CN1061364C - Silicon propyl resin for paint and its producing method - Google Patents
Silicon propyl resin for paint and its producing method Download PDFInfo
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- CN1061364C CN1061364C CN97106656A CN97106656A CN1061364C CN 1061364 C CN1061364 C CN 1061364C CN 97106656 A CN97106656 A CN 97106656A CN 97106656 A CN97106656 A CN 97106656A CN 1061364 C CN1061364 C CN 1061364C
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- organosilicon
- acrylic resin
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- cyclotetrasiloxanes
- acrylate monomer
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Abstract
The present invention relates to silicon propyl resin for paint and a production method thereof. The silicon propyl resin is prepared by the copolymerization of a linear organosilicon intermediate substance and an acrylate monomer, wherein the linear organosilicon intermediate substance is produced by the catalytic polymerization of octavinyl cyclo tetrasiloxane and octa-alkylcyclo tetrasiloxane. The product of the silicon propyl resin has the advantages of regular structure, high transparence and high stability. The silicon propyl resin has the advantages of simple production technology, energy saving and low cost. Paint prepared by the silicon propyl resin can be formed into films at normal temperature or low temperature, and the paint has good performance of oil stain resistance, aging resistance, ultraviolet radiation resistance, hard coated film and good adhesive force.
Description
The present invention relates to a kind of organosilicon acrylic resin and production method thereof.
Organosilicon acrylic resin coating is a kind of coating with weathering resistance and anti-stain characteristic, is widely used in high level, multi-storey building metope, bridge, and highway ground etc. are as protective layer and decoration.
Organosilicon acrylic resin is by line style organosilicon intermediate and acrylate monomer copolymerization and make, owing to introduced organosilicon functional group in the acrylic resin, utilize organosilicon Si-O key that bigger ionic dissociation energy is arranged, improved heat, light stability, thereby improved the weathering resistance of organosilicon acrylic resin, thermotolerance, hydrophobic nature and anti-stain characteristic.
The organosilicon intermediate is one of raw material of synthetic organosilicon acrylic resin, and bibliographical information has two types basically.A kind of is the organosilicon intermediate that contains methoxy or ethoxy, mainly be to be raw material with phenyltrimethoxysila,e and phenyl methyl dimethoxy silane, through partial hydrolysis and or be raw material with the Ethoxysilane, in the presence of acid, get (war Feng Chang through partial hydrolysis, " tailor-(made) coating ", P.114, Chemical Industry Press); Another kind is the organosilicon intermediate of hydroxyl, is to make (Liu Changyin, Shanghai coating, No.1, i.e. .28-34,1992) by the phenyl-trichloro-silicane hydrolysis.By containing methoxy or ethoxy organosilicon intermediate is the organosilicon acrylic resin that raw material is made, water tolerance is relatively poor, and the organosilicon intermediate of hydroxyl then has in reaction from the condensation tendency, has reduced the polymerization chance with acrylic resin, make organosilicon acrylic resin structure irregularity, resin is muddy shape.Therefore be that the performance of the organosilicon acrylic resin that makes of raw material all can not be satisfactory by above two types organosilicon intermediate.
As everyone knows, the performance of organosilicon acrylic resin coating depends primarily on the performance of organosilicon acrylic resin, and therefore synthetic new organosilicon acrylic resin makes it to have more excellent performance, also just can make the organosilicon acrylic resin coating of preparation have more excellent ageing resistance and anti-stain characteristic, be a research work highly significant.
For this reason, the object of the invention provides a kind of silicon propyl resin for paint and production method thereof.Organosilicon acrylic resin is by forming through line style organosilicon intermediate and the acrylate monomer copolymerization that catalytic polymerization generates with eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes.The organosilicon acrylic resin product structure is regular, transparency height, good stability.Organosilicon acrylic resin coating with this organosilicon acrylic resin preparation has excellent ageing resistance and anti-stain characteristic.
Silicon propyl resin for paint of the present invention is the product that is formed by line style organosilicon intermediate and acrylate monomer copolymerization, described line style organosilicon intermediate is to be generated through catalytic polymerization by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes, and its structural formula can be represented by the formula:
R=C in the formula
1-C
4Alkyl, n=5-10.
The production method of silicon propyl resin for paint of the present invention comprises:
The first step is earlier carried out polyreaction with eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes and is got above-mentioned line style organosilicon intermediate under alkali metal hydroxide catalysis.The catalyzer alkali metal hydroxide can be a sodium hydroxide, one or more in potassium hydroxide or the ammonium hydroxide etc., and consumption is 0.5-2% (weight %).The part by weight of eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes is 1-4: 1, and temperature of reaction 70-150 ℃, reaction times 5-8 hour.
