. While mixing at 450 rpm continued, the
mixture was sonicated at a power setting of 5 using a
Vibra-Cell.TM. sonicator for 2 minutes. Before sonication, the
mixture was a semi-opaque emulsion which had undergone phase
inversion. After sonication, an opaque, low viscosity oil/water
emulsion was obtained. After 14 days, water separation had occurred
to an extent of 58%, but no free oil layer was observed.
[0369] Exemplary Oil Emulsions 15-20 and Conventional Oil Emulsions
1-3
[0370] Exemplary Oil Emulsions 15-20 and Conventional Oil Emulsions
1-3 were prepared using the following procedure. At 25.degree. C.,
a specified quantity of Drakeol 7 mineral oil and
diethylaminoethanol (DEAE) were blended. The amount of
diethylaminoethanol added was sufficient to completely react with
any remaining carboxylic acid functionalities remaining on the
polymer after the resin cut had been added. Thus, the amount of
diethylaminoethanol used varied slightly from one oil emulsion to
another. An aqueous resin cut of about prepared from an exemplary
or conventional resin was mixed with water, and warmed, if
necessary, to clarify the solution. The aqueous resin-containing
solution was then cooled to 30.degree. C. and then added to the
oil/diethylaminoethanol mixture over 5 minutes while generally
increasing the mixing speed from 200 to 600 rpm. After addition was
complete, the emulsion was generally mixed for 5 minutes at 750
rpm. While mixing was continued, the emulsion was sonicated for 2
minutes using a Vibra-Cell.TM. sonicator at a power setting of 5.
The mixer speed was generally decreased from 750 to 400 rpm as the
emulsions thinned. The following table provides stability and
composition data for Exemplary Oil Emulsions 3-12 and Conventional
Oil Emulsions 1-3.
90TABLE 93 Composition of Oil Emulsions Exemplary Oil Emulsions
5-20 and Conventional Oil Emulsions 1-3.sup.a Shelf Stability of
Resin Resin Cut Oil Emulsions Ex. Resin Resin in Mineral Amount of
Nonvol in DEAE Water Sep. Days to Oil used in Resin Cut Oil Amt.
Resin Cut Resin Cut DN.sup.b used at 14 days Free Oil Emuls. Resin
Cut (% w/w) (% w/w) Used (% w/w) (% w/w) % (% w/w) (%) Form.
15.sup.c Ex. Res. 44 25.00 5.00 82.51 30.3 83.9 1.43 Broken 1 16
Ex. Res. 44 20.00 10.00 66.00 30.3 83.9 1.14 Broken 0 17 Ex. Res.
44 2.00 28.00 6.60 30.3 83.9 0.11 51 >14 18 Ex. Res. 44 0.50
29.50 1.65 30.3 83.9 0.03 53 >14 19 Ex. Res. 44 0.10 29.90 0.33
30.3 83.9 0.01 53 >14 20.sup.d Ex. Res. 44 0.00 30.00 0.00 -- --
0.11 Broken 0 Con. Oil Emuls. 1 Con. Res. 12 10.00 20.00 19.80 50.5
97.4 0.12 Broken 0 2 Con. Res. 14 10.00 20.00 32.47 30.8 85.5 0.67
56 >14 3 Con. Res. 14 10.00 20.00 32.47 30.8 85.5 0.35.sup.e 54
>14 .sup.aEach of the oil emulsion formulations except Exemplary
Oil Emulsions 15 and 20 phase-inverted on sonication to produce
oil/water emulsions. .sup.bDN (degree of neutralization) is the
percent that the exemplary resin is neutralized with ammonia prior
to adjustment with DEAE to 100% neutralization.
.sup.cphase-inversion occurred prior to sonication producing a
semi-opaque oil/water emulsion. Sonication produced no apparent
improvement. .sup.da two-phase mixture remained until sonication
was performed. After sonication, a transient opaque emulsion formed
that immediately broke and separated after agitation. .sup.e28%
ammonia was used in place of the diethylaminoethanol.
