Thickening polymer

Abstract

Polymer obtainable by radical emulsion polymerization of (A) at least one acidic vinyl monomer or salt thereof; (B) at least one nonionic vinyl monomer, particularly preferably a hydrophobic nonionic vinyl monomer; (C) at least one monomer containing an unsaturated end group and a polyoxyalkylene part; (D) at least one crosslinking monomer; and (E) optionally, a protective colloid, characterized in that the polymerization is controlled such that (F) the gel effect occurs, at least at times, achieved by adding monomers of type (A), (B), and (C) (dosing time) during 120 minutes; and such that (G) the crosslinking monomer (D) is added, at the very earliest, 10 minutes after the first addition of the monomers (A), (B), and (C).

Claims

1. A polymer, wherein the polymer is obtainable by radical emulsion polymerization of (A) at least one acidic vinyl monomer or salt thereof, (B) at least one nonionic vinyl monomer, (C) at least one monomer containing an unsaturated end group and a polyoxyalkylene moiety, (D) at least one crosslinking monomer, (E) optionally, a protective colloid, the polymerization being controlled such that (F) at least at times the gel effect occurs, achieved by adding monomers (A), (B) and (C) within 120 minutes, and (G) the crosslinking monomer (D) is added at the earliest 10 minutes after a first addition of monomers (A), (B) and (C).

2. The polymer of claim 1, wherein (B) comprises a hydrophobic nonionic vinyl monomer.

3. The polymer of claim 1, wherein no associative monomers are present.

4. The polymer of claim 1, wherein (A) comprises at least one of methacrylic acid, an alkali metal salt thereof, an alkaline earth metal salt thereof, an ammonium salt thereof, and an alkylammonium salt thereof.

5. The polymer of claim 1, wherein (B) comprises at least one monomer selected from C1-C22-alkyl acrylates and C1-C22-alkyl methacrylates.

6. The polymer of claim 1, wherein (C) comprises at least one monomer selected from vinylpolyalkylene glycols and polymerizable surfactants.

7. The polymer of claim 1, wherein (C) comprises at least one monomer selected from ethoxylated and propoxylated 1,4-butanediol vinyl ether having 30 ethyleneoxy and propyleneoxy units, allylpolyethylene glycol ethers having 30 ethyleneoxy units, allylpolyethylene glycol ethers having 20 ethyleneoxy units, vinylpolyethylene glycol ethers having 20 ethyleneoxy units, CH.sub.2═CHCH.sub.2O[(CH.sub.2CH.sub.2O).sub.n(CH.sub.2(CH.sub.3)CHO)].sub.mCH.sub.3 where m+n=5 to 100 and n/m=1, and polyalkylene glycol allyl butyl ethers having 25 ethyleneoxy and 8 propyleneoxy units.

8. The polymer of claim 1, wherein (D) comprises at least one monomer selected from polyol (meth)acrylates having at least two (meth)acrylate groups and mixed esters of polyols with acrylic acid and/or methacrylic acid.

9. The polymer of claim 1, wherein the polymer comprises from 10% to 75% of (A), from 10% to 90% of (B), from 0.5% to 40% of (C), and up to 1% of (D).

10. The polymer of claim 1, wherein the polymer comprises from 20% to 60% of (A), from 40% to 80% of (B), from 1% to 10% of (C), and from 0.05% to 0.5% of (D).

11. The polymer of claim 1, wherein a mass ratio (A):(B) is from 1:2.2 to 1.5:1.

12. A polymer, wherein the polymer is obtainable by radical emulsion polymerization of (A) at least one acidic vinyl monomer or salt thereof, (B) at least one nonionic vinyl monomer, (C) at least one monomer containing an unsaturated end group and a polyoxyalkylene moiety, (D) at least one crosslinking monomer, (E) optionally, a protective colloid, the polymerization being controlled such that (F) at least at times the gel effect occurs, achieved by adding monomers (A), (B) and (C) within 60 minutes and (G) the crosslinking monomer (D) is added at the earliest 15 minutes after a first addition of monomers (A), (B) and (C), and wherein (A) comprises at least one of methacrylic acid, an alkali metal salt thereof, an alkaline earth metal salt thereof, an ammonium salt thereof, and an alkylammonium salt thereof, (B) comprises at least one monomer selected from C1-C22-alkyl acrylates and C1-C22-alkyl methacrylates, (C) comprises at least one monomer selected from ethoxylated and propoxylated 1,4-butanediol vinyl ether having 30 ethyleneoxy and propyleneoxy units, allylpolyethylene glycol ethers having 30 ethyleneoxy units, allylpolyethylene glycol ethers having 20 ethyleneoxy units, vinylpolyethylene glycol ethers having 20 ethyleneoxy units, CH.sub.2═CHCH.sub.2O[(CH.sub.2CH.sub.2O).sub.n(CH.sub.2(CH.sub.3)CHO)].sub.mCH.sub.3 where m+n=5 to 100 and n/m=1, and polyalkylene glycol allyl butyl ethers having 25 ethyleneoxy and 8 propyleneoxy units, and (D) comprises at least one monomer selected from polyol (meth)acrylates having at least two (meth)acrylate groups and mixed esters of polyols with acrylic acid and/or methacrylic acid.

