CN100343311C - Vinyl trimethoxysilane oligomer preparation method - Google Patents
Vinyl trimethoxysilane oligomer preparation method Download PDFInfo
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- CN100343311C CN100343311C CNB2005100405390A CN200510040539A CN100343311C CN 100343311 C CN100343311 C CN 100343311C CN B2005100405390 A CNB2005100405390 A CN B2005100405390A CN 200510040539 A CN200510040539 A CN 200510040539A CN 100343311 C CN100343311 C CN 100343311C
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Abstract
The present invention relates to a method for preparing vinyl trimethoxysilane oligomer. The method comprises the following steps: 1) vinyl trimethoxysilane is put into a reactor, acid is added so as to adjust the pH value to be 4 to 7; 2) metallic catalyst is added and mixed for uniform dispersion, and the dosage of the metallic catalyst is from 10 to 1000 ppm according to pure metal; 3) water is dropped for polycondensation reaction for 6 to 12 hours at a temperature of 60 to 160 DEG C, and the total weight of the water in a reaction system is 0.05 to 0.15 times of that of vinyl trimethoxysilane; 4) methanol which is a by-product generated in hydrolysis polycondensation is removed via distilling; 5) alkali is added for neutralizing residual acid, and vinyl trimethoxysilane oligomer is prepared after suction filtration. The present invention has the advantages of simple process and easy operation. The vinyl trimethoxysilane oligomer prepared by the method of the present invention has a high boiling point and a high flash point, so the vinyl trimethoxysilane oligomer has good safety and good operability in application. Alcohol released from the vinyl trimethoxysilane oligomer in use process is much less than that of single strand section vinyl trimethoxysilane, so the vinyl trimethoxysilane oligomer prepared by the method has environmental protection performance.
Description
Technical field
The present invention relates to a kind of preparation method of vinyl trimethoxysilane oligomer.
Background technology
Vinyltrimethoxy silane, U.S.'s union carbide corporation trade mark is A-171, is a kind of silane coupling agent with extensive use.Be mainly used in polyvinyl crosslinking agents, the glass surface treatment of glass filament reinforced plastics, synthetic speciality coating, the surface of electronic devices and components is moistureproof handles the surface treatment of inorganic siliceous filler etc.But because vinyltrimethoxy silane is the material of strand joint, boiling point (about 110 ℃) and flash-point (about 22 ℃) are all lower, so are being used for polyvinyl crosslinking agents, have potential safety hazard during the glass surface treatment of glass filament reinforced plastics.
Summary of the invention
The present invention will solve is exactly the boiling point of vinyltrimethoxy silane and flash-point is lower, have the problem of potential safety hazard in application process.
The present invention by making vinyltrimethoxy silane hydrolytie polycondensation in acid system obtain a kind of vinyl trimethoxysilane oligomer with higher boiling point and flash-point, specifically comprises the steps: under the metal catalyst existence condition
1) vinyltrimethoxy silane is dropped in the reactor, add acid its pH value is adjusted between 4～7;
2) add metal catalyst, stirring is uniformly dispersed it, and the weight consumption of metal catalyst is counted the 10-1000ppm of vinyltrimethoxy silane with pure metal; The aforementioned metal catalyzer is cupric oxide or ferric oxide, aluminum oxide, copper halide, iron halide, aluminum halide, copper hydroxide, ironic hydroxide, aluminium hydroxide;
3) drip distilled water or deionized water at 60-160 ℃ of following hydrolysis condensation reaction 6-12 hour, the dropping time was controlled at 0.15～1.0 hour, in the reaction system gross weight of water be vinyltrimethoxy silane weight 0.05-0.15 doubly;
4) the byproduct methyl alcohol that hydrolytie polycondensation produces is removed in distillation;
5) add in the Carbon Dioxide calcium and residual acid, and promptly make through suction filtration.
100ppm～900ppm (weight) that amount of metal catalyst is counted vinyltrimethoxy silane with pure metal among the present invention is better.
Institute of the present invention water with deionized water for well.Because hydrolysis reaction is thermopositive reaction, for preventing that heat release is violent in the hydrolytic process, can slow down rate of addition, can in deionized water, convert in addition to be added drop-wise in the reaction system again after the methyl alcohol dilution.
Hydrolysising reacting temperature generally is controlled under 60～160 ℃ and carries out, with 70～140 ℃ for well.Reaction times is 6～12h, with 8～10h for well.In the reaction process, for guaranteeing the pure available nitrogen protection of reaction system.
Reaction process of the present invention is to carry out under normal pressure, and removing byproduct methyl alcohol that hydrolytie polycondensation produces then needs to carry out at-0.1MPa.
