CN105061486B - A kind of preparation method of acidic crosslinking agent - Google Patents
A kind of preparation method of acidic crosslinking agent Download PDFInfo
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- CN105061486B CN105061486B CN201510476763.8A CN201510476763A CN105061486B CN 105061486 B CN105061486 B CN 105061486B CN 201510476763 A CN201510476763 A CN 201510476763A CN 105061486 B CN105061486 B CN 105061486B
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Abstract
The present invention relates to a kind of preparation method of acidic crosslinking agent；Belong to technical field of organic chemistry.The present invention is using propyl trimethoxy silicane and glacial acetic acid as raw material；HMPA is catalyst, reacts synthetic acidic crosslinking agent product by base exchange, in course of reaction, the methanol of by-product is steamed into reaction system in time so that is chemically reacted to the movement of generation acidic crosslinking agent direction.The present invention is a kind of alternative of synthetic acidic crosslinking agent, and this method technique is simple, can be adapted to industrial-scale production, does not produce that corrosivity is strong and intractable accessory substance compared with existing acidic crosslinking agent preparation method；The side reaction of acidic crosslinking agent product quality, especially product content are not influenceed；In addition, the present invention is not raw materials used chloride, so, the acidic crosslinking agent product free chlorine of preparation is low.
Description
Technical field
The present invention relates to a kind of preparation method of acidic crosslinking agent；Belong to technical field of organic chemistry.
Background technology
Acidic crosslinking agent is one kind in silane coupler, and its acyloxy is compared with other groups such as methoxyl group, ethyoxyl
More active, decomposition rate is fast, water-disintegrable more preferably to be advantageous to improve operating efficiency, and it is weaker to hydrolyze the acetic acid of precipitation, to reaction
System harm is smaller.Therefore more preferable to adhesive effects such as enhancing aluminium alloy, nylon, glass and ceramics, it is mainly used as RTV-1 silicon
The crosslinking agent of rubber sealant；The surface conditioning agent of glass fibre；Coupling agent and silated reagent.
The raw material propyl trimethoxy silicane of synthetic acidic crosslinking agent is by the accessory substance of γ-r-chloropropyl trimethoxyl silane
It is prepared, γ-r-chloropropyl trimethoxyl silane is a series of important raw and processed materials for synthesizing γ-functional group's silane couplers.
In current industrial production, often with the accessory substance generation for accounting for product quality 20%.With the expansion of its application field, demand
Amount is also increasing rapidly, so as to cause a large amount of appearance of accessory substance.The Main Ingredients and Appearance of the accessory substance be tetramethoxy-silicane and
N- propyl trimethoxy silicanes, tetramethoxy-silicane can be used for selling, and propyl trimethoxy silicane market is small, it is impossible to completely
Sell, thus with its synthetic acidic crosslinking agent product, it is possible to achieve turn waste into wealth, environmental protection and economy, be advantageous to organic silicon resource
Comprehensive utilization.At present, the preparation method of acidic crosslinking agent comparative maturity has the following two kinds：
First method is as follows using carboxylic acid as acyl-oxygen agent, reaction equation：
CH3CH2CH2SiCl3+ 3CH3COOH CH3CH2CH2Si (OOCCH3)3 + 3HCl
The major advantage of this method is that raw material is easily purchased, and cheaply, but react relatively difficult, produce corrosive accessory substance
Hydrogen chloride, while side reaction be present, product content is influenceed, and product free chlorine is difficult to control.
Second method is as follows using acetic anhydride as acyl-oxygen agent, reaction equation：
CH3CH2CH2SiCl3 + 3[CH3CO]2OCH3CH2CH2Si (OOCCH3)3 + 3CH3COl
The major advantage of this method is simple for reaction, no side reaction, but raw material is not easy to purchase, and somewhat expensive, and generation is not easy
The corrosive byproducts chloroacetic chloride of processing, while product free chlorine is difficult to control.
