CN105542094A - High-thixotropy epoxy-modified acrylic core-shell emulsion, and preparation method and application thereof - Google Patents
High-thixotropy epoxy-modified acrylic core-shell emulsion, and preparation method and application thereof Download PDFInfo
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- CN105542094A CN105542094A CN201610031362.6A CN201610031362A CN105542094A CN 105542094 A CN105542094 A CN 105542094A CN 201610031362 A CN201610031362 A CN 201610031362A CN 105542094 A CN105542094 A CN 105542094A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of anhydrides
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a preparation method for high-thixotropy epoxy-modified acrylic core-shell emulsion. The content of macromonomers M in a core part or a shell part is controlled by introducing the macromonomers M in different polymerizing stages in initial seed emulsion polymerizing or subsequent core-shell emulsion polymerizing stages; the obtained modified emulsion is endowed with thixotropy regulation performance by introducing carboxylic acid-containing monomers when the shell emulsion is polymerized; the content of the carboxylic acid-containing monomers is 2 to 8 percent. According to the preparation method, epoxy resin-type macromonomers are introduced into core-shell structural acrylic resin emulsion to serve as a modifying component, so that the modified emulsion has the advantages of epoxy resin and acrylic resin; meanwhile, the innovative product also has an alkalic thickening characteristic; the disadvantage that the film thickness of the conventional resin emulsion paint film is difficult to increase is overcome.
Description
Technical field
The present invention relates to environmental protection coating material use fluoropolymer resin field, be specifically related to a kind of strong thixotropy epoxy-modified acrylic acid core-shell emulsion and its preparation method and application.
Background technology
Coating plays an important role in all fields of national economy and people's daily life, not only can implement available protecting to material surface, and has brought beautiful visual enjoyment.Film-forming resin, color stuffing, solvent and auxiliary agent are the chief components of coating; carry out in coating decoration process at coating; often along with the volatilization of a large amount of solvent, film-forming resin and color stuffing (comprising auxiliary agent) then can be stayed substrate surface and form tight supercoat.Except interior decoration emulsion paint, traditional industry coating is main mainly with organic solvent type, and its volatile organic compounds (being called for short VOC) quantity discharged is usually up to 500g/L.Along with the increasingly stringent of countries in the world environmental regulation, coatings industry is faced with the application techniques revolution adopting low VOC environment-friendly type coating comprehensively to substitute conventional organic solvents type coating.Such as: American and Britain, De Deng developed country put into effect the discharge of the regulation limitations VOC such as CAA, TA-LUFF, EPA in succession, just require in the clean air regulation that Germany came into force in nineteen ninety-five, when spraying application, VOC quantity discharged must not be greater than 35g/m2.Japan is that the country restricted is discharged in Asia at first to coating VOC, and current limiting emission amount is 60g/m2.Although and China's also pay attention to day by day environmental protection Sustainable development, within 2009, new national standard regulation car paint VOC limiting emission amount is 90g/m2, but actual average quantity discharged is about about 120g/m2 during painting dressing automobiles, with America and Europe Japan etc. developed country's coatings industry environmental requirement greatly differ from each other.
China's Economic development in nearly ten years is swift and violent, and coating demand increases fast, and coating annual production in 2014 1648 ten thousand tons, occupies the first in the world.But coatings industry Ye Shi China VOC discharges rich and influential family, because in industrial paint systems, low VOC environment-friendly type coating portion is less than 15%.In addition, although China is coating material production big country, be not coating technology power.The production technology of the mid-to high-end product of current domestic industry coating production enterprise still dependence on import raw materials for production and Introduced From Abroad, because domestic automobile industrial development is uneven, wherein high-grade car use car paint is almost all by transnational paint company is monopolized, as Aksu, He Baici, PPG, the Northwest and BASF etc.China's aqueous industrial coating product technology develops backwardness relatively, and aqueous industrial coating research starting is also relatively late, until the beginning of the nineties, China just starts the test carrying out exploration.Along with China's Coating Market and international integrate with, allowing of no optimist of Environmental Protection in China situation, China also will formulate stringent legislation, be controlled the discharge of VOC, play China imposes 4% more than the coating of the 450g/L excise to VOC discharge in February, 2015.The environment-friendly water-basedization trend of industrial coating is increasingly urgent, and the preparation of environment-friendly aqueous industrial coating and key raw material (resin, auxiliary agent etc.) thereof and industrial application are the gordian techniquies that our domestic coating technology developer is badly in need of solving.
Research and development aqueous industrial coating and application techniques, have vast potential for future development in the market competition in future.Current China aqueous industrial coating is just at the early-stage, the basic dependence on import of its starting material such as resin and auxiliary agent.Exploitation high-performance environment protection type aqueous industrial coating and key raw material technology of preparing thereof, realize the transformation of solvent-borne type finishing system hydrotropismsization finishing system, accelerate the transition and upgrade of coating industry, contribute to breaking the monopoly position of transnational company to water-borne coatings, promote international competition strength.Meanwhile, this water-base resin and coating products thereof can also be applied to main equipment, engineering, field of electronics etc., and range of product variation, has wide market and huge development potentiality.
