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

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. ##STR00001##

Claims

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) ##STR00009## wherein R.sup.1 is hydrogen, methyl or ethyl, A is a linear C.sub.1-C.sub.12 alkylene or a branched C.sub.1-C.sub.12 alkylene, and Q.sup.+ is H.sup.+, NH.sub.4.sup.+, an organic ammonium ion [NHR.sup.5R.sup.6R.sup.7].sup.+, Li.sup.+, Na.sup.+, K.sup.+, ½ Ca.sup.++, ½ Mg.sup.++, ½ Zn.sup.++, ⅓ Al.sup.+++, or is a mixture of these ions, wherein R.sup.5, R.sup.6, and R.sup.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.sub.6-C.sub.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.sup.5, R.sup.6, and R.sup.7 is not hydrogen and b) 1.0 to 79.99 mol % of at least one independent repeating structural unit of the formula (2) ##STR00010## wherein R.sup.1a is hydrogen, methyl or ethyl, X.sup.+ is H.sup.+, NH.sub.4.sup.+an organic ammonium ion [NHR.sup.5R.sup.6R.sup.7].sup.+, Li.sup.+, Na.sup.+, K.sup.+, ½ Ca.sup.++, ½ Mg.sup.++, ½ Zn.sup.++, ⅓ Al.sup.+++, or is a mixture of these ions, wherein R.sup.5, R.sup.6, and R.sup.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.sub.6-C.sub.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.sup.5, R.sup.6, and R.sup.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.sub.2CH.sub.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.sup.+in the at least one structural unit of the formula (1) is selected from the group consisting of NH.sub.4.sup.+Li.sup.+, Na.sup.+, Ca.sup.++Mg.sup.++ and mixtures of these ions, and the counterion X.sup.+ in the at least one structural unit in the formula (2) is selected from the group consisting of H.sup.+, NH.sub.4.sup.+Li.sup.+, Na.sup.+, Ca.sup.++Mg.sup.++, 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) ##STR00011## wherein R.sup.1 is hydrogen, methyl or ethyl, R.sup.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.sup.7—).sub.oR.sup.8, or —(CO—NR.sup.5—R.sup.7—).sub.pR.sup.8,, l, m, n, o, and p, each independently, are an integer from 0 to 300, Y is a chemical bond, O, NR.sup.3, S, PR.sup.3, CH.sub.2, CH.sub.2O, CH.sub.2NR.sup.3, CH.sub.2S, C(O), —C(O)O, OC(O), C(O)NR.sup.3, NR.sup.3C(O), C(NR.sup.4)NR.sup.3, C(O)S, R.sup.6OC(O)O, R.sup.6OC(O)NR.sup.3, R.sup.6OC(O)S, R.sup.6P(O)O, R.sup.6OP(O)O, R.sup.6S(O), R.sup.6S(O)(O), R.sup.6S(O)O, R.sup.6S(O)(O)O, R.sup.6OS(O)O or R.sup.6OS(O)(O)O, R.sup.3, R.sup.4, R.sup.5, and R.sup.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.sup.6 is a chemical bond or CH.sub.2, and R.sup.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) ##STR00012## wherein R.sup.1 is hydrogen, methyl or ethyl and R.sup.2 and R.sup.3, each independently, are hydrogen, methyl, ethyl, n-propyl or isopropyl, and at least one of the radicals R.sup.2 and R.sup.3 is not hydrogen, and at least one of the structural unit of the formula (6) ##STR00013## wherein R.sup.1 is hydrogen, methyl or ethyl and R.sup.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 contains Li.sup.+, Na.sup.+, K.sup.+, Ca.sup.++, Mg.sup.++, Zn.sup.++ or Al.sup.+++.

10. A cosmetic, dermatological or pharmaceutical composition comprising at least one water-soluble or water-swellable polymer of claim 1.

11. The composition of claim 10, wherein the composition is in the form of a fluid, gel, oil, foam, spray, lotion or cream.

12. The composition of claim 10 further comprising at least one surfactant.

13. The composition of claim 10, further comprising at least one substance selected from the group consisting of organic salts and inorganic salts.

14. The composition of claim 10, further comprising at least one substance selected from the group consisting of alpha-hydroxy acids and beta-hydroxy acids.

15. The composition of claim 10, further comprising at least one substance selected from the group consisting of vitamin C and vitamin C derivatives.