For many deficiencies of current acidic crosslinking agent preparation technology, it is necessary to study a kind of acidic crosslinking agent preparation side
Method, can overcome the shortcomings of existing preparation technology, and and can is adapted to industrialization to mass produce.
The content of the invention
It is an object of the invention to：There is provided it is a kind of can overcome the shortcomings of existing preparation technology, and can is adapted to industrialization big
The preparation method of the acidic crosslinking agent of large-scale production.
The technical scheme is that：
A kind of preparation method of acidic crosslinking agent, it is characterised in that：It comprises the following steps：
1）It is being connected with magnetic agitation, still head, condenser west tube, the adapter of sub-thread vacuum tail, 1000ml single port receiving bottles
2000ml three-necked flasks in, propyl trimethoxy silicane, glacial acetic acid and HMPA are added, at 80 ~ 100 revs/min
Mixing speed under be warming up to 50 ~ 75 DEG C, keep 3 ~ 6h of the thermotonus, react whole and keep normal pressure, have in course of reaction few
Amount methanol is collected into receiving flask；
2）The crude product that step 1 reaction is obtained, carries out normal pressure steaming under conditions of pressure 101KPa, 65 ~ 120 DEG C of temperature
Evaporate, the air-distillation time is 1 ~ 2h, collect ester exchange reaction by-product methanol, then 0 ~ -0.098Mpa of pressure, temperature 120 ~
It is evaporated under reduced pressure again under conditions of 140 DEG C, a small amount of low boiling is distilled totally, obtains propyl group triacetoxysilane crude product；
3）The propyl group triacetoxysilane crude product that step 2 obtains is cooled to 70-80 DEG C, then adds activated carbon,
2h is stirred with 80 ~ 100 revs/min of speed, after be cooled to less than 40 DEG C and filtered, the colourless transparent liquid being filtrated to get
As propyl group triacetoxysilane product.
The reaction equation of the present invention is as follows：
CH3CH2CH2Si(OCH3)3 + 3CH3COOHCH3CH2CH2Si (OOCCH3)3 + 3 CH3OH
It is an advantage of the invention that：
The present invention is using propyl trimethoxy silicane and glacial acetic acid as raw material；HMPA is catalyst, passes through base
Group exchange reaction synthetic acidic crosslinking agent product, catalyst charge for propyl trimethoxy silicane inventory 0.002% ~
0.01%, early stage is in 50 DEG C ~ 75 DEG C of kettle temperature, 3 ~ 6h of reaction under condition of normal pressure, then side reaction, side air-distillation ester exchange by-product
Methanol, distillation time is 1 ~ 2h, and kettle temperature is 65 ~ 120 DEG C, after air-distillation, is continued in 0 ~ -0.098Mpa of pressure, temperature
It is evaporated under reduced pressure again under conditions of 120 ~ 140 DEG C of degree, a small amount of low boiling is distilled totally, propyl group triacetoxysilane is obtained and slightly produces
Product；Crude product obtains content >=96.0%, free chlorine≤10ppm, mass yield after decolourizing, filtering（With propyl trimethoxy silicon
Alkane inventory calculates）>=140% propyl group triacetoxysilane product：Instant invention overcomes current acidic crosslinking agent to prepare work
Many deficiencies of skill, it is adapted to industrialization large-scale production.
