CN101475661A - Fluorine-silicon / or oil modified acrylic ester copolymer cation emulsion - Google Patents
Fluorine-silicon / or oil modified acrylic ester copolymer cation emulsion Download PDFInfo
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- CN101475661A CN101475661A CNA2009100368366A CN200910036836A CN101475661A CN 101475661 A CN101475661 A CN 101475661A CN A2009100368366 A CNA2009100368366 A CN A2009100368366A CN 200910036836 A CN200910036836 A CN 200910036836A CN 101475661 A CN101475661 A CN 101475661A
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Abstract
The invention relates to the preparation of silicon fluorine/or oil modified acrylate copolymer cationic emulsion. The emulsion is obtained through the emulsion polymerization in the presence of a cationic surfactant and a nonionic surfactant. The emulsion comprises an acrylic acid alkyl ester and (methyl) acrylic acid alkyl ester, ethylene carbonate, aroma substituted olefin and functional monomers such as N-hydroxyalkyl acrylamide, (methyl) acrylic acid alkyl fluoride ester, ethynyl/acryloyl oxygen ethyl trialkoxy silane or polymerisable acryloyl oxygen alkyl urethane oil, (methyl) acryloyl oxygen ethyl trialkyl ammonium chloride and/or (methyl) acrylic acid dimethylamine group ethyl ester and a crosslinking agent. The cationic emulsion has excellent performance and can be widely applied to paper products, plastics, coating agents for leather and top grade coatings.
Description
Technical field:
The present invention relates to a kind of function monomer of using, such as (methyl) fluoroalkyl acrylate and vinyl trialkyl oxysilane/or the preparation of the acrylic ester copolymer cation emulsion of polymerisable acryloyloxyalkyl ammonia ester oil modification.
Background technology:
The cation acrylic emulsion is different with anionic emulsion, its polymer surfaces has positive charge, and it not only helps the neutralization on electronegative surface, absorption and bonding, but also has sterilization, prevent dust and antistatic property, thereby be widely used in fabric, the processing of paper and leather, the antistatic treatment of macromolecular material, and acrylic resin inherent tackyness, weathering resistance and film-forming properties, thereby the vinylformic acid cation emulsion also can be used for building coating.
Introducing of relevant fluorinated silicone modified acrylic anionic emulsion is more, but its cation emulsion is less, at present the domestic conceptual phase that rests on.
Summary of the invention:
The object of the present invention is to provide a kind of function monomer of using, such as (methyl) fluoroalkyl acrylate, vinyl trialkyl oxysilane/or the acrylic ester copolymer cation emulsion of polymerisable acryloyloxyalkyl ammonia ester oil modification.
The present invention, the component of its preparation and weight ratio are:
Alkyl acrylate 8-15, (methyl) alkyl acrylate 12-25 comprises vinylformic acid/or (methyl) acrylic acid hydroxy alkyl ester, its alkyl is the C1-C8 alkyl; NSC 11801 5-20; Function monomer 0.5-10; Linking agent 0.5-5 comprises dimethyl diallyl ammonium halide and polyethyleneglycol diacrylate; Emulsifying agent 2-5 in the monomer total amount, comprises positively charged ion and nonionogenic tenside; Initiator 0.5-2 in the monomer total amount, comprises superoxide and reductive agent; Buffer reagent is an amount of; Water 50-70, wherein, function monomer is one or more mixing in the following function monomer:
(1) N-hydroxyalkyl acrylamide, its alkyl are the C1-C3 alkyl;
(2) (methyl) fluoroalkyl acrylate, its molecular formula is: CH2=(R1) CH (O=) CO (R2Fn), R1 is H or CH3 in the formula, and R2 is C2-C8, and F is a fluorine atom, and n equals 1-3;
(3) vinyl trialkyl oxysilane, its alkyl are methyl or ethyl or 2-methoxy ethyl; Methyl allyl acyloxypropyl trimethoxysilane;
(4) polymerisable acryloyloxyalkyl ammonia ester oil, its alkyl is ethyl or propyl group, and its urethano is aromatic series or aliphatics urethano, and its oleic acid ester group is a C12-C18 unsaturated fatty acid ester base;
(5) (methyl) acrylyl oxy-ethyl tri alkyl ammomium chloride, its alkyl is methyl or ethyl;
(6) (methyl) propylene dimethylin ethyl ester or (methyl) acrylamide ethyl ethylene-urea.
NSC 11801 of the present invention comprises vinyl-acetic ester, and tertiary ethylene carbonate, its tertiary monocarboxylic acid are 10 or 11 carbonic acid; The fragrance substituted olefine is such as vinylbenzene and homologue thereof.
