Polymers based on arcrylic, methacrylic or ethacrylic amidoalkyl sulfonic acid or salts and carboxyalky acrylate, methacrylate or ethacrylate or oligomers of said carboxy compounds

Patent metadata

Field	Value
Publication number	US-9834635-B2
Application number	US-201013258857-A
Country	US
Kind code	B2
Filing date	Mar 20, 2010
Priority date	Mar 25, 2009
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

Water-soluble or water-swellable polymers are described, containing a) 20.0 to 98.99 mole percent of one or more independently recurring structural units of the formula (1) and b) 1.0 to 79.99 mole percent of one or more independently recurring structural units of the formula (2), and c) 0.01 to 8.0 mole percent of one or more independently recurring cross-linking structural units, which are obtained from one or more monomers having at least two olefinic double bonds. The polymers are suitable, for example, as thickeners or yield point formers, in particular in cosmetic, dermatological or pharmaceutical compositions.

First claim

The invention claimed is:

1. A water-soluble or water-swellable polymer comprising
a) 20.0 to 98.99 mol % of at least one independent repeating structural unit of the formula (1)

wherein
R 1 is hydrogen, methyl or ethyl,
A is a linear C 1 -C 12 alkylene or a branched C 1 -C 12 alkylene, and
Q + is H + , NH 4 + , an organic ammonium ion [NHR 5 R 6 R 7 ] + , Li + , Na + , K + , ½ Ca ++ , ½ Mg ++ , ½ Zn ++ , ⅓ Al +++ , or is a mixture of these ions,
wherein R 5 , R 6 , and R 7 , independently of one another, are hydrogen, a linear alkyl group having 1 to 22 carbon atoms, a branched alkyl group having 1 to 22 carbon atoms, a linear and singularly unsaturated alkenyl group having 2 to 22 carbon atoms, a linear and multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a branched and singularly unsaturated alkenyl group having 2 to 22 carbon atoms, a branched and multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a C 6 -C 22 alkylamidopropyl group, a linear monohydroxyalkyl group having 2 to 10 carbon atoms, a linear di-hydroxyalkyl group having 3 to 10 carbon atoms, or a branched di-hydroxyalkyl group having 3 to 10 carbon atoms, and wherein at least one of the radicals R 5 , R 6 , and R 7 is not hydrogen

and
b) 1.0 to 79.99 mol % of at least one independent repeating structural unit of the formula (2)

wherein
R 1a is hydrogen, methyl or ethyl,
X + is H + , NH 4 + an organic ammonium ion [NHR 5 R 6 R 7 ] + , Li + , Na + , K + , ½ Ca ++ , ½ Mg ++ , ½ Zn ++ , ⅓ Al +++ , or is a mixture of these ions,
wherein R 5 , R 6 , and R 7 , independently of one another, are hydrogen, a linear alkyl group having 1 to 22 carbon atoms, a branched alkyl group having 1 to 22 carbon atoms, a linear and singularly unsaturated alkenyl group having 2 to 22 carbon atoms, a linear and multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a branched and singularly unsaturated alkenyl group having 2 to 22 carbon atoms, a branched and multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a C 6 -C 22 alkylamidopropyl group, a linear monohydroxyalkyl group having 2 to 10 carbon atoms, a linear di-hydroxyalkyl group having 3 to 10 carbon atoms, or a branched di-hydroxyalkyl group having 3 to 10 carbon atoms, and wherein at least one of the radicals R 5 , R 6 , and R 7 is not hydrogen,

B is a linear alkylene group having 1 to 6 carbon atoms or a branched alkylene group having 1 to 6 carbon atoms, and
n is an integer from 1 to 10,
and
c) 0.01 to 8.0 mol %, of at least one crosslinking structural unit, wherein the at least one crosslinking structural unit is glycerol propoxylate triacrylate (GPTA),
wherein mol % is based on the total number of moles of monomers in the polymer, and where the degree of neutralization of the at least one structural unit of the formula (1) is from 50.0 to 100 mol %, wherein the degree of neutralization is the ratio of moles of neutralized units of formula (1) to the total number of moles of units of formula (1).

2. The water-soluble or water-swellable polymer as claimed in claim 1 , wherein the at least one structural unit of the formula (1) is derived from 2-acrylamido-2-methylpropanesulfonic acid.

3. The water-soluble or water-swellable polymer as claimed in claim 1 , wherein the fraction of the at least one structural unit of the formula (2) in which n is an integer of two to ten within component b) is from 10.0 mol % to 79.99 mol %.

4. The water-soluble or water-swellable polymer as claimed in claim 1 , wherein the at least one structural unit of the formula (2), B is the group —CH 2 CH 2 —and n is an integer from 1 to 5.