Embodiment
Embodiment 1
It is being connected with magnetic agitation, still head, condenser west tube（It is connected with cooling running water）, sub-thread vacuum tail adapter,
In the 2000ml three-necked flasks of 1000ml single port receiving bottles, 492g propyl trimethoxy silicanes, 540g glacial acetic acids and 0.03g are added
HMPA, 75 DEG C are warming up under 100 revs/min of mixing speed, keep thermotonus 6h, reacted whole and keep
Normal pressure, there is a small amount of methanol to be collected into receiving flask in course of reaction；Obtained crude product will be reacted after completion of the reaction, in pressure
Air-distillation is carried out under conditions of 101KPa, 75 DEG C of temperature, the air-distillation time is 2h, collects the methanol of ester exchange reaction by-product
256g, then it is evaporated under reduced pressure again under conditions of 0 ~ -0.098Mpa of pressure, 130 DEG C of temperature, collects remaining low boiling 50g,
Obtain propyl group triacetoxysilane crude product；Obtained propyl group triacetoxysilane crude product is cooled to 80 DEG C, Ran Houjia
Enter 5g activated carbons, 2h stirred with 100 revs/min of speed, after be cooled to less than 40 DEG C and filtered, be filtrated to get colourless
The propyl group triacetoxysilane product 726g of prescribed liquid, product content：96.5%；Free chlorine：5ppm；Mass yield：
147.5%。
Embodiment 2
It is being connected with magnetic agitation, still head, condenser west tube（It is connected with cooling running water）, sub-thread vacuum tail adapter,
In the 2000ml three-necked flasks of 1000ml single port receiving bottles, 492g propyl trimethoxy silicanes, 540g glacial acetic acids, 0.03g are added
HMPA, 70 DEG C are warming up under 90 revs/min of mixing speed, keep thermotonus 5h, reacted whole and keep
Normal pressure, there is a small amount of methanol to be collected into receiving flask in course of reaction；Obtained crude product will be reacted after completion of the reaction, in pressure
Air-distillation is carried out under conditions of 101KPa, 120 DEG C of temperature, the air-distillation time is 1.5h, collects ester exchange reaction by-product
Methanol 250g, then it is evaporated under reduced pressure again under conditions of 0 ~ -0.098Mpa of pressure, 140 DEG C of temperature, collects remaining low boiling
70g, obtain propyl group triacetoxysilane crude product；Obtained propyl group triacetoxysilane crude product is cooled to 75 DEG C, so
Add 5g activated carbons afterwards, 2h stirred with 90 revs/min of speed, after be cooled to less than 40 DEG C and filtered, be filtrated to get nothing
The propyl group triacetoxysilane product 712g of color transparency liquid, product content：96.8%；Free chlorine：7ppm；Mass yield：
144.7%。
Embodiment 3
It is being connected with magnetic agitation, still head, condenser west tube（It is connected with cooling running water）, sub-thread vacuum tail adapter,
In the 2000ml three-necked flasks of 1000ml single port receiving bottles, 492g propyl trimethoxy silicanes, 540g glacial acetic acids, 0.05g are added
HMPA, 60 DEG C are warming up under 100 revs/min of mixing speed, keep thermotonus 5h, reacted whole and keep
Normal pressure, there is a small amount of methanol to be collected into receiving flask in course of reaction；Obtained crude product will be reacted after completion of the reaction, in pressure
Air-distillation is carried out under conditions of 101KPa, 90 DEG C of temperature, the air-distillation time is 1.5h, collects the first of ester exchange reaction by-product
Alcohol 248g, then it is evaporated under reduced pressure again under conditions of 0 ~ -0.098Mpa of pressure, 130 DEG C of temperature, collects remaining low boiling
63g, obtain propyl group triacetoxysilane crude product；Obtained propyl group triacetoxysilane crude product is cooled to 80 DEG C, so
Add 5g activated carbons afterwards, 2h stirred with 100 revs/min of speed, after be cooled to less than 40 DEG C and filtered, be filtrated to get nothing
The propyl group triacetoxysilane product 721g of color transparency liquid, product content：96.3%；Free chlorine：3ppm；Mass yield：
146.5%。
Embodiment 4
