Stock material or miscellaneous articles – Composite – Of epoxy ether
Reexamination Certificate
2001-01-25
2003-03-18
Dawson, Robert (Department: 1712)
Stock material or miscellaneous articles
Composite
Of epoxy ether
C428S510000, C428S511000, C523S401000, C523S406000, C523S410000, C523S412000, C523S413000, C525S327300, C525S330300, C525S330700, C525S331900, C525S333300
Reexamination Certificate
active
06534177
ABSTRACT:
BACKGROUND OF THE INVENTION
1) Field of the Invention
The present invention relates to crosslinkable polymer compositions in the form of their aqueous polymer dispersions or polymer powders redispersible in water, processes for their preparation and their use.
2) Background Art
The preparation of polymers containing epoxy groups by copolymerization of monomers containing epoxy groups is known. WO-A 95/04767 describes a process for the preparation of aqueous polymer dispersions or polymer powders obtainable therefrom, in which a hydrophobic copolymer optionally substituted by epoxy groups is prepared in the presence of a low molecular weight water-soluble polymer substituted by carboxyl groups. WO-A 93/22353 discloses the preparation of polymers in the form of their aqueous polymer dispersions or polymer powders redispersible in water, vinyl esters of branched carboxylic acids having 11 to 15 C atoms being copolymerized, inter alia, also with comonomers having epoxide functional groups, such as glycidyl methacrylate. EP-A 721004 relates to crosslinkable polymer powders which are redispersible in water and which are composed of a film-forming polymer component having functional groups, such as hydroxyl groups, and a crosslinking component, for example epoxy resins.
Common to all these processes is the fact that the second reactive component is not mixed with the polymer dispersion or with the polymer powder until after the preparation of the crosslinkable polymer. Although precrosslinking can thus be prevented, only low degrees of crosslinking and inhomogeneous products result in the case of poorly compatible components.
It was thus the object to provide crosslinkable polymer compositions which have a long shelf life and form homogeneous films with a high degree of crosslinking.
SUMMARY OF THE INVENTION
The invention relates to crosslinkable polymer compositions in the form of their aqueous polymer dispersions or polymer powders redispersible in water, containing
A) a copolymer of one or more comonomers from the group consisting of vinyl esters of straight-chain or branched alkanecarboxylic acids having 1 to 18 C atoms, acrylates or methacrylates of branched or straight-chain alcohols having 1 to 15 C atoms, dienes, olefins, vinylaromatics and vinyl halides, and of from 0.1 to 10% by weight, based on the total weight of the comonomers, of one or more ethylenically unsaturated comonomers containing epoxide groups, and
B) one or more non-copolymerizable compounds having at least two epoxide groups.
The invention furthermore relates to a process for the preparation of crosslinkable polymer compositions in the form of their aqueous polymer dispersions or polymer powders redispersible in water by emulsion polymerization of one or more comonomers from the group consisting of vinyl esters of straight-chain or branched alkanecarboxylic acids having 1 to 18 C atoms, acrylates or methacrylates of branched or straight-chain alcohols having 1 to 15 C atoms, dienes, olefins, vinylaromatics and vinyl halides, and of from 0.1 to 10% by weight, based on the total weight of the comonomers, of one or more ethylenically unsaturated comonomers containing epoxide groups, and optionally drying of the resulting polymer dispersions in the presence of one or more protective colloids, one or more non-copolymerizable compounds having at least two epoxide groups being added before, during or after the emulsion polymerization.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Suitable vinyl esters are vinyl esters of straight-chain or branched carboxylic acids having 1 to 18 atoms. Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of &agr;-branched monocarboxylic acids having 9 to 11 C atoms, for example VeoVa9
R
or VeoVa10
R
(trade names of Shell). Vinyl acetate is particularly preferred.
Suitable monomers from the group consisting of the esters of acrylic acid or methacrylic acid are esters of straight-chain or branched alcohols having 1 to 15 C atoms. Preferred methacrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate are particularly preferred.
Suitable dienes are 1,3-butadiene and isoprene. Examples of copolymerizable olefins are ethene and propene. Vinylaromatics which can be polymerized are styrene and vinyltoluene. From the group consisting of the vinyl halides, vinyl chloride is usually used.
Optionally from 0.05 to 10% by weight, based on the total weight of the monomer mixture, of auxiliary monomers can also be copolymerized. Examples of auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxamides and carbo-nitriles, preferably acrylamide and acrylonitrile; mono- and diesters of fumaric acid and maleic acid, such as the diethyl and diisopropyl esters; and maleic anhydride; ethylenically unsaturated sulfonic acids and their salts, preferably vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Further examples are precrosslinked comonomers, such as polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or postcrosslinked comonomers, for example acrylamidoglycolic acid (AGA), methyl methacrylamidoglycolate (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl-carbamate, alkyl ethers, such as isobutoxy ether, or esters of N-methylolacrylamide, of N-methylolmethacrylamide and of N-methylolallylcarbamate. Further examples are comonomers having silicon functional groups, such as acryloyloxypropyltri(alkoxy)- and methacryloyloxypropyltri(alkoxy)silanes or vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, it being possible, for example, for ethoxy and ethoxypropylene glycol ether radicals to be present as alkoxy groups.
Suitable comonomers containing epoxide groups are glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinylcyclohexene oxide, limonene oxide, myrcene oxide, caryophyllene oxide, styrenes and vinyltoluenes substituted by a glycidyl radical in the aromatic moiety and vinyl benzoates substituted by a glycidyl radical in the aromatic moiety. Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and vinyl glycidyl ether are preferred. Preferably, the amount of the comonomer units having epoxide functional groups is from 0.1 to 5.0% by weight, based on the total weight of the comonomers.
Most preferred are the copolymers mentioned below which also have the above-mentioned comonomer units containing epoxide groups, in the amounts described above. The data in % by weight and the amount of comonomer units containing epoxide groups sum in each case to 100% by weight.
From the group consisting of the vinyl ester polymers:
Vinyl acetate polymers;
vinyl ester/ethylene copolymers, such as vinyl acetate/ethylene copolymers, having an ethylene content of from 1 to 60% by weight;
vinyl esters/ethylene/vinyl chloride copolymers having an ethylene content of from 1 to 40% by weight and a vinyl chloride content of from 20 to 90% by weight, preferably vinyl acetate and/or vinyl propionate and/or one or more copolymerizable vinyl esters, such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of an alpha-branched carboxylic acid, in particular vinyl versatate (VeoVa9
R
, VeoVa10
R
), being present as vinyl esters;
vinyl acetate copolymers with from 1 to 50% by weight of one or more copolymerizable vinyl esters, such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of an alpha-branched carboxylic acid, in particular vinyl versatate (VeoVa9
R
, VeoVa10
R
), which optionally also contain from 1 to 40% by weig
Adler Klaus
Eck Herbert
Kohlhammer Klaus
Lutz Hermann
Aylward D.
Brooks & Kushman P.C.
Dawson Robert
Wacker-Chemie GmbH
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