CN103387585A - A synthetic method for a silane acidic cross-linking agent - Google Patents
A synthetic method for a silane acidic cross-linking agent Download PDFInfo
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- CN103387585A CN103387585A CN2013103080592A CN201310308059A CN103387585A CN 103387585 A CN103387585 A CN 103387585A CN 2013103080592 A CN2013103080592 A CN 2013103080592A CN 201310308059 A CN201310308059 A CN 201310308059A CN 103387585 A CN103387585 A CN 103387585A
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Abstract
The invention relates to a synthetic method for a silane acidic cross-linking agent, and belongs to the silane cross-linking agent synthesis field. According to the method, silicon tetrachloride and anhydrous sodium acetate are used as raw materials, and are reacted to produce a mixture of silicon tetraacetate and a salt sodium chloride. Then, tertiary butanol used as a raw material is added to partially replace an acetoxyl group, and a product di-(tert-butoxy)-diacetoxysilane and a byproduct acetic acid are produced. Then the silane acidic cross-linking agent is obtained by removing the salt through filtration, and removing solvent and the byproduct through distillation under reduced pressure. The method employs the anhydrous sodium acetate as the raw material to avoid mass production of acetylchloride caused by using acetic anhydride as a raw material. The method has advantages of environmental friendly production, simple technology, stable quality, high reaction conversion rate, high yield, low production cost, and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of silane acidic crosslinking agent, belong to the synthetic field of silane crosslinker.
Background technology
Linking agent is a kind ofly can play the crane span structure effect line style is intermolecular, a plurality of thread-like molecules is reacted to each other be cross-linked into the material of network structure.Linking agent mainly is used in macromolecular material (rubber and thermosetting resin), its effect produces chemical bond exactly between the molecule of line style, thread-like molecule is connected with each other, form reticulated structure, can improve like this performances such as intensity, elasticity, thermotolerance, wear resistance, solvent resistance of rubber.
Ditert-butyldiacetyl oxygen-base silane, be a kind of self-vulcanizing linking agent for the production of depickling type organosilicon sealant, and this class seal gum is the organosilicon sealant of market consumption maximum.Saying for single-component room-temperature vulcanized silicone rubber, is chainextender, is again a water absorbent, is applied to the tensile strength that can obviously improve tackiness agent in tackiness agent, tensile yield, tear strength and bond strength, and the stability in storage of raising product.The main ingredient of synthetic ditert-butyldiacetyl oxygen-base silane is silicon tetrachloride, aceticanhydride, the trimethyl carbinol and solvent, after existing synthetic method is acidylate, and resterification.This synthesis technique poor operability, yield is low, and product quality is unstable, and produces a large amount of Acetyl Chloride 98Min.s, needs multiple times of filtration, and very high to the requirement of filter plant.
Summary of the invention
The object of the invention is to: provide a kind of and can effectively improve the quality of products and the stability of product quality, and improve yield, reduce costs, and technological operation is simple, the synthetic method of the silane acidic crosslinking agent of environmentally safe.
Technical scheme of the present invention is:
A kind of synthetic method of silane acidic crosslinking agent is characterized in that it comprises the steps:
1), drop into sodium acetate, anhydrous and toluene in three mouthfuls of reaction flasks, under the stirring that per minute 100-300 turns, drip silicon tetrachloride, reaction generates tetrem acyloxy silane and sodium chloride salt;
The mol ratio of silicon tetrachloride and sodium-acetate is 1:4-4.2, the add-on of toluene is the 70-150% of silicon tetrachloride and sodium acetate, anhydrous quality sum, temperature of reaction is controlled at 25-70 ℃, time for adding is controlled at 1-3 hour, after dripping, continue reaction 0.5-1 hour, reaction generates the mixture of acetoxysilane and sodium-chlor.
2), after acylation reaction finishes, start to drip the trimethyl carbinol, to carry out esterification.Temperature of reaction is controlled at 1-5 ℃, and the add-on of the trimethyl carbinol and the mol ratio of silicon tetrachloride are 2:1, and time for adding is controlled at 0.5-1 hour, after dripping, continues reaction 0.5-2 hour.
3), the solids removed by filtration thing, obtain the ditert-butyldiacetyl oxygen-base silane crude product, then distillation, except the acetic acid of desolventizing and generation, obtains the ditert-butyldiacetyl oxygen-base silane finished product, i.e. the silane acidic crosslinking agent.
