CN1174059C - Solvent type organic silicone modified acrylate coating material and its production method - Google Patents
Solvent type organic silicone modified acrylate coating material and its production method Download PDFInfo
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- CN1174059C CN1174059C CNB011276835A CN01127683A CN1174059C CN 1174059 C CN1174059 C CN 1174059C CN B011276835 A CNB011276835 A CN B011276835A CN 01127683 A CN01127683 A CN 01127683A CN 1174059 C CN1174059 C CN 1174059C
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- acrylate
- modified acrylate
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Abstract
The present invention relates to solvent type organic silicon modified acrylic ester paint and a production method thereof. The paint can be used for the wall surfaces of high buildings and multi-storey buildings, bridge beams, highway guard fences, road fences, etc. The production method comprises the steps that orthosilicate ester is hydrolyzed and polycondensated into an organic silicon oligomer in an acidic medium, the organic silicon oligomer, an acrylate monomer and an organic silicon monomer containing an unsaturated double bond and is copolymerized into organic silicon modified acrylate resin and filling materials. The organic silicon modified acrylate resin, a pigment, a filling material and the like are prepared into the paint. The paint produced by the method has the advantages of high adhesive force, good water resistance, good stain resistance, good washing resistance, good heat resistance and good ageing resistance.
Description
The present invention relates to a kind of production method of solvent type organic silicone modified acrylate coating material.
Acrylic resin has 30% to be used to prepare coating approximately, although its film have the transparency good, good mechanical property, anti-freezing, weather-proof and difficult jaundice under uviolizing, but the hardness of filming is on the low side, poor heat resistance, easily be clamminess after being heated (high temperature after-tacks), not only easily be stained with dust and moisture etc., but also can reduce its other performance.For this reason, there are many reports to mention the method for using organosilicon-modified acrylic coating in the literature.For example JP89-60618 field octamethylcyclotetrasiloxane and methyl ethylene cyclosiloxane are made the silicon intermediate, produce the organosilicon-modified acrylate resin with the method for acrylate monomer copolymerization again.JP95-196975 makes organosilicon-modified acrylate resin with the acrylate monomer copolymerization with 3-methacrylic acid group Trimethoxy silane in solvent.Above-mentioned organic-silicon-modified acrylate resin, common characteristic is to have introduced organosilicon functional group on its macromolecular main chain and the side chain, the bond energy that utilizes the Si-O covalent linkage is than the high 25Kcal/mol of C-C bond energy, improves acrylic resin greatly to heat, to the stability of light.By its coatings formulated, characteristics such as filming has the sticking power height, and contamination resistance is water-fast, and is heat-resisting and ageing-resistant.But silicon intermediate manufacturing technique requirent is tight, and gelatin phenomenon easily takes place the organosilicon-modified acrylate resin package stability instability that the silicon monomer that direct use contains unsaturated double-bond synthesizes.
The present invention is directed to above-mentioned two types and produce the weak points that the organosilicon-modified acrylate resin exists, adopt organosilicon oligopolymer and the silicon monomer bonded method that contains unsaturated double-bond to produce organosilicon-modified acrylate resin in the coating.Purpose provides a kind of high adhesive force that has, and hard films, water tolerance, contamination resistance, abrasion resistance, the production method of the solvent based coating that thermotolerance and ageing-resistant performance are good.
For achieving the above object, the production method of solvent type organic silicone modified acrylate coating material provided by the invention is characterized in that may further comprise the steps:
(a) positive silicon ester being dissolved in the alcohol, is under the 50-100 ℃ of condition hydrolysis 1-3 hour with diluted acid in temperature again; In temperature is 120-170 ℃, under the vacuum condition polycondensation 2-4 hour, makes the organosilicon oligopolymer;
(b) with organosilicon oligopolymer 5 gram, after acrylate monomer 88 grams dissolve with organosilane monomer 7 grams that contain unsaturated double-bond and initiator, be added to temperature and be in 120-150 ℃ the solvent, polyase 13-6 hour makes the organosilicon-modified acrylate resin;
(c) this resin, color stuffing, dispersion agent, flow agent, defoamer, UV light absorber and solvent are made into coating with ordinary method.
Above-mentioned production method, the positive silicon ester of its use can be methyl silicate, tetraethoxy or positive silicic acid propyl ester; Used alcohol can be methyl alcohol, ethanol or n-propyl alcohol; Used diluted acid is a dilute hydrochloric acid; Used acrylate monomer can be the one or more combination of methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate or butyl acrylate; The used organosilane monomer that contains unsaturated double-bond can be vinyltrimethoxy silane, vinyltriethoxysilane or 3-methacryloxy Trimethoxy silane; Used initiator can be benzoyl peroxide or azo isobutyronitrile.
The present invention will be by organosilicon oligopolymer, acrylate monomer and is contained organosilicon-modified acrylate resin that the silicon monomer copolymerization of unsaturated double-bond forms and color stuffing etc. and be mixed with coating, this coating has high sticking power, outstanding contamination resistance, abrasion resistance, water tolerance, thermotolerance and ageing resistance.
The present invention is further illustrated below in conjunction with embodiment:
(1) preparation organosilicon oligopolymer
Having reflux exchanger, in the there-necked flask of thermometer and stirring, adding after tetraethoxy 104 grams and ethanol 35 grams mix, adding 0.05% hydrochloric acid, 7.5 grams again, be warmed up to 50～100 ℃ and be hydrolyzed and reacted 1-3 hour.Temperature is raised to 120-170 ℃ subsequently, under vacuum, takes ethanol away, condensation reaction 2-4 hour, obtain the organosilicon oligopolymer.