Linking agent of the present invention is the dialkyl diallyl ammonium halide, and its alkyl is the C1-C4 alkyl, and its halogen atom is a chlorine or bromine; Polyethyleneglycol diacrylate, its polyoxyethylene glycol MOL number equals 2-8.
Emulsifying agent of the present invention comprises cats product and nonionogenic tenside, and cats product is such as quaternary ammonium salt, benzyl quaternary ammonium salt or imidazoles quaternary ammonium salt; Such as alkylphenol polyoxyethylene, its alkyl is the C4-C9 alkyl, and polyoxyethylene Mol number equals 3-40; Alkanol or fatty alcohol-polyoxyethylene ether, its alkyl are the C4-C12 alkyl, and polyoxyethylene Mol number equals 3-40 or vinyl Soxylat A 25-7, and polyoxyethylene Mol number equals 7-40.
Initiator of the present invention comprises superoxide and reductive agent, and superoxide is 2, and 2-azo diisobutyl is narrowed hydrochloride, azo isobutyronitrile, benzoyl peroxide, Peracetic Acid, hydrogen peroxide or persulphate; Described reductive agent is sulphite, rongalite, dimension C, ferrous sulfate or acetate.
Buffer reagent of the present invention comprises Secondary ammonium phosphate, sodium bicarbonate, and acetate etc., it act as the pH value of regulating emulsion, and addition is for making pH to 3-5.5.
The present invention, with vinyl trialkyl oxysilane/or methacryloxypropyl trialkoxy silane and acrylic ester copolymer after, its multipolymer has good sticking power to ground.
The present invention, behind (methyl) fluoroalkyl acrylate and acrylic ester copolymer, its polymkeric substance has excellent cohesive force and antistatic to plastic bottom material and leather, anti-stain characteristic, its cationic polymers improves to the sticking power and the water tolerance of ground.
The present invention adds linking agent, can improve the weathering resistance and the tensile strength of paint film.
The present invention, behind polymerisable acryloyloxyalkyl ammonia ester oil and acrylic ester copolymer, its paint film fullness ratio significantly improves.
Embodiment:
Embodiment 1, butyl acrylate 55, (methyl) methyl acrylate 19.0g, vinylbenzene 20.0g, N hydroxymethyl acrylamide 1.4g, vinyltrimethoxy silane 1.0g, dodecyl benzyl dimethyl ammonium chloride 2.35, OP-10 emulsifying agent 1.0g, deionized water 149.0g, add buffer reagent and regulate pH to 3-5.5,2,2-azo isobutyl-is narrowed hydrochloride and is had (add-on is 0.96g) down, makes silicon modified cation emulsion in 70-85 ℃ through conventional emulsion polymerization technique.
Embodiment 2, butyl acrylate 63.8, (methyl) methyl acrylate 27.4g, (methyl) fluoroalkyl acrylate 13,1g, vinylbenzene 26.2g, N hydroxymethyl acrylamide 1.4g, Hydroxyethyl acrylate 2.0g, acryloyl-oxy propyl trimethoxy silicane 1.4g, (methyl) acryloyl oxyethyl group tri alkyl ammomium chloride 5.4g, dodecyl benzyl dimethyl ammonium chloride 2.0g, alkyl polyoxyethylene ether 2.0g, deionized water 211.0g adds buffer reagent and regulates pH to 3-5.5, in the presence of Peracetic Acid (add-on is 2.7g), make fluorinated silicone modified cation emulsion through conventional emulsion polymerization technique in 70-85 ℃.
Embodiment 3, butyl acrylate 51.0g, (methyl) methyl acrylate 23.0g, vinylbenzene 26.0g, N hydroxymethyl acrylamide 1.5g, (methyl) acryloyl-oxy propyl trimethoxy silicane 1.5g, (methyl) acrylamide ethyl ethylene-urea 5.0g, two dimethyl diallyl ammonium chloride 1.6g, Trimethyllaurylammonium bromide 2.0g, OP-10 emulsifying agent 1.0g, deionized water 202.8g adds buffer reagent and regulates pH to 3-5.5, in the presence of hydrogen peroxide and S-WAT (add-on is respectively 1.09g and 0.54g), make the self-crosslinking cation emulsion through conventional emulsion polymerization technique in 60-75 ℃.
Embodiment 4, butyl acrylate 50.0g, (methyl) methyl acrylate 30.0g, Propylene glycol monoacrylate 2.0g, vinylbenzene 18.0g, N hydroxymethyl acrylamide 2.0g, (methyl) acryloyl-oxy propyl trimethoxy silicane 2.0g, acrylyl oxy-ethyl ammonia ester oil 11.5g, dimethyl diallyl ammonium chloride 2.0g, Dodecyl trimethyl ammonium chloride 2.1g, alkylphenol polyoxyethylene 2.0g, deionized water 218.2g, add buffer reagent and regulate pH to 3-5.5, in the presence of the azo isobutyronitrile (add-on is 1.2g), in 65-85 ℃ through conventional emulsion polymerization technique and must oily modified cation emulsion.