Chemical equation of the present invention is as follows:
Reaction principle of the present invention:
Silicon tetrachloride, sodium-acetate and toluene add according to certain ratio, and reaction generates tetrem acyloxy silane solids and sodium chloride salt, and wherein toluene, as solvent, can reduce the viscosity of mixture, and heat and mass is effective.
After reaction finished, reaction system did not need to separate, and then started cooling.Slowly add a certain proportion of trimethyl carbinol again in system, start to stir, the trimethyl carbinol can displace acetoxyl group, produces by product acetic acid.Then filter, distill, obtain silane acidic crosslinking agent product.Through gas chromatographic analysis, product yield reaches more than 95%, and product purity reaches more than 96%, and toluene (containing acetic acid) solvent material can recycle in reaction next time, and is without the generation of any waste liquid, free from environmental pollution.
The present invention's advantage compared with prior art is as follows:
1), in the present invention by controlling the mol ratio of silicon tetrachloride and sodium-acetate, reach the purpose of synthetic mesophase product.
2), the present invention optimized technique, simple to operate, intermediates do not need to filter out.
3), do not produce Acetyl Chloride 98Min. in reaction process of the present invention, do not greatly reduce the requirement to equipment, both reduced cost, environmental protection more again in whole production process.
Embodiment
Embodiment 1:
With mechanical stirring, drop into sodium acetate, anhydrous 656.2g and toluene 700g in three mouthfuls of reaction flasks of the 2000ml of constant pressure funnel and condenser, drop into silicon tetrachloride 340g simultaneously in constant pressure funnel.The mol ratio of silicon tetrachloride and sodium acetate, anhydrous is 1:4, and the solvent toluene add-on is 70% of sodium acetate, anhydrous and silicon tetrachloride total mass.Then start mechanical stirring, start to drip the silicon tetrachloride reaction under the stirring that per minute 100 turns, temperature of reaction is controlled at 25 ℃, and the silicon tetrachloride time for adding is 1 hour.After dripping, continue reaction 1 hour, reaction generates the mixture of acetoxysilane and sodium-chlor.React after 1 hour, reaction system is transferred under the ice-water bath condition, drop into trimethyl carbinol 299g in constant pressure funnel, again start mechanical stirring, drip trimethyl carbinol reaction under the condition that per minute 400 turns, temperature of reaction is controlled at 1 ℃, and trimethyl carbinol time for adding is 1 hour, after dripping, continued stirring reaction 1 hour.Filtration under diminished pressure is removed white depositions, and filtrate is carried out underpressure distillation, obtains the ditert-butyldiacetyl oxygen-base silane finished product, i.e. silane acidic crosslinking agent 555.6g.
Product yield reaches 95.0%, main content 96.1%.
Embodiment 2:
With mechanical stirring, drop into sodium acetate, anhydrous 656.2g and toluene 847g in the 2000ml four-hole reaction flask of constant pressure funnel and condenser, drop into silicon tetrachloride 340g simultaneously in constant pressure funnel.The mol ratio of silicon tetrachloride and sodium acetate, anhydrous is 1:4, and the solvent toluene add-on is 85% of sodium acetate, anhydrous and silicon tetrachloride total mass.Then start mechanical stirring, drip the silicon tetrachloride reaction under the stirring that per minute 200 turns, temperature of reaction is controlled at 50 ℃, and the silicon tetrachloride time for adding is 2.5 hours.After dripping, continue reaction 1 hour.Then reaction system is transferred under the ice-water bath condition, drop into trimethyl carbinol 299g in constant pressure funnel, again start mechanical stirring, drip trimethyl carbinol reaction under the stirring that per minute 400 turns, temperature of reaction is controlled at 4 ℃, time for adding is 1 hour, after dripping, continues stirring reaction 1.5 hours.Filtration under diminished pressure is removed white depositions, and filtrate is carried out underpressure distillation, obtains the ditert-butyldiacetyl oxygen-base silane finished product, i.e. silane acidic crosslinking agent 564.3g.
Product yield reaches 96.5%, main content 97.0%.
