US4892916A
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Polymeric thickeners and their production
Assignee: Ciba Specialty Chemicals Water Treatments Ltd
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Filing: 1987-09-22
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Granted: 1990-01-09
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Expires: 2007-09-22
Abstract
Abstract Polymers are made by polymerization of an ionic monomer such as methacrylic acid or dialkylaminoalkyl (meth)-acrylate or -acrylamide and/or a substantially non-ionic monomer, optionally a cross linking agent, and an allyl ether of the formula CH 2 ═CR'CH 2 OA m B n A p R where R' is hydrogen or methyl, A is propyleneoxy or butyleneoxy, B is ethyleneoxy, n is zero or an integer, m and p are zero or an integer less than n, and R is a hydrophobic group of at least 8 carbon atoms. The polymers are preferably made by oil in water emulsion polymerization. They can be used as thickeners particularly in environments containing surfactant and/or electrolyte, including especially emulsion paints, print pastes, alkaline liquors and acidic liquors.
Inventors
- 👤 Malcolm Hawe
- 👤 David Farrar
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 16:06
CPC Classifications
C; C08; C08J; C08J3/00; C08J3/02; C08J3/03; A; A61; A61L; A61L15/00; A61L15/16; A61L15/42; A61L15/60; C02; C02F; C02F1/00; C02F1/52; C02F1/54; C07; C07C; C07C41/00; C07C41/01; C07C41/16; C08F; C08F16/00; C08F16/12; C08F16/14; C08F16/26; C08F2/00; C08F2/32; C08F216/00; C08F216/12; C08F220/00; C08F220/02; C08F220/04; C08F220/06; C08F220/10; C08F220/26; C08F220/28; C08F220/285; C08F220/286; C08F246/00; C08J3/09; C09; C09J; C09J133/00; C09J133/04; C09J133/06; C09J133/062; C09J157/00; C09J157/04; C09K; C09K8/00; C09K8/02; C09K8/04; C09K8/14; C09K8/18; C09K8/22; C09K8/24; C08J2300/00; C08J2300/10; C08J2300/14
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
160 words
A polymer that is substantially non swelling and insoluble in water but soluble or swellable in aqueous acid or alkali, and formed by oil in water emulsion polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 5 to 90% by weight of monolthylenically unsaturated ionic monomer (b) 5 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 90% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 O n R where R' is hydrogen or methyl and in which B, n and R are as defined above and monomer (d) consists essentially of polyethylenically unsaturated monomer.
Claim 2
Dependent Claim
160 words
A polymer that is substantially non swelling and insoluble in water but soluble or swellable in aqueous acid or alkali, and formed by oil in water emulsion polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 5 to 90% by weight of monolthylenically unsaturated ionic monomer (b) 5 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 90% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 O n R where R' is hydrogen or methyl and in which B, n and R are as defined above and monomer (d) consists essentially of polyethylenically unsaturated monomer.
Claim 3
Dependent Claim
50 words
A polymer according to claim 1 formed from 20 to 60% by weight (meth) acrylic acid, 2 to 50% by weight alkyl (meth) acrylate where alkyl is methyl, ethyl or butyl, 2 to 50% by weight of the allyl ether and 0 to 0.2% of the said cross linking monomer.
Claim 4
Dependent Claim
22 words
A polymer according to claim 1 in which monomer (a) is selected from the group consisting of acrylic acid and methacrylic acid.
Claim 5
Dependent Claim
16 words
A polymer according to claim 1 in which monomer (a) comprises a vinyl tertiary amine monomer.
Claim 6
Dependent Claim
22 words
A polymer according to claim 1 in which monomer (a) comprises a dialkylaminoalkyl (meth) acrylate monomer or a dialkylaminoalkyl (meth) acrylamide monomer.
Claim 7
Dependent Claim
38 words
A polymer according to claim 1 in which monomer (b) is selected from styrene, alkyl-substituted styrenes, halo-substituted styrenes, (meth) acrylonitrile, vinyl alkanoates, vinyl halides, vinylidene halides, hydroxy alkyl (meth) acrylates, alkoxy alkyl (meth) acrylates and alkyl (meth) acrylates.
Claim 8
Dependent Claim
17 words
A polymer according to claim 1 in which, in monomer (c), n is from 2 to 100.
