CN103554350B - The preparation method of organosilicon modified crylic acid resin - Google Patents
The preparation method of organosilicon modified crylic acid resin Download PDFInfo
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- CN103554350B CN103554350B CN201310567609.2A CN201310567609A CN103554350B CN 103554350 B CN103554350 B CN 103554350B CN 201310567609 A CN201310567609 A CN 201310567609A CN 103554350 B CN103554350 B CN 103554350B
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Abstract
A preparation method for organosilicon modified crylic acid resin, is characterized in that in turn including the following steps: 1. raw material premix, introduces organosilane monomer in raw material; 2. organic cosolvent is heated; 3. polyreaction being incubated; 4. initiator is added; 5. neutralize; 6. precipitation, sloughs unnecessary organic cosolvent; 7. deionized water is added.Compared with prior art, the invention has the advantages that: gained resin has good water-soluble, the electrophoretic paint configured, there is the characteristic of good cathode electrophoresis dope, particularly, be significantly improved in hardness, scoring resistance, wear resistance etc.
Description
Technical field
The present invention relates to a kind of preparation method of acrylic resin, particularly relate to a kind of preparation method introducing organic-silicon-modified acrylic resin, the acrylic resin of gained is in cathode electrophoresis dope film forming.
Background technology
Along with the continuous enhancing of people's ecological awareness, the Application and Development of environment-friendly materials more and more comes into one's own, water soluble electrocoating as environmental type is subject to people and pays close attention to widely, and being that the water soluble electrocoating of matrix is resin dedicated with water-borne acrylic resin becomes one of study hotspot.Along with the continuous expansion of cathode electrophoresis dope range of application, various household electrical appliances, hardware and office appliance etc. also use electrophoretic painting to the exigent ornamental articles for use of outward appearance, be most widely used in hardware products metal finishing especially, five metals material oiliness on alternative market is sprayed paint, water washing spray lacquer craftwork, the electroplating surface coating process of Electroplate Factory, as: window decorations goods, door and window accessory, plated item closes protection, bathroom product, lockset, clothing item, the external coating of finishing material etc., not only can obtain the application outward appearance of the various color and lusters with metal sense, solidity to corrosion and bonding force improve, and evaded the environmental stress adopting application of spraying paint to produce, simplify complete processing, its application prospect is very wide.
Unsaturated organosilicon monomer is incorporated in cation water-based acrylic resin, effectively can improves the hardness of fluoropolymer resin film, scoring resistance and self-cleaning property, and the transparency of film can be kept.Current organosilicon is main mode of adding based on physics in the polymer, and organosilyl natural high-quality characteristic is difficult to be embodied, and easily causes the film forming properties of polymkeric substance to decline.As electrophoretic paint, the organosilicon that physics adds, due to the difference of electrophoretic force, in electrophoretic painting process, cannot realize deposition painting synchronous with film-forming resin, implements to produce adverse influence to electrophoresis coating technique." coatings industry " the 9th phase in 2011, Xing Ping Liang to report with hydroxyethyl methylacrylate (HEMA), Dimethylaminoethyl Methacrylate (DMAEMA) etc. as raw material, has prepared acrylic cathodic electrophoretic coating resin; " basis and forward position research " the 20th phase in 2010, Hu Yingmo etc. report with methyl acrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) as main raw material has synthesized Key wordscationic polyacrylate tetrapolymer; " technical research " the 22nd volume the 12nd phase in 2007, Wang Xianghui reports with butyl glycol ether, propylene glycol monomethyl ether as solubility promoter, with dimethylaminoethyl acrylate methyl ammonia ethyl ester, Hydroxyethyl acrylate, methyl methacrylate for raw material, synthesize electrophoretic paint acrylic cationic resin, and inquire into the application in electrophoretic paint.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with the organosilicon modified crylic acid resin of good cathode electrophoresis dope characteristic for the above-mentioned state of the art.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of organosilicon modified crylic acid resin, it is characterized in that in turn including the following steps:
1. raw material premix, is uniformly mixed each reaction monomers and initiator and dissolves completely, reaction monomers and weight proportion as follows:
Initiator addition is 0.8% ~ 1.4% of reaction monomers gross weight, and 1.2 is best;
2. heat organic cosolvent, organic cosolvent is warming up to 90 DEG C ~ 100 DEG C;
3. polyreaction, is added drop-wise in organic cosolvent by the raw material after premix, carries out polyreaction, and is incubated, and the addition of organic cosolvent is 20% ~ 40% of reaction monomers, 30% is best;
4. add initiator, the addition adding initiator is 0.08% ~ 1.4% of reaction monomers gross weight, and the best is 1.2%;
5. neutralize, add organic acid, neutralize;
6. precipitation, sloughs unnecessary organic cosolvent;
7. add deionized water, addition is 15% ~ 25% of reaction monomers gross weight, and the best is 20%.