Technology of the present invention is simple, and is easy to implement.After tested, be about 1.1 by 20 degrees centigrade of density of the vinyl trimethoxysilane oligomer of the present invention preparation, boiling point is greater than 220 degrees centigrade, and dioxide-containing silica is about 54%, and flash-point is about 87 degrees centigrade, and 20 degrees centigrade of viscosity are about 6 li pools.Because it has higher boiling point and flash-point, thus better security and operability when using, had, and because its alcohol that in use discharges ratio uses strand joint vinyltrimethoxy silane much less, so have more the feature of environmental protection.
Embodiment
Embodiment one
Add the 300g vinyltrimethoxy silane in the 500ml there-necked flask of being furnished with agitator, thermometer, discharge nozzle, dripping hydrochloric acid to pH value is 5 while stirring, adds 0.03 gram copper hydroxide then, stirs 10min and makes its thorough mixing.At the uniform velocity drip 31 gram deionized waters, dropwise in the 15min.The methyl alcohol that generates is removed in-0.1MPa distillation under 120 ℃ of conditions.Add then in the 20g Carbon Dioxide calcium and remaining acid, fully stir suction filtration behind the 30min, collect filtrate and get product, be yellow transparent liquid slightly, productive rate is 92%.
Embodiment two
Add the 300g vinyltrimethoxy silane in the 500ml there-necked flask of being furnished with agitator, thermometer, discharge nozzle, dripping glacial acetic acid to pH value while stirring is 4, adds 0.03 gram aluminum chloride then, stirs 10min and makes its thorough mixing.At the uniform velocity drip the 43g deionized water, dropwise in the 15min.The methyl alcohol that generates is removed in-0.1MPa distillation under 110 ℃ of conditions.Add then in the 20g Carbon Dioxide calcium and remaining acid, fully stir suction filtration behind the 30min, collect filtrate and get product, be colourless transparent liquid, productive rate is 96%.
Embodiment three
Add the 300g vinyltrimethoxy silane in the 500ml there-necked flask of being furnished with agitator, thermometer, discharge nozzle, dripping sulfuric acid to pH value while stirring is 6, adds 0.03 gram ferric oxide then, stirs 10min and makes its thorough mixing.Nitrogen protection at the uniform velocity drips 44g distilled water, dropwises in the 15min.The methyl alcohol that generates is removed in-0.1MPa distillation under 110 ℃ of conditions.Add then in the 30g Carbon Dioxide calcium and remaining acid, fully stir suction filtration behind the 30min, collect filtrate and get product, be yellow transparent liquid slightly, productive rate is 86%.
Embodiment four
Add the 300g vinyltrimethoxy silane in the 500ml there-necked flask of being furnished with agitator, thermometer, discharge nozzle, dripping sulfuric acid to pH value while stirring is 4, adds 0.03 gram iron(ic) chloride then, stirs 10min and makes its thorough mixing.Nitrogen protection at the uniform velocity drips 43g distilled water, dropwises in the 15min.The methyl alcohol that generates is removed in-0.1MPa distillation under 130 ℃ of conditions.Add then in the 30g Carbon Dioxide calcium and remaining acid, fully stir suction filtration behind the 30min, collect filtrate under 160 ℃ of conditions-0.1MPa distill once more product.Be yellow transparent liquid slightly, productive rate is 76%.
Claims (6)
1, a kind of preparation method of vinyl trimethoxysilane oligomer is characterized in that comprising the steps:
1) vinyltrimethoxy silane is dropped in the reactor, add acid its pH value is adjusted between 4～7;
2) add metal catalyst, stirring is uniformly dispersed it, and the weight consumption of metal catalyst is counted the 10-1000ppm of vinyltrimethoxy silane with pure metal; The aforementioned metal catalyzer is cupric oxide or ferric oxide, aluminum oxide, copper halide, iron halide, aluminum halide, copper hydroxide, ironic hydroxide, aluminium hydroxide;
3) drip distilled water or deionized water at 60-160 ℃ of following hydrolysis condensation reaction 6-12 hour, the dropping time was controlled at 0.15～1.0 hour, in the reaction system gross weight of water be vinyltrimethoxy silane weight 0.05-0.15 doubly;
4) the byproduct methyl alcohol that hydrolytie polycondensation produces is removed in distillation;
5) add in the Carbon Dioxide calcium and residual acid, and promptly make through suction filtration.
2, the preparation method of vinyl trimethoxysilane oligomer according to claim 1 is characterized in that dripping and is blended into methyl alcohol before the water in water and dilutes.
3, the preparation method of vinyl trimethoxysilane oligomer according to claim 1 and 2 is characterized in that described acid is sulfuric acid or hydrochloric acid, glacial acetic acid, p-methyl benzenesulfonic acid, Witco 1298 Soft Acid.
4, the preparation method of vinyl trimethoxysilane oligomer according to claim 1 and 2 is characterized in that the weight consumption of metal catalyst counts the 100-900ppm of vinyltrimethoxy silane with pure metal.