16. The composition of claim 10, further comprising at least one substance selected from the group consisting of benzoic acid, sorbic acid, salicylic acid, lactic acid, and para-methoxybenzoic acid.

17. The composition of claim 10, further comprising at least one substance selected from the group consisting of organic UV filters and inorganic UV filters.

18. The composition of claim 10, having a pH of 2 to 10.

19. The composition of claim 10, wherein the composition is in the form of a shower gel or shampoo.

20. A process for thickening, modifying the consistency, emulsifying, adding sensorial properties, solubilizing, dispersing, modifying lubricity, modifying adherency, stabilizing or modifying yield point formation of a cosmetic, dermatological or pharmaceutical composition comprising the step of adding at least one water-soluble or water-swellable polymer of claim 1, to the cosmetic, dermatological or pharmaceutical composition.

21. A process for thickening or forming a yield point in a cosmetic, dermatological or pharmaceutical composition comprising the step of adding at least one water-soluble or water-swellable polymer of claim 1, to the cosmetic, dermatological or pharmaceutical composition.

22. A process for thickening or forming a yield point in liquid compositions comprising one or more surfactants comprising the step of adding at least one water-soluble or water-swellable polymer of claim 1, to the liquid composition.

23. A process for stabilizing an emulsion, comprising the step of adding at least one water-soluble or water-swellable polymer of claim 1, to the emulsion.

Description

EXAMPLES

(1) The examples and applications below are intended to illustrate the invention in more detail without, however, limiting it thereto.

1. Polymerization

(2) General polymerization procedure for preparing the polymers of the invention by the precipitation process in tert-butanol

(3) A 1 liter Quickfit flask with reflux condenser, gas inlet, internal thermometer, and stirrer is charged with 400 g of tert-butanol, which is admixed with the calculated amount of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS®, Lubrizol). Then neutralization is carried out by introduction of NH.sub.3 (target pH 6-7) and the calculated amount of 2-carboxyethyl acrylate (Sigma-Aldrich) or 2-carboxyethyl acrylate oligomer mixture (Bimax Chemicals Ltd) and the calculated amount of crosslinker are added to the reaction mixture. If further comonomers should be required, they can be added after the neutralization of the acrylamido-2-methyl-1-propanesulfonic acid (AMPS®, Lubrizol). Should the pH of the reaction mixture have drifted into the acidic range following the addition of comonomer, neutralization is repeated by introduction of NH.sub.3 (target pH 6-7). After the mixture has been rendered inert using N.sub.2 or argon, dimethyl 2,2′-aobisisobutyrate (V-601) initiator is added, at an internal temperature of 60° C., and the polymerization reaction is initiated. After a few minutes, the completed polymer is precipitated. The mixture is heated at reflux for two hours and the polymer is then freed from the solvent on a suction filter and dried under reduced pressure. This procedure can be applied generally to all polymerization reactions described below.

(4) The 2-carboxyethyl acrylate oligomer mixture that is used, from Bimax Chemicals Ltd., is composed of 10-20% by weight acrylic acid, 30-60% by weight 2-carboxyethyl acrylate, and 30-60% by weight higher oligomers of 2-carboxyethyl acrylate.

2. Example 1

(5) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(6) TABLE-US-00002 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90 89.5 2-Carboxyethyl acrylate oligomer mixture 8.25 10.0 Glycerol propoxylate triacrylate (GPTA) 0.58 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.1 — *based on the monomer concentration used

3. Example 2

(7) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(8) TABLE-US-00003 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90 89.25 2-Carboxyethyl acrylate oligomer mixture 8.25 10.0 Glycerol propoxylate triacrylate (GPTA) 0.88 0.75 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.1 — *based on the monomer concentration used

4. Example 3

(9) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(10) TABLE-US-00004 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90.0 87.5 2-Carboxyethyl acrylate oligomer mixture 8.4 12 Pentaerythritol diacrylate monostearate (PEAS) 1.26 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.1 — *based on the monomer concentration used

5. Example 4

(11) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(12) TABLE-US-00005 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90 85.5 2-Carboxyethyl acrylate oligomer mixture 8.6 10.0 Dimethylacryamide (DMAAm) 2.0 4.0 Pentaerythritol diacrylate monostearate (PEAS) 1.29 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.2 — *based on the monomer concentration used

6. Example 5

(13) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(14) TABLE-US-00006 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90 79.5 2-Carboxyethyl acrylate oligomer mixture 9.3 10.0 Dimethylacryamide (DMAAm) 5.4 10.0 Pentaerythritol diacrylate monostearate (PEAS) 1.36 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.3 — *based on the monomer concentration used