[0371] Exemplary Oil Emulsion 21
[0372] Exemplary Oil Emulsion 21 was prepared with mineral oil and
a resin cut prepared from Exemplary Resin 46 having 24.7% solids
and having enough ammonia added to neutralize 104% of the
carboxylic acid groups. Exemplary Oil Emulsion 21 was prepared by
mixing 20.27 parts of the resin cut, 15 parts of mineral oil, and
64.73 parts of water at 360 rpm and 55.degree. C. After the mineral
oil was mixed in, the stirred mixture was sonicated for 2 minutes
at 55-58.degree. C. at a power level of 5 using a Vibra-Cell.TM.
sonicator. The resulting emulsion was stirred at 360 rpm for an
additional 10 minutes at 55-58.degree. C. before it was
force-cooled to 30.degree. C. by immersion in an ice bath.
[0373] The reaction mixture was translucent before sonication, and
a very smooth, opaque white oil/water emulsion was observed after
sonication.
[0374] Exemplary Wax Emulsion 1
[0375] Epolene E-15 wax (24 parts) and Exemplary Resin 2 (12 parts)
were melted and mixed thoroughly. Diethylaminoethanol (5 parts) was
then added to the molten mixture. The resulting mixture was then
added to 59 parts of water at 98.degree. C. with good agitation. A
fluid emulsion resulted, and the hot emulsion was cooled rapidly to
room temperature. The final emulsion was a thick, tan mixture with
a viscosity of 15,000 cps at 41.2 percent solids and a pH of 9.4.
The emulsion contained no grit or undispersed material. Addition of
water to reduce the emulsion solids to about 30 percent resulted in
a more workable viscosity.
[0376] Exemplary Wax Emulsion 2
[0377] A wax emulsion was prepared using the method for Exemplary
Wax Emulsion 1. All amounts and conditions were the same except
that Exemplary Resin 4 was used in place of Exemplary Resin 2. The
final emulsion was tan and contained some grit. The final emulsion
had a viscosity of 55 cps at 40 percent solids and a pH of 8.6.
Some separation was observed with aging, however, the separated
material easily redispersed.
[0378] Exemplary Wax Emulsion 3
[0379] Exemplary Wax Emulsion 3 was prepared by charging 17.5 parts
of AC 629, 8.75 parts Exemplary Resin 2, 3.5 parts of
diethylaminoethanol and 14 parts water to a vessel. This mixture
was heated and mixed to uniformity at about 150.degree. C. and
maintained at that temperature for about 15 minutes. The remaining
56.25 parts of water was added at about 99.degree. C. and 120 psi.
This mixture was stirred at 500 rpm under a pressure of 80 psi for
10 minutes. The emulsion was force-cooled. A thin tan emulsion was
obtained which had a viscosity of about 15 cps at 25.7 percent
solids and a pH of 9.5. The emulsion was stable.
[0380] Exemplary Wax Emulsions 4-23
[0381] Exemplary Wax Emulsions 4-13 were prepared using Exemplary
Resins 40, 41, 51, 44, 39, 47, 48, 49, 50, and 52 respectively.
Similarly, Exemplary Wax Emulsions 14-23 were prepared using
Exemplary Resins 40, 41, 51, 44, 39, 47, 48, 49, 50, and 52
respectively. Each of Exemplary Wax Emulsions 4-13 was prepared
using 24 parts of AC-629 polyethylene wax whereas Exemplary Wax
Emulsions 14-23 were prepared using 20 parts of AC-629 polyethylene
wax. Exemplary Wax Emulsions 4-13 contained 12 parts of an
exemplary resin cut prepared from an exemplary resin and having
33.3% solids and 83-93% of the carboxylic acid groups neutralized
with ammonia whereas Exemplary Wax Emulsions 14-23 contained 10
parts of an exemplary resin cut with the same specifications. Water
was also included in each of Exemplary Wax Emulsions 4-23. In
Exemplary Wax Emulsions 4-13, 59 parts of water was used, whereas
in Exemplary Wax Emulsions 14-23, 65-66 parts of water was used.