Claim 9
Dependent Claim
35 words
A polymer according to claim 1 in which, in monomer (c), R is a hydrophobic hydrocarbyl group of 8 to 30 carbon atoms selected from alkyl, aralkyl, aryl, alkaryl and cycloalkyl and R' is hydrogen.
Claim 10
Dependent Claim
35 words
A polymer according to claim 1 in which, in monomer (c), R contains 10 to 24 carbon atoms and is selected from alkyl and alkaryl and n is an integer of from 5 to 100.
Claim 11
Dependent Claim
51 words
A composition comprising a polymer according to claim 1 which is in the form of an aqueous emulsion at a pH such that the polymer is insoluble and substantially unswollen and non-thickening but can be converted to a dissolved or swollen and thickening state by the addition of acid or alkali.
Claim 12
Dependent Claim
39 words
An aqueous composition that has been thickened by adding to the composition a thickening amount of a polymer according to claim 1 and, before or after the addition, adjusting the pH such that the polymer is dissolved or swollen.
Claim 13
Dependent Claim
13 words
A composition according to claim 11 selected from print pastes and emulation paints.
Claim 14
Dependent Claim
24 words
A composition according to claim 12 and which also contains surfactant in an amount of 0.05 to 1 part per part by weight polymer.
Claim 15
Dependent Claim
131 words
A linear polymer having intrinsic viscosity of at least 0.5 (measured as single point at 0.05% concentration in methanol) and formed by polymerisation in the absence of a cross-linking agent of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 OB n R where R' is hydrogen or methyl and B, n and R are as defined above.
Claim 16
Dependent Claim
131 words
A linear polymer having intrinsic viscosity of at least 0.5 (measured as single point at 0.05% concentration in methanol) and formed by polymerisation in the absence of a cross-linking agent of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 OB n R where R' is hydrogen or methyl and B, n and R are as defined above.
Claim 17
Dependent Claim
179 words
A linear, water soluble, polymer having intrinsic viscosity at least 0.5 (measured as single point at 0.05% concentration in methanol) and formed by polymerisation in the absence of a cross-linking agent of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R' is a hydrophobic hydrocarbyl group of at least 8 carbon atoms and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 OB n R where R is hydrogen or methyl and B, n and R are as defined above and in which monomers (a) and (b) are water soluble and the polymer is formed from 2 to 15% by weight of the allyl ether and from 5 to 98% by weight of the monomers (a) and (b), and the polymer has molecular weight above 0.5 million.
Claim 18
Dependent Claim
179 words
A linear, water soluble, polymer having intrinsic viscosity at least 0.5 (measured as single point at 0.05% concentration in methanol) and formed by polymerisation in the absence of a cross-linking agent of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R' is a hydrophobic hydrocarbyl group of at least 8 carbon atoms and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 OB n R where R is hydrogen or methyl and B, n and R are as defined above and in which monomers (a) and (b) are water soluble and the polymer is formed from 2 to 15% by weight of the allyl ether and from 5 to 98% by weight of the monomers (a) and (b), and the polymer has molecular weight above 0.5 million.
Claim 19
Dependent Claim
22 words
A polymer according to claim 15 in which monomer (a) is selected from the group consisting of acrylic acid and methacrylic acid.
Claim 20
Dependent Claim
16 words
A polymer according to claim 15 in which monomer (a) comprises a vinyl tertiary amine monomer.
Claim 21
Dependent Claim
22 words
A polymer according to claim 15 in which monomer (a) comprises a dialkylaminoalkyl (meth) acrylate monomer or a dialkylaminoalkyl (meth) acrylamide monomer.
Claim 22
Dependent Claim
37 words
A polymer according to claim 15 formed from 5 to 50% by weight monoethylenically unsaturated carboxylic acid or sulphonic acid monomer, 50 to 90% by weight acrylamide and 2 and 30% by weight of the allyl ether.
Claim 23
Dependent Claim
17 words
A polymer according to claim 15 in which, in monomer (c), n is from 2 to 100.
Claim 24
Dependent Claim
35 words
A polymer according to claim 15 in which, in monomer (c), R is a hydrophobic hydrocarbyl group of 8 to 30 carbon atoms selected from alkyl, aralkyl, aryl, alkaryl and cycloalkyl and R' is hydrogen.
Claim 25
Dependent Claim
35 words
A polymer according to claim 15 in which, in monomer (c), R contains 10 to 24 carbon atoms and is selected from alkyl and alkaryl and n is an integer of from 5 to 100.
