Functionalized copolymers for preparing coating compositions

• US 20020007009A1
• Filed: 05/07/2001
• Published: 01/17/2002
• Est. Priority Date: 05/11/2000
• Status: Active Grant

• Current Assignee: Wacker Chemie AG (Dr. Alexander Wacker Familiengesellschaft Mit Beschrã¤Nkter Haftung)
• Original Assignee: Wacker-Chemie GmbH (Dr. Alexander Wacker Familiengesellschaft Mit Beschrã¤Nkter Haftung)
• Inventors: Buppelmann, Klaus, Stark, Kurt, Ball, Peter, Tschirner, Peter, Kotschi, Udo
• Granted Patent: US 6,624,243 B2
• Time in Patent Office: Days
• US Class Current: 524/806
• CPC Class Codes: C08F 230/085 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• CPC Class Codes: C08F 246/00 Copolymers in which the nature of only the monomers in minority is defined
• CPC Class Codes: C09D 143/04 Homopolymers or copolymers of monomers containing silicon

Abstract

The invention provides functionalized copolymers in the form of their aqueous dispersions or water-redispersible powders, based on

a) one or more monomers from the group consisting of vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having 1 to 15 carbon atoms, vinyl aromatics, olefins, dienes, and vinyl halides,

b) from 0.05 to 5.0% by weight of one or more hydrolyzable silane monomers from the group consisting of ethylenically unsaturated, hydrolyzable silicon compounds and hydrolyzable silicon compounds from the group consisting of epoxysilanes, aminosilanes, and mercaptosilanes,

c) from 0.05 to 5.0% by weight of one or more monomers from the group consisting of ethylenically unsaturated epoxide compounds,

d) from 0 to 2.0% by weight of one or more monomers from the group consisting of ethylenically unsaturated 1,3-dicarbonyl compounds, the figures in % by weight being based in each case on the overall weight of the monomers a) used.

Claims

1. A functionalized copolymer in the form of its aqueous dispersion or water-redispersible powder, said copolymer being the polymerized product of monomers comprising:

a) one or more monomers selected from the group consisting of vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having 1 to 15 carbon atoms, vinyl aromatics, olefins, dienes, and vinyl halides,

b) from 0.05 to 5.0% by weight of one or more hydrolyzable silane monomers selected from the group consisting of ethylenically unsaturated, hydrolyzable silicon compounds, epoxysilanes, aminosilanes, and mercaptosilanes,

c) from 0.05 to 5.0% by weight of one or more monomers selected from the group consisting of ethylenically unsaturated epoxide compounds,

d) from 0 to 2.0% by weight of one or more monomers selected from the group consisting of ethylenically unsaturated 1,3-dicarbonyl compounds, all percents being % by weight based on the overall weight of the monomers a) used.

2. The functionalized copolymer of claim 1, wherein the comonomers a) are selected so as to give aqueous copolymer dispersions and aqueous redispersions of the copolymer powders which have a minimum film formation temperature MFFT of <

10°

C. without the addition of film forming auxiliaries.

3. The functionalized copolymer of claim 1, comprising vinyl ester copolymers of vinyl acetate with further vinyl esters;

vinyl ester-ethylene copolymers;

vinyl ester-ethylene-vinyl chloride copolymers;

or vinyl ester-acrylate copolymers.

4. The functionalized copolymer of claim 1, comprising acrylate copolymers;

methyl methacrylate copolymers;

styrene-1,3-butadiene copolymers;

or styrene-(meth)acrylate copolymers.

5. The functionalized copolymer of claim 3, comprising vinyl acetate-ethylene copolymers and copolymers of vinyl acetate, ethylene and vinyl esters of an alpha-branched carboxylic acid having 9 or 10 carbon atoms, optionally containing from 0.05 to 10 weight percent, based on monomers a), of auxiliary monomers, said functionalized copolymer composition selected such that the aqueous dispersion obtainable therefrom has an MFFT of <

10°

C.

6. The functionalized copolymer of claim 1, wherein hydrolyzable silicon compounds b) comprise ethylenically unsaturated silicon compounds of the general formula R¹SiR_0-2(OR²)_1-3, where R is C₁ to C₃ alkyl radical, C₁ to C₃ alkoxy radical or halogen, R¹ is CH₂═

CR³—

(CH₂)_0-1 or CH₂═

CR³CO₂(CH₂)_1-3, R² is an unbranched or branched, unsubstituted or substituted alkyl radical having 1 to 12 carbon atoms or is an acyl radical having 2 to 12 carbon atoms, it being possible for R² to be interrupted by an ether group, R³ is H or CH₃, and the sum of the moieties R and OR² are such that silicon is tetravalent.