Diethylaminoethanol was also used to prepare Exemplary Wax
Emulsions 4-23. While 5 parts of DEAE was used to prepare Exemplary
Wax Emulsions 4-13, 4 to 5 parts of DEAE was used to prepare
Exemplary Wax Emulsions 14-23.
[0382] The exemplary wax emulsions were prepared by first
melt-blending the AC-629 polyethylene wax and exemplary resin in a
porcelain casserole at 140-155.degree. C. Diethylaminoethanol was
then blended into the resulting mixture. Next, the water was
separately heated to 98.degree. C. in a reaction vessel. The mixed
blend of the AC-629 polyethylene wax, the diethylaminoethanol, and
the exemplary resin was then slowly added while mixing the
resulting product at 500 rpm. After addition was complete, the
resulting mixture was stirred for 15 minutes at 500 rpm and
88-95.degree. C. before it was force-cooled to 30.degree. C. by
immersion in an ice bath. While very good oil/water emulsions were
formed with each of the exemplary resins, best results were
observed for Exemplary Wax Emulsions 14, 17, 19-21, and 23.
[0383] Exemplary Wax Emulsions 24-43 and Conventional Wax Emulsions
1-4
[0384] Exemplary Wax Emulsions 24-43 and Conventional Wax Emulsions
1-4 were formed with paraffin wax using the same procedure.
Exemplary Wax Emulsions 24-33 and Conventional Wax Emulsions 1-2
were formed using resin cuts obtained from Exemplary Resins 39-41,
44, and 47-52 and Conventional Resins 12 and 14 respectively.
Similarly, Exemplary Wax Emulsions 34-43 and Conventional Wax
Emulsions 3-4 were prepared using resin cuts obtained from
Exemplary Resin 39-41, 44, and 47-52 and Conventional Resins 12 and
14 respectively, but with different amounts than used in the other
examples. The resin cuts used to prepare the various emulsions
contained 30-50% solids. Additionally, 85-90% of the carboxylic
acid groups in the resin cuts had been neutralized with
ammonia.
[0385] The emulsions were prepared by combining water (80 parts for
Exemplary Wax Emulsions 24-33 and Conventional Wax Emulsions 1-2;
60 parts for Exemplary Wax Emulsions 34-43 and Conventional Wax
Emulsions 3-4) with the resin cut (5 parts for Exemplary Wax
Emulsions 24-33 and Conventional Wax Emulsions 1-2; 10 parts for
Exemplary Wax Emulsions 34-43 and Conventional Wax Emulsions 3-4)
while mixing at 200 rpm and 55.degree. C. The paraffin wax (15
parts for Exemplary Wax Emulsions 24-33 and Conventional Wax
Emulsions 1-2; 30 parts for Exemplary Wax Emulsions 34-43 and
Conventional Wax Emulsions 3-4) was added to the resulting mixture
at 60.degree. C. while mixing was continued at the same speed.
After the wax had melted, the resulting mixture was stirred at 400
rpm for an additional 2 to 3 minutes. While stirring continued, the
mixture was sonicated for two minutes at a power setting of 5 using
a Vibra-Cell.TM. sonicator equipped with a one-half inch diameter
probe. After sonication, the mixture was stirred for an additional
10 minutes at 400 rpm at 65.degree. C. and then force-cooled by
immersion in a 30.degree. C. ice bath.
[0386] Exemplary Wax Emulsions 24-43 obtained from the exemplary
resins were characterized as good to excellent oil/water emulsions.
No emulsion was obtained if the resin cut was omitted form the
mixture. While excellent emulsions were formed using Conventional
Resin 14, only poor emulsions were obtained using Conventional
Resin 12.
[0387] Exemplary Wax Emulsion 44 and Conventional Wax Emulsions
5-6
[0388] Exemplary Wax Emulsion 44 and Conventional Wax Emulsions 5
and 6 were prepared using the same general procedure with carnauba
wax. Exemplary Wax Emulsion 44 was prepared using a resin cut
prepared from Exemplary Resin 44 the resin cut having 30.3% solids
and having 83.8% of the carboxylic acid groups neutralized with
ammonia. Conventional Wax Emulsions 5 and 6 were respectively
prepared using resin cuts of Conventional Resins 12 and 14.