Gained organosilicon intermediate product water white transparency, purity 100%, viscosity (being coated with-4 glasss) is 180～200 seconds, molecular weight Mn is 700～1000 (VPO)
Second step then carried out copolyreaction with above-mentioned line style organosilicon intermediate and acrylate monomer and promptly gets organosilicon acrylic resin.The weight percent of reactant each component is as follows in this copolyreaction:
Reactant each component weight %
Organosilicon intermediate 0.8-1.2
Acrylate monomer 38-48
Vinylformic acid 0.3-0.5
Dimethylbenzene and N-BUTYL ACETATE mixed solvent (7: 3 proportionings) 50-60
Benzoyl peroxide 0.3-0.8
Acrylate monomer can be a methyl methacrylate, methyl acrylate, ethyl propenoate, one or more in propyl acrylate or the butyl acrylate etc.
Polymeric reaction temperature 120-130 ℃, 5 hours reaction times.
The production method of organosilicon acrylic resin of the present invention is not because the first step and the second step reaction all have by product produces, must aftertreatment, so processing method is simple and convenient, and energy conservation, cost is low.Product organosilicon acrylic resin compound with regular structure, outward appearance is as clear as crystal, does not have mechanical impurity, has good film forming properties under normal temperature or low temperature, and storage stability is good, and viscosity is 2000-4000CPS (rotary viscosity method), and molecular weight Mn is 2.5 * 10
4-3.0 * 10
4
Adopt organosilicon acrylic resin of the present invention, can be mixed with coating routinely, bottom closing paint, mill base etc.For example adopt organosilicon acrylic resin of the present invention, add color stuffing by following proportioning, methodology such as dispersion agent, flow agent, matting agent, ultraviolet absorbers, defoamer and solvent etc. routinely mix, and grind through high speed dispersion and can make versicolor organosilicon acrylic resin coating.Coating stirs in container, no caking phenomenon.
Organosilicon acrylic resin coating is formed by following prescription:
Constituent weight %
Organosilicon acrylic resin 40-50
Color stuffing 20-25
Dispersion agent 0.5-1
Flow agent 0.5-1
Matting agent 5-10
Defoamer 0.5-1
Ultraviolet absorbers 0.5-1
Solvent 15-30
Each constituent is the present invention except silicon third resin in the above-mentioned prescription, and all the other all are the commercial goods, and the color of pigment can need be selected from the commercial goods by the coating color matching, and solvent can be dimethylbenzene or N-BUTYL ACETATE.
The performance of listing the coating (B) that coating (A) that organosilicon acrylic resin of the present invention is made into and commercially available organosilicon acrylic resin be made into below is relatively:
| Performance project | Coating (A) | Coating (B) |
| Anti-stain characteristic (5 circulations) | ＜7％ | 10-15％ |
| Ageing resistance (non-foaming, as not peel off flawless) | 3500 hours | 1000 hours |
| Ultraviolet radiation resisting | 2000 hours | 500 hours |
| Wear resistance (510N, 1000 times) | 0.031 gram | 0.05 gram |
| Permeability resistance (upstream face) MPa | ＞1.5 | 1.4 |
Show that by above-listed coating (A) and performance project contrasting data (B) coating that organosilicon acrylic resin of the present invention is made into has excellent anti-stain characteristic, ageing resistance, ultraviolet radiation resisting, wear resistance and permeability resistance.
Advantage of the present invention: because organosilicon acrylic resin of the present invention is to form by line style organosilicon intermediate and the acrylate monomer copolymerization that is generated by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxane polyreactions, therefore the organosilicon acrylic resin product structure is regular, appearance transparence is good, and storage stability is good.With this organosilicon acrylic resin coatings formulated can be under normal temperature or cold condition film forming, have excellent anti-stain characteristic, ageing resistance, ultraviolet radiation resisting and wear resistance, it is hard to film, sticking power is good.The production method of organosilicon acrylic resin of the present invention is not because the first step and the second step reaction all have by product produces, must aftertreatment, so processing method is easy, and energy conservation, cost is low.
The present invention is further elaborated by following examples, but does not place restrictions on scope of the present invention.
Embodiment 1, the preparation of organosilicon intermediate
With 49.5 parts of eight vinyl cyclotetrasiloxanes, 49.5 parts of octamethylcyclotetrasiloxanes, add in the reactor, under agitation condition, add potassium hydroxide, each 0.5 part in ammonium hydroxide in 70-80 ℃ of reaction 8 hours, promptly gets the organosilicon intermediate, viscosity 180 seconds (being coated with-4 glasss), molecular weight Mn724.