As the best: reaction monomers and weight proportion as follows:
As preferably, described alkyl acrylate is the mixture of methyl methacrylate and butyl acrylate, and the weight ratio between methyl methacrylate and butyl acrylate is 1:1.5 ~ 1:3.0, as best 1:2.
As preferably, described acrylate be in dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate one of at least.
As preferably, described unsaturated organosilicon monomer be in vinyltrimethoxy silane and vinyltriethoxysilane one of at least.
As preferably, described initiator is benzoyl peroxide or azo-bis-isobutyl cyanide.
As preferably, described organic cosolvent be in Virahol, propyl carbinol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether one of at least.
As preferably, described organic acid be in acetic acid, propionic acid, butyric acid, lactic acid one of at least.
Further, described acrylate be in dimethylaminoethyl methacrylate (DMAEMA) and diethylaminoethyl methacrylate (DMAM) one of at least, described organic acid addition is the mole number 60% ~ 100% of acrylate, and the best is 80%.
As preferably, described organic acid is lactic acid, and addition is 25% ~ 40% of acrylate weight, and the best is 32%.
As preferably, in described polyreaction, soaking time is 1.8 ~ 2.2 hours.
Further, 75 DEG C are cooled to before adding organic acid.
Compared with prior art, the invention has the advantages that: with olefin(e) acid alkyl ester, hydroxyalkyl acrylates, acrylate, unsaturated organosilicon monomer for main raw material, adopt the mode dripped, by the method for solution polymerization, through technological processs such as premix, polymerization, cooling neutralization, precipitation, water dilutions, gained resin has good water-soluble.The electrophoretic paint configured, has the characteristic of good cathode electrophoresis dope, particularly, is significantly improved in hardness, scoring resistance, wear resistance etc.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1, take methyl methacrylate 40g, butyl acrylate 80g, hydroxyethyl methylacrylate 30g, dimethylaminoethyl methacrylate (DMAEMA) 30g, vinyltrimethoxy silane 12g, Diisopropyl azodicarboxylate 2g, add in the dropping funnel that 500mL tetra-mouthfuls of reaction flasks are equipped with stand-by after mixing.
In 500mL tetra-mouthfuls of reaction flasks that stirring, thermometer, reflux exchanger and dropping funnel are housed, add co-solvent ethylene gylcol monobutyl ether 20, Virahol 40g, 95 DEG C are warming up under the state stirred, start the hybrid reaction monomer dripped in dropping funnel, under maintenance 95 DEG C of states, 3 hours used times, average rate reaction monomers mixture is dropwised.After being added dropwise to complete, the catalyzer (Diisopropyl azodicarboxylate) of 0.2g is added in reaction flask, 2 hours are incubated under whipped state, now complete the polyreaction of resin, be cooled to 75 DEG C, add after 10g acetic acid is uniformly mixed, the reflux exchanger of 500mL tetra-mouthfuls of reaction flask configurations is replaced with the prolong being furnished with receiving bottle and vacuum interface, open vacuum pump, under the state stirred, slowly increasing the vacuum tightness in reaction flask, is solubility promoter in reaction flask deviating from from polymkeric substance gradually, condensation, recovery.When the solubility promoter deviate from reaches the 40g of add-on, remove vacuum, close vacuum pump, add deionized water 40g, obtain transparent, the acrylic resin modified 253g of the special cationic silicones of faint yellow water-soluble cathode electrodip painting of the present invention.
