CN101293940B - Method for preparing water-proof, oil-proof fluorine acrylic acid containing cation/non-tonic surface active agent emulsions - Google Patents
Method for preparing water-proof, oil-proof fluorine acrylic acid containing cation/non-tonic surface active agent emulsions Download PDFInfo
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- CN101293940B CN101293940B CN2007100403430A CN200710040343A CN101293940B CN 101293940 B CN101293940 B CN 101293940B CN 2007100403430 A CN2007100403430 A CN 2007100403430A CN 200710040343 A CN200710040343 A CN 200710040343A CN 101293940 B CN101293940 B CN 101293940B
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Abstract
The invention aims to provide a preparation method of a hydrophobic lipophobic fluorine-containing acrylic acid cation/non-ionic surfactant emulsion. The preparation method comprises the steps of: mixing copolymerization monomers with cationic surfactant quarternary ammonium salt, a non-ionic surfactant Peregal O and an initiator to obtain a pre-emulsion under high shearing condition, and allowing copolymerization with N-methylol acrylamide. The cation/non-ionic surfactant emulsion is obtained by using a high-speed shearing machine, so that the mechanical void effect makes the reactants to reach nanometer scale. The polymerization rate is stable and the composition distribution of the polymer is uniform. The inventive surfactant emulsion has good mechanical stability, pH stability, chemical stability, dilution stability, and storage stability. The textile post-treated by the inventive emulsion has excellent hydrophobic, lipophobic and anti-fouling properties.
Description
Technical field
The present invention relates to the preparation method of fabric post-treatment agent, particularly the preparation method of the fluorine-containing cationic/nonionic tensio-active agent of water and oil repellant.
Background technology
Fluorine-containing alkyl copolymer belongs to the fabric post-treatment agent, gives grounds such as fabric, leather, paper excellent waterproof and oilproof soil-repellent finishing effect.China starts late at this area research, and most of production technology is by 3M, Du Pont, and companies such as Da Jin grasp, and cause valuable product, and the production cost of dyeing and printing products increases sharply, and greatly reduces the competitive power of China's product in the world market.
China also has part company and unit to be engaged in this Project Study, but has following point:
1. the simple emulsification in advance of tensio-active agent does not reach nano level.
2. the polymerization system surfactant activity is low, and consumption is big, and polymerization system is unstable.
3. fluorochemical monomer and non-fluorochemical monomer intermiscibility are poor, the skewness of the content of component and chain in the polymkeric substance, and the fluctuation of component content is big.
Fluorine-containing alkyl acrylate copolymer system comprises solution-type and emulsion-type, in recent years, considers safety-problems and environmental problem, and the fluorine-containing alkyl copolymer of this type is refused oil resistance water finishing composition and is mostly the water-dispersion emulsion-type.
CN1613883A has introduced the preparation method of water-and oil-repellent agent with perfluorinated acrylate multipolymer dispersion miniemulsion, and its thin emulsifying technology mainly is to adopt ultrasonic technology.
Emulsifying technology is the New Emulsion polymerization method that latest developments are got up in advance.It is through obtaining the pre-emulsion of very little 100 nanometers of finely dispersed particle diameter under the shear conditions; Add initiator then and directly in monomer droplet, cause nucleation; Each monomer has all become relatively independent reaction nuclear, avoids the problem of monomer indissoluble and migration in water.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of water and oil repellant fluorine-containing cationic/nonionic tensio-active agent.
In order to realize the object of the invention, the technical scheme that is adopted is as follows:
A kind of preparation method of water and oil repellant fluorine-containing cationic/nonionic surface active agent emulsions comprises the steps:
(1) with copolymerized monomer mixture: emulsifying agent is according to mass ratio 30～50: 2～3; Add initiator V-50, it with the multipolymer monomer mass than 1～2: 30～50, under high shear conditions pre-emulsion; Median size 30～150 nanometers of pre-emulsion, polymolecularity is normal distribution; Said emulsifying agent is made up of cats product quaternary amine and nonionogenic tenside paregal O;
(2) in reactor drum, add 1/4 pre-emulsion; Logical nitrogen; Drip remaining pre-emulsion and the copolyreaction of linking agent N hydroxymethyl acrylamide down at 40～80 ℃; Insulation was 2 hours after reaction finished, and was chilled to the room temperature filtration and made fabric water and oil repellant fluorine-containing cationic/nonionic surface active agent emulsions; Linking agent is 2～3: 30～50 with multipolymer monomer mass ratio.
