CN101475661B - 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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- CN101475661B CN101475661B CN2009100368366A CN200910036836A CN101475661B CN 101475661 B CN101475661 B CN 101475661B CN 2009100368366 A CN2009100368366 A CN 2009100368366A CN 200910036836 A CN200910036836 A CN 200910036836A CN 101475661 B CN101475661 B CN 101475661B
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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, and its polymer surfaces has positive charge, and it not only helps the neutralization on electronegative surface; Absorption and bonding, but also have sterilization, dustproof and antistatic property; Thereby be widely used in fabric, the processing of paper and leather, the antistatic treatment of macromolecular material; And vinyl resin inherent tackyness, weathering resistance and film-forming properties, thereby the vinylformic acid cation emulsion also can be used for trade sales 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 acrylic amide, 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) acrylic amide 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 TX10, its alkyl is the C4-C9 alkyl, and T 46155 Mol number equals 3-40; Alkanol or AEO, its alkyl are the C4-C12 alkyl, and T 46155 Mol number equals 3-40 or vinyl Soxylat A 25-7, and T 46155 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, Lucidol, Peracetic Acid, hydrogen peroxide or persulphate; Said 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, Bing Xisuandingzhi 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 adds buffer reagent and regulates 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 the 70-85 ℃ of conventional emulsion polymerization technique of warp.
Embodiment 2, Bing Xisuandingzhi 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; Add buffer reagent and regulate pH to 3-5.5, in the presence of Peracetic Acid (add-on is 2.7g), make fluorinated silicone modified cation emulsion in the 70-85 ℃ of conventional emulsion polymerization technique of warp.
Embodiment 3, Bing Xisuandingzhi 51.0g, (methyl) methyl acrylate 23.0g, vinylbenzene 26.0g; N hydroxymethyl acrylamide 1.5g, (methyl) acryloyl-oxy propyl trimethoxy silicane 1.5g, (methyl) acrylic amide 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; Add buffer reagent and regulate 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 in the 60-75 ℃ of conventional emulsion polymerization technique of warp.
Embodiment 4, Bing Xisuandingzhi 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, DTAC 2.1g; TX10 2.0g, deionized water 218.2g adds buffer reagent and regulates pH to 3-5.5; In the presence of the azo isobutyronitrile (add-on is 1.2g), get oily modified cation emulsion in the 65-85 ℃ of conventional emulsion polymerization technique of warp.
Embodiment 5, Bing Xisuandingzhi 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; Add buffer reagent and regulate 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 the 60-75 ℃ of conventional emulsion polymerization technique of warp, this emulsion can be used as tackiness agent.
Claims (6)
1. fluorine silicon/or oil modified acrylic ester copolymer cation emulsion, its component and weight part 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 a Secondary ammonium phosphate, sodium hydrogencarbonate or acetate, and addition is for making pH to 3-5.5; Water 50-70,
Wherein, function monomer is one or more mixing in the following function monomer:
(1) N-hydroxyalkyl acrylic amide, 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, its urethano is aromatic series or aliphatics urethano;
(5) (methyl) acrylyl oxy-ethyl tri alkyl ammomium chloride, its alkyl is methyl or ethyl;
(6) (methyl) propylene dimethylaminoethyl or (methyl) acrylic amide ethyl ethylene-urea.
2. fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: described NSC 11801, comprise vinyl-acetic ester, tertiary ethylene carbonate, its tertiary monocarboxylic acid are 10 or 11 carbonic acid.
3. fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: said linking agent is the dimethyl diallyl ammonium halide, its halogen atom is a chlorine or bromine; Polyethyleneglycol diacrylate, its polyoxyethylene glycol MOL number equals 2-8.
4. fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion, it is characterized by: said 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, it is characterized by: said nonionogenic tenside is a TX10, and its alkyl is the C4-C9 alkyl, and T 46155 Mol number equals 3-40; Alkanol or AEO, its alkyl are the C4-C12 alkyl, and T 46155 Mol number equals 3-40 or vinyl Soxylat A 25-7, and T 46155 Mol number equals 7-40.
6. fluorine silicon according to claim 1/or oil modified acrylic ester copolymer cation emulsion; It is characterized by: said superoxide is 2,2-azo diisobutyl amidine hydrochloride, azo isobutyronitrile, Lucidol, Peracetic Acid, hydrogen peroxide or persulphate; Said reductive agent is sulphite, rongalite, dimension C, ferrous sulfate or acetate.
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| CN102443102B (en) * | 2010-10-11 | 2014-04-23 | 董绍胜 | Liquid film-forming material and synthetic method thereof |
| CN102408808B (en) * | 2011-09-16 | 2013-07-24 | 陕西科技大学 | Aqueous fluorocarbon coating for painting metal base materials |
| CN107434866B (en) * | 2012-06-19 | 2021-05-28 | 陶氏环球技术有限责任公司 | Water-based blend compositions and methods of making the same |
| JP6298812B2 (en) * | 2012-06-19 | 2018-03-20 | ダウ グローバル テクノロジーズ エルエルシー | Aqueous blend composition and process for producing the same |
| CN103665231B (en) * | 2012-09-10 | 2016-09-14 | 中国石油化工集团公司 | A kind of vinyl acetate-ethylene-tertiary ethylene carbonate copolymer emulsion and synthetic method |
| CN102924649B (en) * | 2012-10-25 | 2014-08-27 | 陕西科技大学 | Preparation method of high-hydrophobicity leather coating agent |
| EP4321543A3 (en) * | 2017-04-21 | 2024-04-10 | Consorcio Comex, S. A. De C. V. | Elastomeric latices and coating compositions containing the same |
| CN108192011B (en) * | 2017-12-30 | 2020-10-09 | 浙江工业大学 | Vinyl acetate-vinyl versatate polymer emulsion and preparation and application thereof |
| CN109553719B (en) * | 2018-12-04 | 2020-11-10 | 太仓宝霓实业有限公司 | Water-repellent antistatic copolymer and preparation method and composition thereof |
| CN111883726A (en) * | 2020-08-28 | 2020-11-03 | 芜湖天弋能源科技有限公司 | Lithium ion battery diaphragm slurry and preparation method and application thereof |
| CN117003933B (en) * | 2023-08-14 | 2024-01-19 | 江门市金桥新材料有限公司 | Soap-free polymeric cationic dispersion and preparation method thereof |
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| CN1493601A (en) * | 2003-07-23 | 2004-05-05 | 华东理工大学 | Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method |
| CN1546541A (en) * | 2003-12-12 | 2004-11-17 | 华东理工大学 | Shell-core type fluoride containing emulsion |
| CN101016697A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493601A (en) * | 2003-07-23 | 2004-05-05 | 华东理工大学 | Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method |
| CN1546541A (en) * | 2003-12-12 | 2004-11-17 | 华东理工大学 | Shell-core type fluoride containing emulsion |
| CN101016697A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Method of preparing fluorine and silicon containing hydrophobic and oil repellent fabric finishing agent |
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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 |