Embodiment 2, the preparation of organosilicon intermediate
With 74 parts of eight vinyl cyclotetrasiloxanes, 24 parts of eight butyl cyclotetrasiloxanes, add in the reactor, under agitation condition, add sodium hydroxide, each 1 part in ammonium hydroxide in 140-150 ℃ of reaction 5 hours, promptly gets the organosilicon intermediate, viscosity 200 seconds (being coated with-4 glasss), molecular weight Mn980.
Embodiment 3, the organosilicon acrylic resin preparation
0.8 part of organosilicon intermediate is added in the reactor, add 60 parts of dimethylbenzene and ester acid butyl ester mixed solvents (7: 3 proportionings), be warmed up to 120-130 ℃, drip following mixed solution: 28 parts of methyl methacrylates, 10 parts of butyl acrylates, 0.5 part in vinylformic acid reaches 0.7 part of benzoyl peroxide, react after 5 hours, be cooled to 50 ℃ with bottom discharge, filter, get organosilicon acrylic resin, viscosity is 2000CPS (rotary viscosity method), and molecular weight Mn is 2.5 * 10
4, contain 40% solids content, package spare.
Embodiment 4, the organosilicon acrylic resin preparation
1.2 parts of organosilicon intermediates are added in the reactor, add 50 parts of dimethylbenzene and ester acid butyl ester mixed solvents (7: 3 proportionings), be warmed up to 120-130 ℃, drip following mixed solution: 32 parts of methyl methacrylates, 16 parts of ethyl propenoates, 0.3 part in vinylformic acid reaches 0.5 part of benzoyl peroxide, react after 5 hours, be cooled to 50 ℃ with bottom discharge, filter, get organosilicon acrylic resin, viscosity is 4000CPS (rotary viscosity method), and molecular weight Mn is 3.0 * 10
4, contain 50% solids content, package spare.
Embodiment 5, the preparation of organosilicon acrylic resin coating
With 40 parts of organosilicon acrylic resins (solids content 50%), 25 parts of titanium dioxides, 0.5 part of dispersion agent, 5 parts of matting agents, 0.5 part of ultraviolet absorbers, 0.5 part of defoamer, 0.5 part of flow agent, 28 parts of dimethylbenzene, mix, high speed dispersion 15-20 minute, enter sand mill and grind, fineness≤45 μ m is the finished product whitewash.
Embodiment 6, the preparation of organosilicon acrylic resin coating
With 50 parts of organosilicon acrylic resins (solids content 40%), 10 parts of titanium dioxides, 10 parts of phthalocyanine blues, 1 part of dispersion agent, 10 parts of matting agents, 1 part of ultraviolet absorbers, 1 part of defoamer, 1 part of flow agent, 16 parts of acetic acid fourth vinegar mix, high speed dispersion 15-20 minute, enter sand mill and grind, fineness≤45 μ m is the blue look coating of finished product.
Claims (6)
1, a kind of silicon propyl resin for paint, it is the product that is formed by line style organosilicon intermediate and acrylate monomer copolymerization, it is characterized in that described line style organosilicon intermediate is to be got through catalytic polymerization by eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes, its structural formula can be represented by the formula:
The part by weight of eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes is 1-4: 1, the organosilicon intermediate accounts for 0.8-1.2 weight % in the copolyreaction of organosilicon intermediate and acrylate monomer, acrylate monomer accounts for 38-48 weight %, the molecular weight Mn of organosilicon intermediate is 700-1000, and the molecular weight Mn of organosilicon acrylic resin is 2.5 * 10
4-3.0 * 10
4
2, the production method of the described silicon propyl resin for paint of claim 1 is characterized in that it comprises:
Polyreaction under alkali metal hydroxide catalysis makes line style organosilicon intermediate to the first step with eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes earlier, the part by weight of eight vinyl cyclotetrasiloxanes and eight alkyl cyclotetrasiloxanes is 1-4 in the reaction: 1, catalyzer alkali metal hydroxide consumption is 0.5-2% (weight %), temperature of reaction 70-150 ℃, reaction times 5-8 hour, the molecular weight Mn of gained organosilicon intermediate was 700-1000;
Second step then carried out copolyreaction with above-mentioned line style organosilicon intermediate and acrylate monomer and promptly gets organosilicon acrylic resin, and the weight percent of reactant each component is as follows in this copolyreaction:
Reactant each component weight %
Organosilicon intermediate 0.8-1.2
Acrylate monomer 38-48
Vinylformic acid 0.3-0.5
Dimethylbenzene and N-BUTYL ACETATE mixed solvent (7: 3 proportionings) 50-60
Benzoyl peroxide 0.3-0.8
Polymeric reaction temperature 120-130 ℃, in 5 hours reaction times, the molecular weight Mn of gained organosilicon acrylic resin is 2.5 * 10
4-3.0 * 10
4
3, production method according to claim 2 is characterized in that catalyzer alkali metal hydroxide described in the first step reaction is one or more in sodium hydroxide, potassium hydroxide, the ammonium hydroxide.