Claim 26
Dependent Claim
19 words
An aqueous composition thickened by the presence therein of a thickening amount of a polymer according to claim 15.
Claim 27
Dependent Claim
137 words
A cross linked polymer formed by polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0.0005 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 B n R where R' is hydrogen or methyl and B, n and R are as defined above and monomer (d) consists essentially of polyethylenically unsaturated monomer.
Claim 28
Dependent Claim
137 words
A cross linked polymer formed by polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0.0005 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 B n R where R' is hydrogen or methyl and B, n and R are as defined above and monomer (d) consists essentially of polyethylenically unsaturated monomer.
Claim 29
Dependent Claim
172 words
A cross linked, water swellable, polymer formed by polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0.0005 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 B n R where R' is hydrogen or methyl and B, n and R are as defined above, monomer (d) consists essentially of polyethylenically unsaturated monomer, monomers (a) and (b) are water soluble and the polymer is formed from 2 to 95% by weight of the allyl ether and 5 to 98% by weight of the monomers (a) and (b).
Claim 30
Dependent Claim
172 words
A cross linked, water swellable, polymer formed by polymerisation of a polymerisable mixture formed by mixing monomers consisting essentially of (a) 0 to 90% by weight of monoethylenically unsaturated ionic monomer (b) 0 to 90% by weight of monoethylenically unsaturated substantially non-ionic monomer (c) 0.5 to 100% by weight of a monoethylenically unsaturated monomer that carries a pendant group --B n R where B is ethylenoxy, n is zero or a positive integer, and R is a hydrophobic hydrocarbyl group of at least 8 carbon atoms (d) 0.0005 to 0.2% by weight of cross linking monomer, and in which monomer (c) is an allyl ether of the formula CH 2 ═CR'CH 2 B n R where R' is hydrogen or methyl and B, n and R are as defined above, monomer (d) consists essentially of polyethylenically unsaturated monomer, monomers (a) and (b) are water soluble and the polymer is formed from 2 to 95% by weight of the allyl ether and 5 to 98% by weight of the monomers (a) and (b).
Claim 31
Dependent Claim
22 words
A polymer according to claim 25 in which monomer (a) is selected from the group consisting of acrylic acid and methacrylic acid.
Claim 32
Dependent Claim
16 words
A polymer according to claim 25 in which monomer (a) comprises a vinyl tertiary amine monomer.
Claim 33
Dependent Claim
22 words
A polymer according to claim 25 in which monomer (a) comprises a dialkylaminoalkyl (meth) acrylate monomer or a dialkylaminoalkyl (meth) acrylamide monomer.
Claim 34
Dependent Claim
17 words
A polymer according to claim 25 in which, in monomer (c), n is from 2 to 100.
Claim 35
Dependent Claim
18 words
A polymer according to claim 25 in which monomer (a) is acrylic acid and monomer (b) is acrylamide.
Claim 36
Dependent Claim
35 words
A polymer according to claim 25 in which, in monomer (c), R is a hydrophobic hydrocarbyl group of 8 to 30 carbon atoms selected from alkyl, aralkyl, aryl, alkaryl and cycloalkyl and R' is hydrogen.
Claim 37
Dependent Claim
35 words
A polymer according to claim 25 in which, in monomer (c), R contains 10 to 24 carbon atoms and is selected from alkyl and alkaryl and n is an integer of from 5 to 100.
Claim 38
Dependent Claim
24 words
A polymer according to claim 25 in the form of particles having a size of below 4 m and dispersed in a non-aqueous liquid.
Claim 39
Dependent Claim
19 words
An aqueous composition thickened by the presence therein of a thickening amount of a polymer according to claim 33.
Claim 40
Dependent Claim
31 words
A polymer according to claim 25 in the form of absorbent particles having a size of from 50 m to 500 m, and in which the ionic monomer (a) is anionic.
Claim 41
Dependent Claim
17 words
A polymer according to claim 1 in which the polymerisable mixture is free of cross linking monomer.
Claim 42
Dependent Claim
18 words
A polymer according to claim 1 in which the amount of cross linking monomer is 0.0005 to 0.2%.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-01-08 | 1993-07-10 | 1994-01-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-01-08 | 1997-07-10 | 1998-01-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-01-08 | 2001-07-10 | 2002-01-09 | $7700.00 | Window Closed / Lapsed |