Summary of the invention
Technical problem to be solved by this invention, a kind of preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion is proposed exactly, the advantages such as products obtained therefrom has quick-drying, sag prevention, chemicals-resistant, moisture resistance, high gloss, wear resistance is good, surface hardness is good, snappiness is good, sticking power is good.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion, by introducing macromonomer M at the different polymerization stages in initial seed letex polymerization or follow-up core-shell emulsion polymerization stage, thus realize controlling at the content of kernel portion or housing parts macromonomer M, by introducing the thixotroping control of giving gained modified emulsion containing carboxylic acid monomer when shell letex polymerization, be 2-8% containing carboxylic acid monomer's content, specifically comprise the steps:
(1) unsaturated acid monomer and bisphenol A type epoxy resin carry out the macromonomer M that esterification prepares two end band polymerizable double bonds;
(2) get anionic emulsifier sodium lauryl sulphate and/or nonionic emulsifying agent OP-10 is dissolved in 140 parts of deionized waters, being configured to mass concentration is that the emulsifier solution of 0.5-6% is for subsequent use;
(3) be dissolved in by water soluble starter in 20 parts of deionized waters, being configured to mass concentration is that the initiator solution of 0.1-1.5% is for subsequent use;
(4) 30-100 part acrylic ester monomer and 0-10 part macromonomer M are mixed for subsequent use as nuclear layer monomer; The acrylic ester monomer of 20-50 part, 5-10 part are mixed for subsequent use as shell monomers containing carboxylic acid monomer, 6-10 part hydroxyl monomer and 0-10 part macromonomer M;
(5) nuclear layer monomer and all emulsifier solutions and the 6.0 parts of initiator solutions of first getting 1/10 react 20min under 76 DEG C of conditions in four-hole boiling flask, obtained seed emulsion, and period needs mechanical stirring, backflow and logical nitrogen protection;
(6) then drip in four-hole boiling flask with two constant pressure funnels by remaining nuclear layer monomer and 7.0 parts of initiator solutions respectively, time for adding keeps 1h, dropwises rear continuation reaction 1h;
(7) then in reaction system, directly add 130.0 parts of deionized waters, then drip whole shell monomers and remaining initiator solution, drip process lasts 1h, be incubated 1.5h again after dropwising, reaction terminates;
(8) be cooled to 40 DEG C, the aqueous dimethylethanolamine dripping concentration 50% regulates emulsion pH to 7, finally goes out emulsion by 400 order filtered through gauze.
The unsaturated acid monomer used in described step (1) is one or more in methacrylic acid, vinylformic acid or maleic anhydride.
In described step (3), water soluble starter is ammonium persulphate or Potassium Persulphate.
Described in described step (4), acrylic ester monomer is methyl methacrylate or butyl acrylate.
Containing carboxylic acid monomer described in described step (4) is vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, ethyl acrylate, n-octyl, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, glycidyl acrylate, isobornyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, N-Hexyl methacrylate, lauryl methacrylate(LMA), stearyl methacrylate, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, good glycidyl acrylate, isobornyl methacrylate open one or more.
A kind of strong thixotropy epoxy-modified acrylic acid core-shell emulsion prepared by the preparation method of above-mentioned strong thixotropy epoxy-modified acrylic acid core-shell emulsion.
Above-mentioned strong thixotropy epoxy-modified acrylic acid core-shell emulsion is in the application of paint field.
The beneficial effect that the present invention compared with prior art has is: in nucleocapsid structure Emulsion acrylic resin, introduce epoxide resin type macromonomer as modified component, have epoxy resin and acrylic resin advantage concurrently, this innovative product also has alkali thickening characteristic simultaneously, can overcome the shortcoming that conventional resins emulsion paint film is difficult to thickness.
Embodiment
For the understanding the present invention making those skilled in the art more clear and intuitive, below the present invention is further illustrated.