Exemplary Wax Emulsion 44 and Conventional Wax Emulsions 5 and 6
were prepared by mixing 16.5 parts of the resin cut, 15.0 parts of
carnauba wax, and 68.50 parts of water at 360 rpm and 87-90.degree.
C. After the carnauba wax melted, the stirred mixture was sonicated
for 3 minutes at 86-90.degree. C. at a power level of 5 using a
Vibra-Cell.TM. sonicator. Stirring was then continued at
86-90.degree. C. for 10 minutes at 360 rpm before the mixture was
force-cooled to 30.degree. C. by immersion in an ice bath.
[0389] Prior to sonication, beads of molten wax were observed in
the aqueous medium. After sonication, opaque emulsions were
obtained. The products were fairly smooth, opaque oil/water
emulsions which exhibited a slight graininess. Only 1% of a lower
water layer was visible after one day.
[0390] Exemplary Wax Emulsion 45
[0391] Exemplary Wax Emulsion 45 was prepared using carnauba wax
and a resin cut prepared from Exemplary Resin 45 the resin cut
having 30.3% solids and having 83.8% of the carboxylic acid groups
neutralized with ammonia. Exemplary Wax Emulsion 45 was prepared by
mixing 20.83 parts of the resin cut, 15.0 parts of carnauba wax,
and 64.17 parts of water at 360 rpm and 87-90.degree. C. After the
carnauba wax melted, the stirred mixture was sonicated for 3
minutes at 86-90.degree. C. at a power level of 5 using a
Vibra-Cell.TM. sonicator. Stirring was then continued at
86-90.degree. C. for 10 minutes at 360 rpm before the mixture was
force-cooled to 30.degree. C. by immersion in an ice bath.
[0392] Prior to sonication, beads of molten wax were observed in
the aqueous medium. After sonication, a very smooth opaque
oil/water emulsion was obtained.
[0393] Exemplary Wax Emulsion 46
[0394] Exemplary Wax Emulsion 46 was prepared with carnauba wax and
a resin cut prepared from Exemplary Resin 46 having 24.7% solids
and having enough ammonia added to neutralize 104% of the
carboxylic acid groups. Exemplary Wax Emulsion 46 was prepared by
mixing 20.27 parts of the resin cut, 15 parts of carnauba wax, and
64.73 parts of water at 360 rpm and 72.degree. C. After the wax
melted, the stirred mixture was sonicated for 2 minutes at
61-65.degree. C. at a power level of 5 using a Vibra-Cell.TM.
sonicator. The resulting emulsion was stirred at 360 rpm for an
additional 10 minutes at 65-67.degree. C. before it was
force-cooled to 30.degree. C. by immersion in an ice bath.
[0395] The reaction mixture was translucent before sonication, and
a very smooth, opaque white oil/water emulsion was observed after
sonication.
[0396] Preparation of Resin Supported Emulsion Polymers
[0397] Resin supported emulsion polymers are prepared at a total
weight percent solids level of from 35 to 55. In preparing a resin
supported emulsion polymer, sufficient resin, as the resin cut, is
added to the reaction flask to make the resin constitute about 5 to
about 50 percent of the final emulsion polymer solids. One or more
conventional surfactants ranging from about 0 to about 5 weight
percent of the final emulsion polymer, may be added to the reaction
flask at the beginning of the reaction or with the monomer. Typical
conventional surfactants used in resin supported emulsions are
anionic or nonionic surfactants. Additional water may be added to
adjust the desired weight percent solids of the final emulsion
polymer. The mixture of resin, conventional surfactant, and water
is heated to from about 70.degree. C. to about 90.degree. C. A free
radical initiator is added to the hot resin/conventional surfactant
mixture. The initiator is typically from about 0.4 to about 1.3
weight percent of the monomer added to form the emulsion polymer.