Embodiment 5, butyl acrylate 50.0g, Isooctyl acrylate monomer 10.0g, vinyl-acetic ester 30.0g, tertiary ethylene carbonate 10.0g, N hydroxymethyl acrylamide 2.0g, vinyltrimethoxy silane 2.0g, dodecyl benzyl dimethyl ammonium chloride 2.55g, vinyl Soxylat A 25-7 1.09g, deionized water 156.0g adds buffer reagent and regulates pH to 3-5.5, in the presence of ammonium persulphate and S-WAT (add-on is respectively 0.52g and 0.26g), make cation emulsion in 60-75 ℃ through conventional emulsion polymerization technique, this emulsion can be used as tackiness agent.
Claims (6)
1, fluorine silicon/or oil modified acrylic ester copolymer cation emulsion, the component of its preparation and weight ratio are:
Alkyl acrylate 8-15, (methyl) alkyl acrylate 12-25 comprises vinylformic acid/or (methyl) acrylic acid hydroxy alkyl ester, its alkyl is the C1-C8 alkyl;
NSC 11801 5-20;
Function monomer 0.5-10;
Linking agent 0.5-5 comprises dimethyl diallyl ammonium halide and polyethyleneglycol diacrylate;
Emulsifying agent 2-5 in the monomer total amount, comprises positively charged ion and nonionogenic tenside;
Initiator 0.5-2 in the monomer total amount, comprises superoxide and reductive agent;
Buffer reagent is an amount of;
Water 50-70,
Wherein, function monomer is one or more mixing in the following function monomer:
(1) N-hydroxyalkyl acrylamide, its alkyl are the C1-C3 alkyl;
(2) (methyl) fluoroalkyl acrylate, its molecular formula is: CH2=(R1) CH (0=) C0 (R2Fn), R1 is H or CH3 in the formula, and R2 is C2-C8, and F is a fluorine atom, and n equals 1-3;
(3) vinyl trialkyl oxysilane, its alkyl are methyl or ethyl or 2-methoxy ethyl; Methyl allyl acyloxypropyl trimethoxysilane;
(4) polymerisable acryloyloxyalkyl ammonia ester oil, its alkyl is ethyl or propyl group, and its urethano is aromatic series or aliphatics urethano, and its oleic acid ester group is a C12-C18 unsaturated fatty acid ester base;
(5) (methyl) acrylyl oxy-ethyl tri alkyl ammomium chloride, its alkyl is methyl or ethyl;
(6) (methyl) propylene dimethylin ethyl ester or (methyl) acrylamide ethyl ethylene-urea.
2, fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion is characterized by: described NSC 11801, comprise vinyl-acetic ester, and tertiary ethylene carbonate, its tertiary monocarboxylic acid are 10 or 11 carbonic acid; The fragrance substituted olefine is such as vinylbenzene and homologue thereof.
3, fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: described linking agent is the dimethyl diallyl ammonium halide, its halogen atom is a chlorine or bromine; Polyethyleneglycol diacrylate, its polyoxyethylene glycol M0L number equals 2-8.
4, fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: described cats product comprises quaternary ammonium salt, benzyl quaternary ammonium salt or imidazoles quaternary ammonium salt.
5, fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion is characterized by: the agent of described non-ionic surface words property, and such as alkylphenol polyoxyethylene, its alkyl is the C4-C9 alkyl, polyoxyethylene Mo1 number equals 3-40; Alkanol or fatty alcohol-polyoxyethylene ether, its alkyl are the C4-C12 alkyl, and polyoxyethylene Mo1 number equals 3-40 or vinyl Soxylat A 25-7, and polyoxyethylene Mo1 number equals 7-40.
6, fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: described superoxide is 2, and 2-azo diisobutyl is narrowed hydrochloride, azo isobutyronitrile, benzoyl peroxide, Peracetic Acid, hydrogen peroxide or persulphate; Described reductive agent is sulphite, rongalite, dimension C, ferrous sulfate or acetate.
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Address after: 515500, south side of Huaan Road, Jiedong experimental area, Guangdong, Jieyang (No. 16) Patentee after: Guangdong Tianyin Industrial Co., Ltd. Address before: 515500 south section of Huaan Road, Jiedong Economic Development Zone, Jiedong County, Guangdong Patentee before: Tianyin Chemical Industry Co., Ltd., Guangdong |