4, production method according to claim 2 is characterized in that acrylate monomer described in the reaction of second step is one or more in methyl methacrylate, methyl acrylate, ethyl propenoate, propyl acrylate or the butyl acrylate.
5, the purposes of the described organosilicon acrylic resin of claim 1 is characterized in that it can be applicable to become organosilicon acrylic resin coating by following constituent formulated:
Constituent weight %
Organosilicon acrylic resin 40-50
Color stuffing 20-25
Dispersion agent 0.5-1
Flow agent 0.5-1
Matting agent 5-10
Defoamer 0.5-1
Ultraviolet absorbers 0.5-1
Solvent 15-30
6,, it is characterized in that solvent used in the organosilicon acrylic resin formulation for coating material is dimethylbenzene or N-BUTYL ACETATE according to the purposes of the described organosilicon acrylic resin of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106656A CN1061364C (en) | 1997-10-15 | 1997-10-15 | Silicon propyl resin for paint and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106656A CN1061364C (en) | 1997-10-15 | 1997-10-15 | Silicon propyl resin for paint and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178819A CN1178819A (en) | 1998-04-15 |
| CN1061364C true CN1061364C (en) | 2001-01-31 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106656A Expired - Fee Related CN1061364C (en) | 1997-10-15 | 1997-10-15 | Silicon propyl resin for paint and its producing method |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297581C (en) * | 2004-10-15 | 2007-01-31 | 上海市建筑科学研究院有限公司 | Self-emulsified aqueous epoxy emulsion and method for preparing same |
| CN100348637C (en) * | 2004-10-22 | 2007-11-14 | 同济大学 | High-gloss and high temperature resistant silicon-acrylic polyurethane paint and method for preparing same |
| DE102006037270A1 (en) | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Self-dispersible silicone copolymers and process for their preparation and their use |
| SI2006037T1 (en) * | 2007-06-22 | 2010-12-31 | Thyssenkrupp Steel Europe Ag | Flat product made of a metallic substance, in particular a steel substance, use of such a flat product and roller and method for manufacturing such a flat product |
| CN101880485B (en) * | 2010-07-09 | 2012-02-29 | 重庆航利实业有限责任公司 | Rare-earth sol modified composite zinc-aluminum low-temperature sintered coating slurry |
| CN102585108A (en) * | 2012-01-17 | 2012-07-18 | 杭州日耀科技有限公司 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
| CN102627900A (en) * | 2012-03-20 | 2012-08-08 | 江苏同辉照明科技有限公司 | Preparation method of anti-ultraviolet paint |
| CN106977666A (en) * | 2017-04-27 | 2017-07-25 | 重庆三峡油漆股份有限公司 | Coating NC Nitroncellulose substitute and preparation method thereof |
| KR20230044449A (en) * | 2020-07-29 | 2023-04-04 | 다우 글로벌 테크놀로지스 엘엘씨 | Cross-linked polymer of ethylene and monocyclic organosiloxane and method for producing the same |
| CN113527977B (en) * | 2021-06-16 | 2022-10-11 | 广州大学 | Silicone-acrylic resin coating and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61236786A (en) * | 1985-04-11 | 1986-10-22 | Shin Etsu Chem Co Ltd | Cyclic siloxane and production thereof |
| CN85101534A (en) * | 1984-06-22 | 1987-01-17 | N·V·菲利浦斯光灯制造厂 | The method of curable synthetic resin composition and manufacturing multipolymer |
| JPH04261454A (en) * | 1991-02-15 | 1992-09-17 | Japan Synthetic Rubber Co Ltd | Polyorganosiloxane-based emulsion |
-
1997
- 1997-10-15 CN CN97106656A patent/CN1061364C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101534A (en) * | 1984-06-22 | 1987-01-17 | N·V·菲利浦斯光灯制造厂 | The method of curable synthetic resin composition and manufacturing multipolymer |
| JPS61236786A (en) * | 1985-04-11 | 1986-10-22 | Shin Etsu Chem Co Ltd | Cyclic siloxane and production thereof |
| JPH04261454A (en) * | 1991-02-15 | 1992-09-17 | Japan Synthetic Rubber Co Ltd | Polyorganosiloxane-based emulsion |
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| Publication number | Publication date |
|---|---|
| CN1178819A (en) | 1998-04-15 |
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