(2) preparation organosilicon-modified acrylic ketone resin
Having Dropping feeder, stir, in the four-hole boiling flask of reflux exchanger and thermometer, add dimethylbenzene and N-BUTYL ACETATE mixed solvent (3: 1 proportionings) 100 grams, be warmed up to 120-150 ℃, drip mixed solution down: methyl methacrylate 75 grams, butyl acrylate 13 grams, 3-methacryloxy Trimethoxy silane 7 grams, organosilicon oligopolymer 5 grams and benzoyl peroxide 0.7 gram.After the polyreaction 5 hours. be cooled to 50 ℃ with bottom discharge.
(3) preparation Silicone Modified Acrylate Resin Coating
With organosilicon-modified acrylate resin (solids content is 50%) 50 grams, titanium dioxide 20 grams, dimethylbenzene 21 grams, N-BUTYL ACETATE 7 grams, dispersion agent 0.5 gram, defoamer 0.5 gram, UV light absorber 1 gram, after blending dispersion was even, being ground to fineness at sand mill was 45≤μ m, obtains whitewash.
Claims (7)
1. the production method of a solvent type organic silicone modified acrylate coating material is characterized in that production method may further comprise the steps:
(a) positive silicon ester being dissolved in the alcohol, is under the 50-100 ℃ of condition hydrolysis 1-3 hour with diluted acid in temperature again; In temperature is 120-170 ℃, under the vacuum condition polycondensation 2-4 hour, makes the organosilicon oligopolymer;
(b) with organosilicon oligopolymer 5 gram, after acrylate monomer 88 grams dissolve with organosilane monomer 7 grams that contain unsaturated double-bond and initiator, be added to temperature and be in 120-150 ℃ the solvent, polyase 13-6 hour makes the organosilicon-modified acrylate resin;
(c) this resin, color stuffing, dispersion agent, flow agent, defoamer, UV light absorber and solvent are made into coating.
2. production method according to claim 1 is characterized in that used positive silicon ester is methyl silicate, tetraethoxy or positive silicic acid propyl ester.
3. production method according to claim 1 is characterized in that used alcohol is methyl alcohol, ethanol or n-propyl alcohol.
4. production method according to claim 1 is characterized in that used diluted acid is a dilute hydrochloric acid.
5. production method according to claim 1 is characterized in that used acrylate monomer is the one or more combination of methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate or butyl acrylate.
6. production method according to claim 1 is characterized in that the used organosilane monomer that contains unsaturated double-bond is vinyltrimethoxy silane, vinyltriethoxysilane or 3-methacryloxy Trimethoxy silane.
7. production method according to claim 1 is characterized in that used initiator is benzoyl peroxide or azo isobutyronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011276835A CN1174059C (en) | 2001-08-01 | 2001-08-01 | Solvent type organic silicone modified acrylate coating material and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011276835A CN1174059C (en) | 2001-08-01 | 2001-08-01 | Solvent type organic silicone modified acrylate coating material and its production method |
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| Publication Number | Publication Date |
|---|---|
| CN1400265A CN1400265A (en) | 2003-03-05 |
| CN1174059C true CN1174059C (en) | 2004-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011276835A Expired - Fee Related CN1174059C (en) | 2001-08-01 | 2001-08-01 | Solvent type organic silicone modified acrylate coating material and its production method |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746467B (en) * | 2008-04-22 | 2015-01-14 | 东亚合成株式会社 | Curable composition and process for production of organosilicon compound |
| EP2828345B1 (en) | 2012-03-22 | 2016-10-05 | 3M Innovative Properties Company | Polymethylmethacrylate based hardcoat composition and coated article |
| CN103059313B (en) * | 2012-12-17 | 2014-12-10 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| US10689468B2 (en) * | 2014-12-02 | 2020-06-23 | Basf Coatings Gmbh | Copolymer and pigmented coating agent containing the copolymer |
| CN105237693B (en) * | 2015-11-05 | 2018-05-11 | 浩力森涂料（上海）有限公司 | Hybrid inorganic-organic silicon dioxide modified acrylic resin and its coating |
| CN106280626A (en) * | 2016-08-12 | 2017-01-04 | 太仓市美航涂料有限公司 | A kind of environment-friendly type high adhesion force waterborne glass coatings |
| CN110093130A (en) * | 2018-01-31 | 2019-08-06 | 上海宝银电子材料有限公司 | A kind of electromagnetic shielding conductive silver glue and preparation method thereof |
| CN109593420A (en) * | 2018-11-19 | 2019-04-09 | 深圳市烯世传奇科技有限公司 | Organosilicon modified crylic acid resin antifouling paint and preparation method thereof |
| CN109505198B (en) * | 2018-12-20 | 2022-04-01 | 广东玉兰集团股份有限公司 | Transparent slurry, wallpaper and preparation method thereof |
| CN109868026B (en) * | 2019-02-20 | 2020-06-16 | 中南大学 | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating |
| CN110332238B (en) * | 2019-07-11 | 2021-01-05 | 山高智能装备(山东)有限公司 | Electric-insulation high-temperature-resistant hybrid ball bearing and preparation method thereof |
| CN110396341A (en) * | 2019-08-29 | 2019-11-01 | 华南理工大学 | A kind of super-hydrophobic dirt resistance coatings and preparation method thereof based on 3D microballoon |
| CN113480907A (en) * | 2021-07-01 | 2021-10-08 | 江西东维电气有限公司 | Preparation method of spherical stain-resistant pin insulator |
| CN117363208A (en) * | 2023-10-24 | 2024-01-09 | 广东中城海创新材料有限公司 | Inorganic contamination-resistant heat-insulating coating and preparation method thereof |
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