7. Example 6

(15) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(16) TABLE-US-00007 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 71.0 44.5 2-Carboxyethyl acrylate 17.0 15 Dimethylacryamide (DMAAm) 30.5 40 Trimethylolpropane triacrylate (TMPTA) 1.2 0.5 Dilauryl peroxide (DLP) 1.7 — * based on the monomer concentration used

8. Example 7

(17) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(18) TABLE-US-00008 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90 86.5 2-Carboxyethyl acrylate 10.25 12.0 Dimethylacryamide (DMAAm) 0.5 1.0 Diethylene glycol dimethacrylate (DEGDMA) 0.61 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.20 — *based on the monomer concentration used

9. Example 8

(19) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(20) TABLE-US-00009 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90.0 88.0 2-Carboxyethyl acrylate 7.0 9.7 n-Butyl acrylate 1.3 2.0 Glycerol 1,3-diglycerolate diacrylate (GDDA) 0.51 0.3 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.1 — *based on the monomer concentration used

10. Example 9

(21) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(22) TABLE-US-00010 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90.0 86.8 2-Carboxyethyl acrylate 7.0 9.6 Dimethylacryamide (DMAAm) 1.0 2.0 1,6-Hexanediol dimethacrylate (HDDMA) 1.91 1.6 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.11 — *based on the monomer concentration used

11. Example 10

(23) Polymerization was carried out in accordance with the general polymerization procedure in section 1).

(24) TABLE-US-00011 Reactant g mol % Acrylamido-2-methyl-1-propanesulfonic acid 90.0 87.7 2-Carboxyethyl acrylate 7.0 9.8 Poly(ethylene glycol) monoacrylate 3.8 2.0 Glycerol propoxylate triacrylate (GPTA) 0.59 0.5 Dimethyl 2,2′-azobisisobutyrate (V-601)* 1.10 — *based on the monomer concentration used

(25) The 2-carboxyethyl acrylate oligomer mixture used, from Bimax Chemicals Ltd., can be purified by chromatographic methods. For example, the acrylic acid can be removed and the resulting oligomer mixture can be used, for example, in examples 1 to 5 set out above.

(26) B) Examples relating to cosmetic compositions comprising polymers of the invention:

(27) All of the percentage figures below are in weight percent (% by weight), unless explicitly indicated otherwise.

(28) The following cosmetic formulations were prepared with copolymers of the invention:

Example A

Anti-Aging Cream Gel

(29) TABLE-US-00012 A Genapol ® DAT 2.00% PEG-150 Polyglyceryl-2 tristearate and PEG-6 caprylic/capric glyceride B Water ad 100% C Mineral oil 5.00% SilCare ® Silicone 31M50 3.00% Caprylyl trimethicone D Polymer of example 4 1.80% E Glycolic acid 30%* 6.00% Phenonip ® 0.50% Phenoxyethanol (and) methylparaben (and) ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben F Genapol ® LA 070 3.00% Laureth-7 Preparation I Dissolve A in B with stirring and gentle heating II Stir D into C III I to II and stir until a homogeneous gel is obtained IV Add E to III V Add F to IV and stir together

Example B

O/W Sun Protection Cream

(30) TABLE-US-00013 A Hostaphat ® CS 120 5.00% Stearyl phosphate Tegin ® M 2.50% Glyceryl stearate Stearic acid 2.00% Cetyl alcohol 1.00% Abil ® 100 2.00% Dimethicone Mineral oil, low viscosity 3.00% Cetiol ® 868 3.00% Ethylhexyl stearate Velsan ® CCT 3.00% Caprylic/capric triglyceride UV-Titan M210 5.00% Ultrafine titanium dioxide B Polymer of example 5 0.20% C Hostapon ® CLG 0.60% Sodium lauroyl glutamate Eusolex ® 232 4.00% Phenylbenzimidazole sulfonic acid Tris(hydroxymethyl) aminomethane q.s. Tromethamine Allantoin 0.20% Glycerol 5.00% Preservative q.s. Water ad 100%  D Fragrance 0.30% Preparation I Melt A at 80° C., then add component B II Homogenize I III Heat C to 80° C. IV Stir III into II V Stir IV until cooling VI Add D to V at 35° C. VII Homogenize emulsion

Example C

Shampoo with Pearlizer

(31) TABLE-US-00014 A Water ad 100% B Polymer of example 2 2.50% C Genapol ® LRO liq. 38.50% Sodium laureth sulfate Genagen ® CAB 15.00% Cocamidopropyl betaine Hostapon ® KCG 8.30% Sodium cocoyl glutamate D Genapol ® TSM 4.00% Na benzoate 0.40% Preparation I Mix B with A until a homogeneous gel is obtained II Add components of C and stir until fully dissolved III Add components of D to II IV Adjust pH to pH = 4.5.