Typically, persulfate salts, such as ammonium persulfate or
potassium persulfate, are used as free radical initiators, but
other water soluble free radical initiators may also be used. The
monomers are then added to the reaction mixture. The monomers
comprise about 50 to about 95 percent of the final emulsion polymer
solids. A small portion, about 5 to about 15 weight percent, of the
monomers may be added before the addition of the initiator as a
precharge. A wide variety of ethylenically unsaturated monomers,
and various combinations thereof, may be used. Typically, the
monomer is added to the resin cut over a period of about 25 minutes
to 3 hours at temperatures from 70.degree. C. to 90.degree. C. when
a persulfate salt is used as an initiator. Other temperatures and
addition times may be useful when other types of initiators are
used. After the monomer feed has been completed, additional
initiator may be added and the latex should be maintained at the
reaction temperature for a time period sufficient to reduce the
monomer concentration to a very low level. When the latex has
cooled, a preservative is usually added.
91TABLE 94 Emulsion Polymers with 25% Styrene/25% Methyl
Methacrylate/50% 2-Ethylhexyl Acrylate. Alkanol Visc. % % % Resin
Used type pH (cps) solids 2EHA 2EHOH D.sub.n D.sub.w
D.sub.w/D.sub.n SD.sub.n SD.sub.w Con. Resin 14 C0 8.4 520 47.7
0.27 0.03 60.4 251.8 4.17 21.5 272.8 Con. Resin 15 C8 8.4 230 47.8
0.08 0.02 54.0 70.8 1.31 14.5 26.7 Ex. Resin 27 C10 8.3 175 47.9
0.03 0.04 58.1 77.4 1.33 16.4 28.6 Ex. Resin 28 C12 8.2 230 48.1
0.06 0.03 57.0 76.8 1.35 15.9 30.6 Ex. Resin 29 C14 8.0 240 48.0
0.05 0.03 53.6 65.7 1.23 13.0 19.8 Ex. Resin 30 C16 8.3 350 48.0
0.04 0.03 53.6 63.0 1.18 11.6 16.9 Ex. Resin 31 70% C16 8.4 485
48.0 0.04 0.04 51.9 59.3 1.14 10.6 13.4 30% C18 Ex. Resin 32 30%
C16 8.4 555 48.0 0.04 0.02 50.4 57.7 1.14 10.1 14.0 70% C18 Ex.
Resin 33 C18 8.6 735 47.9 0.03 0.04 50.0 55.8 1.12 9.1 11.6 Ex.
Resin 34 C22 8.4 920 47.9 0.11 0.03 45.9 48.2 1.05 5.8 6.4 Ex.
Resin 35 Iso C12 8.4 215 47.9 0.04 0.04 56.1 72.4 1.29 15.2 24.8
Ex. Resin 36 Iso C16 8.5 275 47.8 0.08 0.04 55.4 65.2 1.18 12.7
15.6 Ex. Resin 37 Iso C20 8.4 480 47.8 0.04 0.03 52.7 63.1 1.20
12.1 17.7
[0398]
92TABLE 95 Emulsion Polymers with 100% Styrene. Alkanol Visc. % %
Resin Used type pH (cps) solids Styrene D.sub.n D.sub.w
D.sub.w/D.sub.n SD.sub.n SD.sub.w Con. Resin 14 C0 8.5 225 49.1
0.06 63.3 118.1 1.87 23.2 109.7 Con. Resin 15 C8 8.5 200 48.5 0.05
58.3 72.0 1.23 15.4 19.5 Ex. Resin 27 C10 8.7 140 48.8 0.07 57.0
69.7 1.22 13.8 20.9 Ex. Resin 28 C12 8.3 250 49.2 0.06 54.6 63.6
1.16 11.6 16.3 Ex. Resin 29 C14 8.5 305 49.5 0.07 53.7 62.8 1.17
11.4 16.7 Ex. Resin 30 C16 8.4 290 49.1 0.07 53.0 61.1 1.15 10.7
15.3 Ex. Resin 31 70% C16 8.7 470 48.9 0.06 50.6 57.8 1.14 10.0
14.0 30% C18 Ex. Resin 32 30% C16 8.6 525 49.2 0.06 52.5 59.1 1.13
9.9 13.2 70% C18 Ex. Resin 33 C18 8.7 845 49.2 0.07 49.8 55.8 1.12
9.2 12.4 Ex. Resin 34 C22 8.7 725 49.3 0.07 48.6 51.8 1.07 6.7 8.2
Ex. Resin 35 Iso C12 8.3 180 49.2 0.06 56.5 72.6 1.28 14.8 26.0 Ex.