The preparation method of a kind of strong thixotropy epoxy-modified acrylic acid core-shell emulsion of the present embodiment, by introducing macromonomer M at the different polymerization stages in initial seed letex polymerization, follow-up core-shell emulsion polymerization stage, thus realize controlling at the content of kernel portion, housing parts macromonomer M, by introducing the thixotroping control of giving gained modified emulsion containing carboxylic acid monomer when shell letex polymerization, be 2-8% containing carboxylic acid monomer's content, specifically comprise the steps:
(1) methacrylic acid and bisphenol A type epoxy resin carry out the macromonomer M that esterification prepares two end band polymerizable double bonds;
(2) get anionic emulsifier sodium lauryl sulphate and/or nonionic emulsifying agent OP-10 is dissolved in 140g deionized water, being configured to mass concentration is that the emulsifier solution of 0.5-6% is for subsequent use;
(3) be dissolved in 20g deionized water by water soluble starter ammonium persulphate, being configured to mass concentration is that the initiator solution of 0.1-1.5% is for subsequent use;
(4) 40.0g methyl methacrylate, 20.0g butyl acrylate and 0-10g macromonomer M are mixed as nuclear monomer for subsequent use, and take 15.0g methyl methacrylate, 20.0g butyl acrylate, 5.0g methacrylic acid, 6.0g hydrolytic polymaleic anhydride and 0-10g macromonomer M mix that to make shell monomers for subsequent use;
(5) nuclear layer monomer and all emulsifier solutions and the 6.0g initiator solution of first getting 1/10 react 20min under 76 DEG C of conditions in four-hole boiling flask, obtained seed emulsion, and period needs mechanical stirring, backflow and logical nitrogen protection;
(6) then drip in four-hole boiling flask with two constant pressure funnels by remaining nuclear layer monomer and 7.0g initiator solution respectively, time for adding keeps 1h, dropwises rear continuation reaction 1h;
(7) then in reaction system, directly add 130.0g deionized water, then drip whole shell monomers and remaining initiator solution, drip process lasts 1h, be incubated 1.5h again after dropwising, reaction terminates;
(8) be cooled to 40 DEG C, the aqueous dimethylethanolamine dripping concentration 50% regulates emulsion pH to 7, finally goes out emulsion by 400 order filtered through gauze.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the preparation method of one kind strong thixotropy epoxy-modified acrylic acid core-shell emulsion, it is characterized in that, by introducing macromonomer M at the different polymerization stages in initial seed letex polymerization or follow-up core-shell emulsion polymerization stage, thus realize controlling at the content of kernel portion or housing parts macromonomer M, by introducing the thixotroping control of giving gained modified emulsion containing carboxylic acid monomer when shell letex polymerization, be 2-8% containing carboxylic acid monomer's content, specifically comprise the steps:
(1) unsaturated acid monomer and bisphenol A type epoxy resin carry out the macromonomer M that esterification prepares two end band polymerizable double bonds;
(2) get anionic emulsifier sodium lauryl sulphate and/or nonionic emulsifying agent OP-10 is dissolved in 140 parts of deionized waters, being configured to mass concentration is that the emulsifier solution of 0.5-6% is for subsequent use;
(3) be dissolved in by water soluble starter in 20 parts of deionized waters, being configured to mass concentration is that the initiator solution of 0.1-1.5% is for subsequent use;
(4) 30-100 part acrylic ester monomer and 0-10 part macromonomer M are mixed for subsequent use as nuclear layer monomer; The acrylic ester monomer of 20-50 part, 5-10 part are mixed for subsequent use as shell monomers containing carboxylic acid monomer, 6-10 part hydroxyl monomer and 0-10 part macromonomer M;
(5) nuclear layer monomer and all emulsifier solutions and the 6.0 parts of initiator solutions of first getting 1/10 react 20min under 76 DEG C of conditions in four-hole boiling flask, obtained seed emulsion, and period needs mechanical stirring, backflow and logical nitrogen protection;
(6) then drip in four-hole boiling flask with two constant pressure funnels by remaining nuclear layer monomer and 7.0 parts of initiator solutions respectively, time for adding keeps 1h, dropwises rear continuation reaction 1h;
(7) then in reaction system, directly add 130.0 parts of deionized waters, then drip whole shell monomers and remaining initiator solution, drip process lasts 1h, be incubated 1.5h again after dropwising, reaction terminates;
(8) be cooled to 40 DEG C, the aqueous dimethylethanolamine dripping concentration 50% regulates emulsion pH to 7, finally goes out emulsion by 400 order filtered through gauze.
2. the preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to claim 1, is characterized in that, the unsaturated acid monomer used in described step (1) is one or more in methacrylic acid, vinylformic acid or maleic anhydride.
3. the preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to claim 1, is characterized in that, in described step (3), water soluble starter is ammonium persulphate or Potassium Persulphate.
4. the preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to claim 1, it is characterized in that, described in described step (4), acrylic ester monomer is methyl methacrylate or butyl acrylate.
5. the preparation method of strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to claim 1, it is characterized in that, containing carboxylic acid monomer described in described step (4) is vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, ethyl acrylate, n-octyl, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, glycidyl acrylate, isobornyl acrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, N-Hexyl methacrylate, lauryl methacrylate(LMA), stearyl methacrylate, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, good glycidyl acrylate, isobornyl methacrylate open one or more.
6. the strong thixotropy epoxy-modified acrylic acid core-shell emulsion for preparing of the preparation method of the strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to any one of claim 1-5.
7. strong thixotropy epoxy-modified acrylic acid core-shell emulsion according to claim 6 is in the application of paint field.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508759A (en) * | 2009-03-13 | 2009-08-19 | 上海金山隆捷实业有限公司 | Method of preparing epoxy modified acrylic resin emulsion |
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- 2016-01-18 CN CN201610031362.6A patent/CN105542094A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508759A (en) * | 2009-03-13 | 2009-08-19 | 上海金山隆捷实业有限公司 | Method of preparing epoxy modified acrylic resin emulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511388A (en) * | 2019-08-23 | 2019-11-29 | 湖北双键精细化工有限公司 | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing |
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