Embodiment 3:
With mechanical stirring, drop into sodium acetate, anhydrous 656.2g and toluene 996g in the 2000ml four-hole reaction flask of constant pressure funnel and condenser, drop into silicon tetrachloride 340g simultaneously in constant pressure funnel.The mol ratio of silicon tetrachloride and sodium acetate, anhydrous is 1:4, and the solvent toluene add-on is 100% of sodium acetate, anhydrous and silicon tetrachloride total mass.Then start mechanical stirring, drip the silicon tetrachloride reaction under the stirring that per minute 300 turns, temperature of reaction is controlled at 70 ℃, and the silicon tetrachloride time for adding is 3 hours.After dripping, continue reaction 1 hour.Then reaction system is transferred under the ice-water bath condition, drop into trimethyl carbinol 299g in constant pressure funnel, again start mechanical stirring, drip trimethyl carbinol reaction under the stirring that per minute 400 turns, temperature of reaction is controlled at 5 ℃, trimethyl carbinol time for adding is 1 hour, after dripping, continues stirring reaction 2 hours.Filtration under diminished pressure is removed white depositions, and filtrate is carried out underpressure distillation, obtains the ditert-butyldiacetyl oxygen-base silane finished product, i.e. silane acidic crosslinking agent 567.3g.
Product yield reaches 97.0%, main content 97.5%.
Those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention the present invention.Like this, if within of the present invention these are revised and modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention also is intended to comprise these changes and modification interior.The content that is not described in detail in this specification sheets belongs to the known prior art of this area professional and technical personnel.
Claims (1)
1. the synthetic method of a silane acidic crosslinking agent, is characterized in that, it comprises the steps:
1), drop into sodium acetate, anhydrous and toluene in three mouthfuls of reaction flasks, under the stirring that per minute 100-300 turns, drip silicon tetrachloride, reaction generates tetrem acyloxy silane and sodium chloride salt;
The mol ratio of silicon tetrachloride and sodium-acetate is 1:4-4.2, the add-on of toluene is the 70-150% of silicon tetrachloride and sodium acetate, anhydrous quality sum, temperature of reaction is controlled at 25-70 ℃, time for adding is controlled at 1-3 hour, after dripping, continue reaction 0.5-1 hour, reaction generates the mixture of acetoxysilane and sodium-chlor;
2), after acylation reaction finishes, start to drip the trimethyl carbinol, to carry out esterification; Temperature of reaction is controlled at 1-5 ℃, and the add-on of the trimethyl carbinol and the mol ratio of silicon tetrachloride are 2:1, and time for adding is controlled at 0.5-1 hour, after dripping, continues reaction 0.5-2 hour;
3), the solids removed by filtration thing, obtain the ditert-butyldiacetyl oxygen-base silane crude product, then distillation, except the acetic acid of desolventizing and generation, obtains the ditert-butyldiacetyl oxygen-base silane finished product, i.e. the silane acidic crosslinking agent.
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| CN201310308059.2A CN103387585B (en) | 2013-07-22 | 2013-07-22 | A kind of synthetic method of silane acidic crosslinking agent |
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| CN201310308059.2A CN103387585B (en) | 2013-07-22 | 2013-07-22 | A kind of synthetic method of silane acidic crosslinking agent |
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| CN103387585B CN103387585B (en) | 2016-04-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969298A (en) * | 2016-07-05 | 2016-09-28 | 湖北兴发化工集团股份有限公司 | Production process for acid silicone sealant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208359A (en) * | 1990-07-09 | 1993-05-04 | Huels Aktiengesellschaft | Process for the preparation of di-tert.butoxydiacetoxysilane |
| CN1955184A (en) * | 2005-10-27 | 2007-05-02 | 姜堰市扬子江化工有限公司 | Preparation method of di-tert-butoxydiacetoxysilane |
| CN102286018A (en) * | 2011-08-08 | 2011-12-21 | 浙江大学 | Preparation method of acetoxysilane |
-
2013
- 2013-07-22 CN CN201310308059.2A patent/CN103387585B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208359A (en) * | 1990-07-09 | 1993-05-04 | Huels Aktiengesellschaft | Process for the preparation of di-tert.butoxydiacetoxysilane |
| CN1955184A (en) * | 2005-10-27 | 2007-05-02 | 姜堰市扬子江化工有限公司 | Preparation method of di-tert-butoxydiacetoxysilane |
| CN102286018A (en) * | 2011-08-08 | 2011-12-21 | 浙江大学 | Preparation method of acetoxysilane |
Non-Patent Citations (1)
| Title |
|---|
| 李飞等: "合成乙基三乙酰氧基硅烷的研究进展及应用", 《有机硅材料》, vol. 21, no. 2, 25 March 2007 (2007-03-25), pages 97 - 99 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969298A (en) * | 2016-07-05 | 2016-09-28 | 湖北兴发化工集团股份有限公司 | Production process for acid silicone sealant |
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Address after: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee after: Hubei Jianghan New Material Co.,Ltd. Address before: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee before: JINGZHOU JIANGHAN FINE CHEMICAL Co.,Ltd. |