13. The polymer of claim 12, wherein the polymer comprises from 28% to 52% of (A), from 40% to 62% of (B), from 2% to 6% of (C), and from 0.1% to 0.3% of (D).

14. A thickened preparation, wherein the preparation comprises the polymer of claim 1.

15. The preparation of claim 14, wherein the preparation is aqueous and comprises from 0.5% to 5% of the polymer.

16. The preparation of claim 1, wherein (A) consists of methacrylic acid, (B) consists of ethylacrylate and (C) consists of allylpolyalkylene glycol ether having 20 ethyleneoxy units and 20 propyleneoxy units.

17. The preparation of claim 16, wherein D consists of trimethylolpropane triacrylate.

18. The polymer of claim 17, wherein the polymer comprises from 28% to 52% of (A), from 40% to 62% of (B), from 2% to 6% of (C), and from 0.1% to 0.3% of (D).

19. The preparation of claim 1, wherein monomers (A), (B) and (C) are added within 60 minutes.

20. The preparation of claim 1, wherein monomer (D) is added at the earliest 15 minutes after the first addition of monomers (A), (B) and (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

Examples

(1) Synthesis of the Copolymers

(2) The examples below are intended to illustrate the present invention without limiting it. The preparation of the examples takes place in accordance with the method described below, the type and amounts of the monomers used in each case as starting components being summarized in Table 2. Parts and percentages refer to the weight.

Example 1

(3) Monomer Phase

(4) Methacrylic acid 37.000 parts

(5) Ethyl acrylate 57.400 parts

(6) Polyglycol A11/1800 5.400 parts

(7) Crosslinker Phase

(8) Trimethylolpropane triacrylate 0.300 parts

(9) Water Phase

(10) Water 33.060 parts

(11) Sodium lauryl sulfate 0.984 parts

(12) Reaction Vessel

(13) Water 173.146 parts

(14) Sodium lauryl sulfate 0.300 parts

(15) Initiator Phase A

(16) Water 1.911 parts

(17) Ammonium persulfate 0.069 parts

(18) Initiator Phase B

(19) Water 2.909 parts

(20) Ammonium persulfate 0.021 parts

(21) The reaction vessel, which is equipped with stirrer, reflux condenser, nitrogen feed, dosing device and internal thermometer, is charged with 173.146 parts of water and 0.300 parts of sodium lauryl sulfate. The mixture is heated to 82° C. with stirring and under a nitrogen atmosphere. The monomer mixture is prepared in a second stirred vessel which is equipped with stirrer and nitrogen feed. For this purpose, the monomer phase with 37.000 parts of methacrylic acid, 57.400 parts of ethyl acrylate and 5.400 parts of polyglycol A11/1800 is introduced, and into this is mixed the water phase with 33.060 parts water and 0.984 parts sodium lauryl sulfate with stirring and under a nitrogen atmosphere.

(22) As soon as a temperature of 82° C. has been reached in the reaction vessel, an initiator phase A, consisting of 0.069 parts ammonium persulfate and 1.911 parts water, is added and the monomer mixture is metered in uniformly at 85-88° C. over the course of 30 minutes. 20 minutes after the start of the monomer dosing, the crosslinker phase is added in its entirety to the monomer phase. After dosing is complete, an initiator phase B, consisting of 0.021 parts ammonium persulfate and 2.909 parts water, is added and then the reaction mixture is post-polymerized for a further 4 hours at 90° C. before being cooled to <40° C.

Examples 2-13

(23) The examples below (Table 1) are prepared analogously to Example 1. The crosslinking process stated in the table describes the type and time of the addition of the crosslinker. The letter “R” refers to an addition of the crosslinker into the reaction vessel, whereas the letter “M” describes an addition of the crosslinker into the monomer phase. The numbers indicate the time of the addition of the crosslinker in minutes after the start of the reaction (start of the monomer dosing). Example 13 was prepared like Example 1, except that the crosslinker was not added at a later time as an individual crosslinker phase, but weighed in the monomer phase with the other monomers and dosed in with the monomer phase within 30 minutes.