By the resin of the present embodiment and Bayer BAYER-3175 closure isocyanate curing agent in 1:0.3 ratio, the electrocoating paint varnish of solid content 15% is configured to deionized water dilution, test piece is at electrophoretic voltage 50V, after electrophoresis 50s, at 160 DEG C, solidify under 30min condition, gained paint film property test result is as follows:
Embodiment 2, in the reaction unit of embodiment 1, add solubility promoter propyl carbinol 15g, ethylene glycol monomethyl ether 25g, 95 DEG C are warming up under the state stirred, drip by methyl methacrylate 32g by 3 hours average rates, butyl acrylate 48g, hydroxyethyl methylacrylate 20g, diethylaminoethyl methacrylate (DMAM) 20g, vinyltriethoxysilane 6g, the mixture that benzoyl peroxide 1.0g forms, after dropwising, add the catalyzer (benzoyl peroxide) of 0.1g, be incubated and be cooled to 70 DEG C after 2 hours, add lactic acid (molecular weight=90) 8g, to be dissolved and after stirring, the reflux exchanger that reaction flask configures is replaced with the prolong being furnished with receiving bottle and vacuum interface, open vacuum pump, when the solubility promoter deviating from reaction system reaches the 20g of add-on, remove vacuum, close vacuum pump, add deionized water 25g, obtain transparent, the acrylic resin modified 169g of the special cationic silicones of faint yellow water-soluble cathode electrodip painting of the present invention.
By the resin of the present embodiment and Bayer BAYER-3175 closure isocyanate curing agent in 1:0.3 ratio, the electrocoating paint varnish of solid content 15% is configured to deionized water dilution, test piece is at electrophoretic voltage 50V, after electrophoresis 50s, at 160 DEG C, solidify under 30min condition, gained paint film property test result is as follows:
Embodiment 3, in the reaction unit of embodiment 1, add co-solvent ethylene gylcol monobutyl ether 80g, 95 DEG C are warming up under the state stirred, drip by methyl methacrylate 30g by 3 hours average rates, butyl acrylate 90g, Rocryl 410 30g, dimethylaminoethyl methacrylate (DMAM) 30g, vinyltrimethoxy silane 12g, the mixture that azo-bis-isobutyl cyanide 2.7g forms, after dropwising, add catalyzer azo-bis-isobutyl cyanide 0.2g, be incubated and be cooled to 80 DEG C after 2 hours, add propionic acid (molecular weight=74) 15g, after propionic acid stirs, the reflux exchanger that reaction flask configures is replaced with the prolong being furnished with receiving bottle and vacuum interface, open vacuum pump, when the solubility promoter deviating from reaction system reaches the 40g of add-on, remove vacuum, close vacuum pump, add deionized water 50g, obtain transparent, the acrylic resin modified 271g of the special cationic silicones of faint yellow water-soluble cathode electrodip painting of the present invention.
By the resin of the present embodiment and Bayer BAYER-3175 closure isocyanate curing agent in 1:0.3 ratio, the electrocoating paint varnish of solid content 15% is configured to deionized water dilution, test piece is at electrophoretic voltage 50V, after electrophoresis 50s, at 160 DEG C, solidify under 30min condition, gained paint film property test result is as follows:
| Title | Index | Title | Index |
| Outward appearance | Glossy clear | Wear resistance/300 turn loss | 0.0035% |
| Thickness/μm | 21 | Scoring resistance/level | 3 |
| Pencil hardness | 5H | Snappiness/mm | 1 |
| Gloss/60 ° | 96 | Shock resistance/50cm | Pass through |
| Sticking power/level | 0 | Fight against press-ganging ketone is cleaned/200 times | Pass through |
Embodiment 4, in the reaction unit of embodiment 1, add embodiment 2 and embodiment 3 reclaims and the solubility promoter 80g mixed, 95 DEG C are warming up under the state stirred, drip by methyl methacrylate 55g by 3 hours average rates, butyl acrylate 105g, Rocryl 410 20g, dimethylaminoethyl methacrylate (DMAM) 20g, vinyltrimethoxy silane 4g, the mixture that azo-bis-isobutyl cyanide 1.7g forms, after dropwising, add catalyzer azo-bis-isobutyl cyanide 0.2g, be incubated and be cooled to 70 DEG C after 2 hours, add butyric acid (molecular weight=88) 7g, after butyric acid stirs, the reflux exchanger that reaction flask configures is replaced with the prolong being furnished with receiving bottle and vacuum interface, open vacuum pump, when the solubility promoter deviating from reaction system reaches the 50g of add-on, remove vacuum, close vacuum pump, add deionized water 50g, obtain transparent, the acrylic resin modified 282g of the special cationic silicones of faint yellow water-soluble cathode electrodip painting of the present invention.