5, the preparation method of vinyl trimethoxysilane oligomer according to claim 1 and 2, the temperature that it is characterized in that hydrolysis reaction is 70-140 ℃, the reaction times is 8-10 hour.
6, the preparation method of vinyl trimethoxysilane oligomer according to claim 1 and 2, it is characterized in that water the total amount of reaction system be vinyltrimethoxy silane weight 0.05-0.12 doubly.
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| CNB2005100405390A CN100343311C (en) | 2005-06-16 | 2005-06-16 | Vinyl trimethoxysilane oligomer preparation method |
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| CNB2005100405390A CN100343311C (en) | 2005-06-16 | 2005-06-16 | Vinyl trimethoxysilane oligomer preparation method |
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| CN100343311C true CN100343311C (en) | 2007-10-17 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202011110266U1 (en) | 2011-11-22 | 2013-03-26 | Evonik Degussa Gmbh | Especially low-VOC mixtures of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE202011110267U1 (en) | 2011-11-22 | 2013-03-26 | Evonik Degussa Gmbh | Composition of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086867A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, and silyloxy crosslinked structural elements derived from alkoxysilanes |
| DE102011086865A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Low-chloride compositions of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086868A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, silyloxy crosslinked structural elements derived from alkoxysilanes, and chloride |
| DE102011086869A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Polymer composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom and silyloxy-crosslinked structural elements, organic polymer and inorganic solid material |
| DE102011086866A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Preparing composition containing olefinically functionalized siloxane oligomers, useful e.g. as adhesive, comprises reacting composition containing olefinically functionalized siloxane oligomers having chlorine content with reducing agent |
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| KR101077274B1 (en) * | 2007-05-28 | 2011-10-27 | 코오롱인더스트리 주식회사 | Polyalkylsilsesquioxane particulates and a preparation method thereof |
| CN102604105B (en) * | 2012-02-29 | 2014-05-07 | 安徽硅宝翔飞有机硅新材料有限公司 | Preparation method of aminosilane polymer |
| CN103396434A (en) * | 2013-07-22 | 2013-11-20 | 荆州市江汉精细化工有限公司 | Synthesis method of vinyltrimethoxysilane oligomer |
| CN109456725B (en) * | 2018-11-02 | 2021-05-04 | 成都硅宝科技股份有限公司 | Environment-friendly silane modified polyether sealant for home decoration and preparation method thereof |
| CN114774007A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | EVA adhesive film for packaging high-water-resistance solar cell and preparation method thereof |
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| US5282998A (en) * | 1991-06-08 | 1994-02-01 | Huls Aktiengesellschaft | Mixtures of linear and cyclic siloxanes or siloxane oligomers and a process for their preparation |
| US5543173A (en) * | 1993-10-12 | 1996-08-06 | Aluminum Company Of America | Surface treating aluminum trihydrate powders with prehydrolized silane |
| EP0814110A1 (en) * | 1996-06-17 | 1997-12-29 | Hüls Aktiengesellschaft | Mixture of oligomers of condensed alkylalkoxysilanes |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202011110266U1 (en) | 2011-11-22 | 2013-03-26 | Evonik Degussa Gmbh | Especially low-VOC mixtures of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE202011110267U1 (en) | 2011-11-22 | 2013-03-26 | Evonik Degussa Gmbh | Composition of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086863A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Especially low-VOC mixtures of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086867A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, and silyloxy crosslinked structural elements derived from alkoxysilanes |
| DE102011086865A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Low-chloride compositions of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086868A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom, fatty acid, silyloxy crosslinked structural elements derived from alkoxysilanes, and chloride |
| DE102011086862A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Composition of olefinically functionalized siloxane oligomers based on alkoxysilanes |
| DE102011086869A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Polymer composition useful e.g. as adhesive, comprises olefinically functionalized siloxane oligomers exhibiting less olefinic group at silicon atom and silyloxy-crosslinked structural elements, organic polymer and inorganic solid material |
| DE102011086866A1 (en) | 2011-11-22 | 2013-05-23 | Evonik Degussa Gmbh | Preparing composition containing olefinically functionalized siloxane oligomers, useful e.g. as adhesive, comprises reacting composition containing olefinically functionalized siloxane oligomers having chlorine content with reducing agent |
| WO2013076035A1 (en) | 2011-11-22 | 2013-05-30 | Evonik Degussa Gmbh | Mixtures, particularly low in volatile organic compounds (voc), of olefinically funtionalised siloxane oligomers based on alkoxy silanes |
| WO2013076032A1 (en) | 2011-11-22 | 2013-05-30 | Evonik Degussa Gmbh | Low chloride compositions of olefinically functionalised siloxane oligomers based on alkoxysilanes |
| WO2013076036A1 (en) | 2011-11-22 | 2013-05-30 | Evonik Degussa Gmbh | Composition of olefinically functionalsied siloxane oligomers based on alkoxy silanes |
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| CN1769323A (en) | 2006-05-10 |
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