Copolymerized monomer mixture of the present invention is by TEB 3K, tetradecyl acrylate, and dodecyl acrylate, dodecafluorhe-ptylacrylate is formed.Wherein methacrylic ester accounts for 20%～40wt% of total monomer weight; Tetradecyl acrylate accounts for 20%～40wt% of total monomer weight; Dodecyl acrylate accounts for 5%～10wt% of total monomer weight, and dodecafluorhe-ptylacrylate accounts for 30%～35wt% of total monomer weight.
Described quaternary ammonium salt cationic tensio-active agent is two alkyl diquaternary amine salt, general formula (CH
2) m [CH
3(CH
2) nN
+(R1) (R2) (R3) X
-], wherein n is 8～18, and R1, R2, R3 represent that carbonatoms is 1～6 alkyl, and m is 2,4,6,8,10, and X is a halogen atom, as is fluorine, chlorine, bromine, iodine.
Described cats product accounts for 50～70wt% of emulsion total amount.
Paregal O tensio-active agent of the present invention is Fatty Alcohol(C12-C14 and C12-C18) and ethylene oxide condensate, does not contain APEO (organic phenols).
Described initiator V-50 is azo two different basic amidine hydrochlorides.
The preparation method of water and oil repellant fluorine-containing cationic/nonionic surface active agent emulsions of the present invention, easy and simple to handle.Adopt the cationic/nonionic surface active agent emulsions of this method preparation owing to adopt high-speed shearing machine, the hole effect of machinery makes reactant can reach nano level.Twin cationic/nonionogenic tenside surfactivity is high, and consumption is little, is half consumption of common tensio-active agent.And rate of polymerization is stable, and the composition of polymkeric substance is evenly distributed.Surface active agent emulsions of the present invention has good mechanical stability, PH stability, chemicalstability, dilution stability, package stability.Emulsion of the present invention to fabric through after after the arrangement, have excellent water, oil and soil repellent performance.
Embodiment
In order to further specify effect of the present invention and method, explain with concrete embodiment at present.
Embodiment 1
(1) with perfluoroalkyl acrylate 30 grams, TEB 3K 35 grams, methylacrylic acid 14 esters 35 grams, deionized water 200 grams; Organic solvent-acetone 65 grams, quaternary ammonium salt cationic tensio-active agent, peregal 0 nonionogenic tenside 3.5 grams, N hydroxymethyl acrylamide 2 grams; High-shear at ambient temperature gets pre-emulsion. and 1/5 pre-emulsion is placed to have stirring rake again, TM is in the four-hole boiling flask of the logical nitrogen device of return line; Be warming up to 60 degree, drip the initiator initiated polymerization, get the white emulsion of blueing light; About solid content 30%, transformation efficiency＞98%, acetone is removed in distillation.
Embodiment 2
(2) with perfluoroalkyl acrylate 35 grams, TEB 3K 30 grams, methylacrylic acid 14 esters 35 grams, deionized water 200 grams; Organic solvent-acetone 65 grams, quaternary ammonium salt cationic tensio-active agent, peregal 0 nonionogenic tenside 3.5 grams, N hydroxymethyl acrylamide 2 grams; High-shear at ambient temperature gets pre-emulsion. 1/5 pre-emulsion placed to have stirring rake, TM again; In the four-hole boiling flask of the logical nitrogen device of return line, be warming up to 60 degree, drip the initiator initiated polymerization.Get the white emulsion of blueing light, solid content about 30%, acetone is removed in transformation efficiency＞98%. distillations.
The method of use that water and oil repellant fluorine-containing positively charged ion non-tonic surface active agent emulsions of the present invention is used for the fabric water and oil repellant is: every premium on currency adds this emulsion (solid content being treated to the emulsion about 20%) 10-30 gram; (the higher effects of concentration maybe be better certainly; Different fabric conditions are different) one soak one and roll; Drying treatment under the temperature of 100-170 degree has good effect to water and oil repellant.