Example D

Suncream with Zinc Oxide

(32) TABLE-US-00015 A Hostaphat ® KL 340 D 1.00% Trilaureth-4 phosphate Mineral oil, low viscosity 8.00% Isopropyl palmitate Velsan ® CCT 2.00% Caprylic/capric triglyceride Glyceryl stearate 0.50% Cetearyl alcohol 0.50% B Polymer of example 4 0.80% C Glycerol 5.00% Alcohol 1.00% Water ad 100%  D Tocopheryl acetate 1.00% Z-Cote HP1 10.00%  Zinc oxide and dimethicone Preservative q.s. E Fragrance 0.30% Preparation I Melt A at 70° C., then add B II Heat C to 40° C. III Stir II into I IV Stir D at 35° C. into III V Add E to IV

Example E

Cream Gel with Water-Soluble Sun Protection

(33) TABLE-US-00016 A Eusolex ® 232 2.00% Phenylbenzimidazole sulfonic acid B Water ad 100%  C Polymer of example 4 2.10% D Tegosoft TN 5.00% C12-15 Alkylbenzoate SilCare ® silicone 31M50 3.00% Caprylyl trimethicone E Nipaguard ® MPA q.s. Benzyl alcohol (and) methylparaben (and) Propylparaben Genapol ® LA 070 2.50% Laureth-7 Fragrance q.s. Preparation I Mix A with B and neutralize to approximately pH 7.3 II Add C and stir until a homogeneous gel is obtained III Mix components of D and add to II IV Add E to III

Example F

Whitening Gel

(34) TABLE-US-00017 A Genapol ® T 250 2.00% Ceteareth-25 Genapol ® DAT 100 1.10% PEG-150 polyglyceryl-2 tristearate B Water ad 100.00%    C Ascorbic acid 2-glucoside 3.00% Nipaguard ® DMDMH q.s. DMDM Hydantoin D Polymer of example 4 3.00% E Sodium hydroxide q.s. Preparation I Dissolve components A in B with stirring and gentle heating II Stir until cooling (25° C.) and add C III Add D and stir until a homogeneous gel is obtained IV Set a pH of 6 with E

Example G

Antidandruff Shampoo

(35) TABLE-US-00018 A Water ad 100%  B Polymer of example 1 2.50% C Genapol ® LRO liq. 38.50%  Sodium laureth sulfate Genagen ® CAB 15.00%  Cocamidopropyl betaine Hostapon ® KCG 8.30% Sodium cocoyl glutamate D Zinc pyrithion 1.80% Preservative q.s. Preparation I Mix B with A and stir until a homogeneous gel is obtained II Add components C and stir until completely dissolved III Add components of D to II

Example H

Shower Gel with Optical Effect (1)

(36) TABLE-US-00019 A Genapol ® LRO liq. 49.95%  Sodium laureth sulfate Genagen ® CAB 5.00% Cocamidopropylbetaine B Water ad 100%  C Polymer of example 2 1.50% D Na sorbate 0.40% E Citric acid q.s. Cirebelle 104 0.20% Preparation I Mix A with B II When dissolved, add C to I and stir until a homogeneous solution is formed III Add D to II IV Set pH to 5.0 with E

Example I

Shower Gel of Optical Effect (2)

(37) TABLE-US-00020 A Genapol ® LRO liquid 30.00% Sodium laureth sulfate Hostapon ® KCG 5.00% Sodium cocoyl glutamate Velsan ® CG 070 2.00% PEG-7 glyceryl cocoate Genagen ® CAB 6.00% Cocamidopropyl betaine Genapol ® LA 030 2.00% Laureth-3 B Water ad 100% C Polymer of example 3 1.50% D Na sorbate 0.30% Preparation I Mix A with B until the components are fully dissolved II Add C to I; stir until a homogeneous solution is formed III Add D to II

(38) The air bubbles included in the course of stirring are stably dispersed by the polymer of the invention.