By the resin of the present embodiment and Bayer BAYER-3175 closure isocyanate curing agent in 1:0.3 ratio, the electrocoating paint varnish of solid content 15% is configured to deionized water dilution, test piece is at electrophoretic voltage 50V, after electrophoresis 50s, at 160 DEG C, solidify under 30min condition, gained paint film property test result is as follows:
Claims (10)
1. a preparation method for organosilicon modified crylic acid resin, is characterized in that in turn including the following steps:
1. raw material premix, is uniformly mixed each reaction monomers and initiator and dissolves completely, reaction monomers and weight proportion as follows:
Initiator addition is 0.8% ~ 1.4% of reaction monomers gross weight;
2. heat organic cosolvent, organic cosolvent is warming up to 90 DEG C ~ 100 DEG C;
3. polyreaction, is added drop-wise in organic cosolvent by the raw material after premix, carries out polyreaction, and is incubated, and the addition of organic cosolvent is 20% ~ 40% of reaction monomers;
4. add initiator, the addition adding initiator is 0.08% ~ 1.4% of reaction monomers gross weight;
5. neutralize, add organic acid, neutralize;
6. precipitation, sloughs unnecessary organic cosolvent;
7. add deionized water, addition is 15% ~ 25% of reaction monomers gross weight.
2. the preparation method of organosilicon modified crylic acid resin according to claim 1, it is characterized in that described alkyl acrylate is the mixture of methyl methacrylate and butyl acrylate, further, the weight ratio between methyl methacrylate and butyl acrylate is 1:1.5 ~ 1:3.0.
3. the preparation method of organosilicon modified crylic acid resin according to claim 1, it is characterized in that described acrylate be in dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate one of at least.
4. the preparation method of organosilicon modified crylic acid resin according to claim 1, it is characterized in that described unsaturated organosilicon monomer be in vinyltrimethoxy silane and vinyltriethoxysilane one of at least.
5. the preparation method of organosilicon modified crylic acid resin according to claim 1, is characterized in that described initiator is benzoyl peroxide or azo-bis-isobutyl cyanide.
6. the preparation method of organosilicon modified crylic acid resin according to claim 1, it is characterized in that described organic cosolvent be in Virahol, propyl carbinol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether one of at least.
7. the preparation method of organosilicon modified crylic acid resin according to claim 1, it is characterized in that described organic acid be in acetic acid, propionic acid, butyric acid, lactic acid one of at least.
8. the preparation method of organosilicon modified crylic acid resin according to claim 7, it is characterized in that described acrylate be in dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate one of at least, described organic acid addition is the mole number 60% ~ 100% of acrylate.
9. the preparation method of organosilicon modified crylic acid resin according to claim 8, it is characterized in that described organic acid is lactic acid, addition is 25% ~ 40% of acrylate weight.
10. the preparation method of organosilicon modified crylic acid resin according to claim 1, is characterized in that in described polyreaction, soaking time is 1.8 ~ 2.2 hours.
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| 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 |
| CN109913059A (en) * | 2019-01-10 | 2019-06-21 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof of high throwing power |
| CN111040069B (en) * | 2019-12-25 | 2022-10-21 | 芜湖春风新材料有限公司 | Preparation method of organic silicon modified matte cathode electrophoresis resin and cathode matte electrophoresis emulsion prepared by same |
| CN112743259B (en) * | 2021-01-25 | 2022-05-17 | 苏州柯仕达电子材料有限公司 | Cleaning-free soldering flux |
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|---|---|---|---|---|
| CN1644635A (en) * | 1996-07-23 | 2005-07-27 | 日本油漆株式会社 | Electrodeposition coating composition having electrodeposition potentiality and process for electrodeposition coating |
| CN1651530A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Fluorinated low surface energy cathode electrophoresis paint and its preparation method |
| CN102206848A (en) * | 2011-01-23 | 2011-10-05 | 浙江大学 | Cathode electrophoresis protective coating modified by silicane and application thereof |
| CN103333596A (en) * | 2013-06-24 | 2013-10-02 | 浩力森涂料（上海）有限公司 | Self-cleaning fluorosilicone-modified acrylic acid cathode electrophoresis paint and preparation method thereof |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644635A (en) * | 1996-07-23 | 2005-07-27 | 日本油漆株式会社 | Electrodeposition coating composition having electrodeposition potentiality and process for electrodeposition coating |
| CN1651530A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Fluorinated low surface energy cathode electrophoresis paint and its preparation method |
| CN102206848A (en) * | 2011-01-23 | 2011-10-05 | 浙江大学 | Cathode electrophoresis protective coating modified by silicane and application thereof |
| CN103333596A (en) * | 2013-06-24 | 2013-10-02 | 浩力森涂料（上海）有限公司 | Self-cleaning fluorosilicone-modified acrylic acid cathode electrophoresis paint and preparation method thereof |
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