7. The functionalized copolymer of claim 1, wherein hydrolyzable silicon compounds b) comprise epoxy silanes, amino silanes, and mercapto silanes of the general formula HS—

(CR⁴₂)_1-3—

SiR⁵₃, where R⁴ is identical or different and is H or C₁ to C₆ alkyl group, R⁵ is identical or different and is a C₁ to C₆ alkyl group or C₁ to C₆ alkoxy group, at least one of the radicals R⁵ being an alkoxy group.

8. The functionalized copolymer of claim 6, wherein said hydrolyzable silicon compound b) comprises one or more silanes selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(1-methoxy)isopropoxysilane, methacryloxypropyltris(2-methoxyethoxy)silane, 3-(triethoxysilyl)propylsuccinic anhydride-silane, 3-mercaptopropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and methacryloxymethyltrimethoxysilane.

9. The functionalized copolymer of claim 8, wherein said hydrolyzable silicon compound b) comprises mixtures of 2 or more silanes, one silane being 3-methacryloxypropyltrimethoxysilane or methacryloxymethyltrimethoxysilane and the second silane being one or more of vinyltrimethoxysilane, vinyltriethoxysilane, glycidyloxypropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane.

10. The functionalized copolymer of claim 1, comprising as comonomer c) containing epoxide groups, one or more monomers selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinylcyclohexene oxide, limonene oxide, myrcene oxide, caryophyllene oxide, vinyltoluenes and styrenes substituted with a glycidyl radical in the aromatic moiety, and vinylbenzoates substituted with a glycidyl radical in the aromatic moiety.

11. The functionalized copolymer of claim 10, comprising as comonomers c) containing epoxide groups one or more monomers selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and vinyl glycidyl ether.

12. The functionalized copolymer of claim 1, containing monomer units of ethylenically unsaturated 1,3-dicarbonyl compounds d) selected from the group consisting of acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxyethyl methacrylate, acetoacetoxybutyl methacrylate, 2,3-di(acetoacetoxy)propyl methacrylate, allyl acetoacetate, and mixtures thereof.

13. The functionalized copolymer of claim 1, comprising from 0.1 to 1.0% by weight of comonomer b) and from 0.25 to 1.5% by weight of comonomer c).

14. A process for preparing the functionalized copolymer of claim 1, said process comprising polymerizing monomers a) through d) in water by means of free-radical polymerization.

22. An adhesive or coating comprising the functionalized copolymer of claim 1.

23. The adhesive of claim 22 which is an adhesive or an exterior insulation system adhesive.

24. The coating of claim 22 which is a low-emission polymer emulsion paint or a polymer dispersion plaster.

26. The adhesive or coating of claim 22 which is a highly filled or supercritically formulated formulation.

15. A process for preparing a functionalized copolymer, said process comprising polymerizing, by means of free-radical polymerization, monomers comprising:

a) one or more monomers selected from the group consisting of vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having 1 to 15 carbon atoms, vinyl aromatics, olefins, dienes, and vinyl halides,

b) from 0.05 to 5.0% by weight of one or more hydrolyzable silane monomers selected from the group consisting of ethylenically unsaturated, hydrolyzable silicon compounds, epoxysilanes, aminosilanes, and mercaptosilanes,

c) from 0.05 to 5.0% by weight of one or more monomers selected from the group consisting of ethylenically unsaturated epoxide compounds,

d) from 0 to 2.0% by weight of one or more monomers selected from the group consisting of ethylenically unsaturated 1,3-dicarbonyl compounds, all percents being % by weight based on the overall weight of the monomers a) used.

16. The process of claim 15, wherein the copolymer is prepared by means of emulsion polymerization in the presence of anionic or nonionic emulsifiers or mixtures thereof.

17. The process of claim 15, wherein the silane fraction b) is metered in in its entirety during the polymerization and the epoxide fraction c) is likewise metered in in its entirety.

18. The process of claim 17, wherein the epoxide fraction c) is metered in toward the end of the polymerization, after a conversion of from 80 to 100%.

19. The process of claim 17, wherein a mixture of two or more different silanes b) is metered in, first one or more silanes being metered in continuously and a further, different silane being metered in together with the epoxide fraction c) after the end of the metered addition of the first silane.

20. The process of claim 15, wherein after the end of the polymerization, post polymerization is carried out for the purpose of removing residual monomer, and any volatile residual monomers and other volatile, nonaqueous constituents of the dispersion are removed.

21. The process of claim 15, wherein water-redispersible polymer powders are prepared from aqueous dispersions by drying following the addition of protective colloids as a spraying aid.

25. The adhesive or coating of claim 21 which is a carbonate-rich or a silicate-rich formulation.