The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (1)
1. the preparation method of a fabric water and oil repellant fluorine-containing cationic/nonionic surface active agent emulsions comprises the steps:
(1) with copolymerized monomer mixture: emulsifying agent is according to mass ratio 30～50: 2～3; Add initiator V-50, it and multipolymer monomer mixture mass ratio 1～2: 30～50, under high shear conditions pre-emulsion; Median size 30～150 nanometers of pre-emulsion, polymolecularity is normal distribution;
Said emulsifying agent is made up of cats product quaternary amine and nonionogenic tenside paregal O; The 50-70wt% of described quaternary ammonium salt cationic surfactant comprise emulsion total amount;
Said copolymerized monomer mixture is by TEB 3K, tetradecyl acrylate, and dodecyl acrylate, dodecafluorhe-ptylacrylate is formed; Wherein methacrylic ester accounts for 20%～40wt% of total monomer weight; Tetradecyl acrylate accounts for 20%～40wt% of total monomer weight; Dodecyl acrylate accounts for 5%～10wt% of total monomer weight, and dodecafluorhe-ptylacrylate accounts for 30%～35wt% of total monomer weight;
Described quaternary ammonium salt cationic tensio-active agent is two alkyl diquaternary amine salt, general formula (CH
2) m [CH
3(CH
2) nN
+(R1) (R2) (R3) X
-], wherein n is 8～18, and R1, R2, R3 represent that carbonatoms is 1～6 alkyl, and m is 2,4,6,8,10, and X is one of fluorine, chlorine, bromine, iodine;
Described paregal O tensio-active agent is Fatty Alcohol(C12-C14 and C12-C18) and ethylene oxide condensate, does not contain organic phenols;
(2) in reactor drum, add 1/4 pre-emulsion; Logical nitrogen; Drip remaining pre-emulsion and the copolyreaction of linking agent N hydroxymethyl acrylamide down at 40～80 ℃; Insulation was 2 hours after reaction finished, and was chilled to the room temperature filtration and made fabric water and oil repellant fluorine-containing cationic/nonionic surface active agent emulsions; Linking agent is 2～3: 30～50 with multipolymer monomer mass ratio.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100403430A CN101293940B (en) | 2007-04-29 | 2007-04-29 | Method for preparing water-proof, oil-proof fluorine acrylic acid containing cation/non-tonic surface active agent emulsions |
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|---|---|---|---|
| CN2007100403430A CN101293940B (en) | 2007-04-29 | 2007-04-29 | Method for preparing water-proof, oil-proof fluorine acrylic acid containing cation/non-tonic surface active agent emulsions |
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| CN101293940A CN101293940A (en) | 2008-10-29 |
| CN101293940B true CN101293940B (en) | 2012-11-21 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011129015A1 (en) * | 2010-04-16 | 2011-10-20 | 株式会社ネオス | Imparting agent for antifouling properties |
| CN102108109B (en) * | 2010-12-29 | 2012-05-23 | 四川理工学院 | Preparation method of fluorine-containing fabric finishing agent |
| CN102465403A (en) * | 2011-06-09 | 2012-05-23 | 上海嘉乐股份有限公司 | Novel finishing process of co-polymerization fluorine antifouling and soil-releasing finishing liquor |
| CN103741456B (en) * | 2013-12-17 | 2016-08-31 | 南通市通州区家纺产业发展服务中心 | A kind of cotton clothes water repellent finishing agent and preparation method thereof |
| CN103980418B (en) * | 2014-05-23 | 2016-08-31 | 深圳天鼎精细化工制造有限公司 | A kind of cation water-based Organic fluoride acrylate polymer as well as preparation method and application thereof |
| CN104387519A (en) * | 2014-10-30 | 2015-03-04 | 浙江工业大学 | Nano cationic fluorocarbon polymer emulsion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN1687180A (en) * | 2005-03-18 | 2005-10-26 | 上海瀛正科技有限公司 | Method for preparing super branched polyacrylate fluorine and application in finishing agent for textile |
| CN1837456A (en) * | 2006-04-25 | 2006-09-27 | 辽宁氟材料研究院有限公司 | Emulsion type fluorine-containing textile finishing agent and preparation method thereof |
| WO2007018783A3 (en) * | 2005-08-08 | 2007-04-05 | Arkema Inc | Polymerization of fluoropolymers using non-fluorinated surfactants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465591B1 (en) * | 2000-04-24 | 2002-10-15 | Avery Dennison Corporation | Acrylic emulsion coating for films, paper and rubber |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN1687180A (en) * | 2005-03-18 | 2005-10-26 | 上海瀛正科技有限公司 | Method for preparing super branched polyacrylate fluorine and application in finishing agent for textile |
| WO2007018783A3 (en) * | 2005-08-08 | 2007-04-05 | Arkema Inc | Polymerization of fluoropolymers using non-fluorinated surfactants |
| CN1837456A (en) * | 2006-04-25 | 2006-09-27 | 辽宁氟材料研究院有限公司 | Emulsion type fluorine-containing textile finishing agent and preparation method thereof |
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