Resin 36 Iso C16 8.4 250 49.3 0.06 54.6 65.5 1.20 13.1 17.0 Ex.
Resin 37 Iso C20 8.4 450 49.3 0.06 53.1 65.6 1.24 12.8 21.2
Particle Size and Surface Tension Measurements
[0399] Particle size measurements were carried out on resin
solutions diluted to 10-21% (w/w) with pH matched deionized water.
Concentration of the solutions was chosen at the lowest level that
resulted in scattered light intensity value suitable for making
measurements with a Microtrac UPA instrument from Honeywell of
Minneapolis, Minn. A Kruss K 12 tensiometer available from Kruss
USA (Charlotte, N.C.) was used to measure the surface tension of 2%
(w/w) resin solutions made with pH matched deionized water. Surface
tension concentration profiles were made in the automatic mode by
controlling the Kruss tensiometer and a coupled automatic 665
Dosimat burette obtained from Metrohm (Herisau, Switzerland) using
the Kruss 122 software program obtained from Kruss USA (Charlotte,
N.C.). The results of these experiments are presented in Table
96.
93TABLE 96 Computed parameters from Surface Tensions-Concentration
Profiles* Surface Surface Tension Area per at CMC.sup.a CMC CMC
Molecule Sample (mN/m) (% w/w) (molar) (.ANG..sup.2) pC20.sup.b
Exemplary 30.9 0.0309 1.38 .times. 10.sup.-4 14.5 4.5 Resin 39
Exemplary 28.6 0.0282 1.55 .times. 10.sup.-4 12.7 3.85 Resin 40
Fluorad 30.5 0.0850 1.4 .times. 10.sup.-3 36.3 3.5 FC 120.sup.c
Sodium 32 0.23 8.2 .times. 10.sup.-3 47.0 2.57 Dodecyl
Sulfate.sup.d *All measurements were conducted at 23.degree. C.
.sup.aCMC is the critical micelle concentration. .sup.bpC20 is
equal to -log 10 (C.sub.20), where C.sub.20 is the molar
concentration at which the surface tension is lowered by 20 mN/m
from that of water. .sup.cFluorad 120 is a brand of
fluorosurfactant available from 3M (Minneapolis, Minnesota).
.sup.dSodium dodecyl sulfate is also known as sodium lauryl sulfate
and was obtained form the Aldrich Chemical Company of Milwaukee,
WI.
[0400] The data illustrated in FIGS. 8-11 was obtained by
conducting measurements on aqueous solutions of the various
materials. The same instrumentation used above was used to obtain
the value of surface tension. For FIG. 8, the temperature was
maintained at 25.degree. C., and measurements were made after
equilibration had been established at each of the concentrations
shown. For FIGS. 9-11, aqueous 2 percent solutions were formed by
dissolving the materials in deionized water at the labeled amount.
The surface tensions of the various surfactant solutions were then
measured as a function of temperature as described above.
[0401] While only a few, preferred embodiments of the invention
have been described, those of ordinary skill in the art will
recognize that the embodiment may be modified and altered without
departing from the central spirit and scope of the invention. Thus,
the preferred embodiments described above are to be considered in
all respects as illustrative and not restrictive, the scope of the
invention being indicated by the following claims, rather than by
the foregoing description, and all changes which come within the
meaning and range of equivalents of the claims are intended to be
embraced.
* * * * *