5. The water-soluble or water-swellable polymer as claimed in claim 1 , wherein the counterion Q + in the at least one structural unit of the formula (1) is selected from the group consisting of NH 4 + Li + , Na + , Ca ++ Mg ++ and mixtures of these ions, and the counterion X + in the at least one structural unit in the formula (2) is selected from the group consisting of H + , NH 4 + Li + , Na + , Ca ++ Mg ++ , and mixtures of these ions.

6. The water-soluble or water-swellable polymer as claimed in claim 1 , comprising
a) 50.0 to 96.99 mol % of the at least one structural unit of the formula (1),
b) 3.0 to 49.99 mol % of the at least one structural unit of the formula (2), and
c) 0.01 to 5.0 mol % of the at least one crosslinking structural unit of component c), wherein mol % is based on the total number of moles of monomers in the polymer.

7. The water-soluble or water-swellable polymer of claim 1 , comprising
ab) 29.99 to 98.99 mol %, of a mixture of the at least one independent repeating structural unit of formula (1) and the at least one independent repeating structural unit of formula (2) of the formulae (1) and (2),
c) 0.01 to 8.0 mol % of the at least one crosslinking structural unit of component c), and further comprising
d) 0.01 to 70.0 mol % of at least one independent repeating noncrosslinking structural unit obtained from at least one compound of the formula (4)

wherein
R 1 is hydrogen, methyl or ethyl,
R 2 is H, a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 1 to 50 carbon atoms, a linear monohydroxyalkyl group having 2 to 6 carbon atoms, a branched monohydroxyalkyl group having 2 to 6 carbon atoms, a linear dihydroxyalkyl group having 2 to 6 carbon atoms, a branched dihydroxyalkyl group having 2 to 6 carbon atoms, —(CO—O—R 7 —) o R 8 , or —(CO—NR 5 —R 7 —) p R 8, ,
l, m, n, o, and p, each independently, are an integer from 0 to 300,
Y is a chemical bond, O, NR 3 , S, PR 3 , CH 2 , CH 2 O, CH 2 NR 3 , CH 2 S, C(O), —C(O)O, OC(O), C(O)NR 3 , NR 3 C(O), C(NR 4 )NR 3 , C(O)S, R 6 OC(O)O, R 6 OC(O)NR 3 , R 6 OC(O)S, R 6 P(O)O, R 6 OP(O)O, R 6 S(O), R 6 S(O)(O), R 6 S(O)O, R 6 S(O)(O)O, R 6 OS(O)O or R 6 OS(O)(O)O,
R 3 , R 4 , R 5 , and R 8 , each independently, are hydrogen, a linear alkyl radical having 1 to 50 carbon atoms, or a branched alkyl radical having 1 to 50 carbon atoms,
R 6 is a chemical bond or CH 2 , and
R 7 is a linear alkylene radical having 1 to 50 carbon atoms or a branched alkylene radical having 1 to 50 carbon atoms.

8. The water-soluble or water-swellable polymer of claim 7 , wherein the at least one structural unit of component d) is selected from at least one structural unit of the formula
(5)

wherein
R 1 is hydrogen, methyl or ethyl and
R 2 and R 3 , each independently, are hydrogen, methyl, ethyl, n-propyl or isopropyl, and at least one of the radicals R 2 and R 3 is not hydrogen, and
at least one of the structural unit of the formula (6)

wherein
R 1 is hydrogen, methyl or ethyl and
R 2 is hydrogen, methyl, ethyl, n-propyl or isopropyl.

9. A process for preparing the water-soluble or water-swellable polymer of claim 1 , wherein monomers from which the structural units of components a) to c) are derived are radically polymerized in a protic solvent, and optionally the monomers are neutralized before the polymerization or the polymer is neutralized after the polymerization, wherein the monomers and the polymer are neutralized with ammonia, organic amines, or a base, and wherein the base contai

Assignees

• Klug Peter
• Fischer Dirk
• Lindner Thomas
• Kunze Matthias
• Moeller Wiebke
• Mildner Carina
• Lo Vasco Sebastiano
• Clariant Int Ltd

Inventors

• Klug Peter
• Fischer Dirk
• Lindner Thomas
• Kunze Matthias
• Moeller Wiebke
• Mildner Carina
• Lo Vasco Sebastiano

Classifications

• A61Q17/04

  Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations · CPC title

• A61K8/36

  Carboxylic acids; Salts or anhydrides thereof · CPC title

• A61Q19/10

  Washing or bathing preparations · CPC title

• A61K8/8158

  Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers · CPC title

• C08F220/26

  Esters containing oxygen in addition to the carboxy oxygen · CPC title