Abbreviations

(24) MAA methacrylic acid

(25) EA ethyl acrylate

(26) A11/1800 polyglycol A11/1800 (Clariant)

(27) Allylpolyalkylene glycol ether (EO 20 mol, PO 20 mol)

(28) TMPTA trimethylolpropane triacrylate

(29) TABLE-US-00001 TABLE 1 Examples 1-13 Polymer 1 2 3 4 5 6 7 8 9 10 11 12 13 MAA 37 37 37 37 45.4 45.4 45.4 45.4 45.4 50 45.4 45.4 37 EA 57.4 57.4 57.4 57.25 49 49 49.05 49 49 44.4 49 49.05 57.4 A11/1800 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 TMPTA 0.3 0.3 0.3 0.45 0.3 0.3 0.15 0.2 0.2 0.2 0.2 0.15 0.30 Crosslinking M20 R30 M25 R30 R20 M20 M20 M20 M15 M20 R20 R20 — process

(30) TABLE-US-00002 TABLE 2 Results Polymer Emulsions Polymer pH Particle size* in mm  1 2.55 86  2 2.53 87  3 2.49 84  4 2.63 90  5 2.51 99  6 2.55 99  7 2.49 95  8 2.59 94  9 2.63 93 10 2.53 104 11 2.53 96 12 2.50 93 13 2.50 89 *The particle size in the polymer emulsion is determined using dynamic light scattering (DLS) in a dilute aqueous sample of the emulsion at 25° C. ± 1° C.

Example 14

(31) Unless stated otherwise, all quantitative data, fractions and percentages are based on the weight and the total amount or on the total weight of the preparation.

(32) The polymer according to the invention is diluted with some of the water phase and added to the surfactant phase with stirring. The other formulation constituents apart from sodium hydroxide solution, citric acid and the suspended bodies are then added with stirring. After the pH has been adjusted to pH 5, the suspended bodies are stirred into the finished gel base with as little shearing as possible.

(33) TABLE-US-00003 TABLE 3 Preparation Shower Gel Sodium laureth sulfate 9.50 Cocoamidopropylbetaine 3.00 Polymer 2.25 PEG-40 hydrogenated castor oil 0.80 PEG-7 glyceryl cocoate 1.00 Sodium benzoate 0.45 Sodium salicylate 0.40 Unispheres UEA-509 0.15 Sodium hydroxide solution ad pH 6.0 Citric acid ad pH 5.0 Perfume 0.5 Water ad 100

(34) TABLE-US-00004 TABLE 4 Results Preparation Shower Gel Polymer in the Viscosity in Turbidity in shower gel tan δ mPas NTU  1 0.24 3335 23  2 0.39 3057 7  3 1.00 3001 14  4 1.22 2761 10  5 0.12 3413 25  6 0.17 3021 26  7 0.24 2906 14  8 0.17 3525 19  9 0.11 4169 25 10 0.22 3089 23 11 0.12 2903 22 12 0.18 2825 18 13 0.07 5785 80

(35) The viscosity of the preparations is measured on a rheometer at 25° C.±1° C. with 40 mm cone/plate geometry (1° cone angle) with a gap of 0.03 mm, charging being carried out in a structure-preserving manner. A suitable constant shear rate time ramp of 0.1-1000 s.sup.−1 is predefined and a corresponding structure recovery time is observed before the test. The viscosity is given for a shear rate of 10 s.sup.−1.

(36) Preparation 13, prepared with the polymer according to Example 13, has an excessively high viscosity and undesired severe turbidity. Moreover, it has a high yield point, which is manifested in a very low tan δ. The high yield point leads to the preparation no longer being flowable and consequently it is unable to flow by itself out of a bottle. Preparations 1-12 do not have this disadvantage.

Example 15

(37) Certain polymers such as Carbopol® AQUA SF-2 (Lubrizol) exhibit increasing turbidity at higher temperatures. This is undesired especially in countries with relatively high daytime temperatures or generally in the summer months, and may be interpreted by the consumer as defective product quality.

(38) A preparation as shown in Table 3 with Carbopol® AQUA SF-2 and the polymer from Example 8 was prepared and compared.

(39) TABLE-US-00005 TABLE 5 Turbidity values compared to AQUA SF-2 22° C. after 22° C. 22° C. 30° C. 35° C. 40° C. 50° C. 22° C. 72 h 1 week Example 8 18 19 18 18 18 19 18 18 Aqua 24 24 26 37 140 31 27 26 SF-2

(40) The polymers according to the invention do not have temperature-dependent turbidity, whereas the Carbopol® AQUA SF-2 becomes more and more turbid with increasing temperature.