It is being connected with magnetic agitation, still head, condenser west tube（It is connected with cooling running water）, sub-thread vacuum tail adapter,
In the 2000ml three-necked flasks of 1000ml single port receiving bottles, 492g propyl trimethoxy silicanes, 540g glacial acetic acids, 0.05g are added
HMPA, 65 DEG C are warming up under 100 revs/min of mixing speed, keep thermotonus 3h, reacted whole and keep
Normal pressure, there is a small amount of methanol to be collected into receiving flask in course of reaction；Obtained crude product will be reacted after completion of the reaction, in pressure
Air-distillation is carried out under conditions of 101KPa, 115 DEG C of temperature, the air-distillation time is 1h, collects the first of ester exchange reaction by-product
Alcohol 222g, then it is evaporated under reduced pressure again under conditions of 0 ~ -0.098Mpa of pressure, 120 DEG C of temperature, collects remaining low boiling
103g, obtain propyl group triacetoxysilane crude product；Obtained propyl group triacetoxysilane crude product is cooled to 80 DEG C, so
Add 5g activated carbons afterwards, 2h stirred with 100 revs/min of speed, after be cooled to less than 40 DEG C and filtered, be filtrated to get nothing
The propyl group triacetoxysilane product 707g of color transparency liquid, product content：96.3%；Free chlorine：3ppm；Mass yield：
143.7%。
Claims (1)
- A kind of 1. preparation method of acidic crosslinking agent, it is characterised in that：It comprises the following steps：1）, be connected with magnetic agitation, still head, condenser west tube, the adapter of sub-thread vacuum tail, 1000ml single port receiving bottles In 2000ml three-necked flasks, propyl trimethoxy silicane, glacial acetic acid and HMPA are added, at 80 ~ 100 revs/min 50 ~ 75 DEG C are warming up under mixing speed, keeps 3 ~ 6h of the thermotonus, reacts whole and keeps normal pressure, have in course of reaction a small amount of Methanol is collected into receiving flask；2）, by the obtained crude product of step 1 reaction, carry out air-distillation under conditions of pressure 101KPa, 65 ~ 120 DEG C of temperature, often Pressure distillation time is 1 ~ 2h, collects the methanol of ester exchange reaction by-product, then in 120 ~ 140 DEG C of 0 ~ -0.098Mpa of pressure, temperature Under conditions of be evaporated under reduced pressure again, a small amount of low boiling is distilled clean, obtains propyl group triacetoxysilane crude product；3）, the propyl group triacetoxysilane crude product that step 2 obtains is cooled to 70-80 DEG C, activated carbon is then added, with 80 ~ 100 revs/min of speed stirring 2h, after be cooled to less than 40 DEG C and filtered, the colourless transparent liquid being filtrated to get is Propyl group triacetoxysilane product；Its reaction equation is as follows：。
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| CN108358963A (en) * | 2018-03-14 | 2018-08-03 | 广州雷斯曼新材料科技有限公司 | A kind of acidic crosslinking agent and preparation method thereof applied to silicone sealant |
| EP4034588A1 (en) * | 2019-09-27 | 2022-08-03 | Evonik Operations GmbH | Silicone (meth)acrylates, process for their preparation and their use in curable compositions |
| CN114315890B (en) * | 2022-01-05 | 2023-11-17 | 湖北江瀚新材料股份有限公司 | Preparation method of methacryloxypropyl triacetoxy silane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187291A (en) * | 1991-04-18 | 1993-02-16 | Huls Aktiengesellschaft | Process for the simultaneous and continuous preparation of acyloxysilanes and carboxylic acid chlorides |
| CN104558012A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Preparation method of propyltriacetoxysilane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187291A (en) * | 1991-04-18 | 1993-02-16 | Huls Aktiengesellschaft | Process for the simultaneous and continuous preparation of acyloxysilanes and carboxylic acid chlorides |
| CN104558012A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Preparation method of propyltriacetoxysilane |
Non-Patent Citations (1)
| Title |
|---|
| 乙基三乙酰氧基硅烷与六甲基二硅烷的合成研究;李飞;《万方学位论文全文数据库》;20100316;第2.3.1.3节-2.3.1.5节，第2.3.2节 * |
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Address after: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee after: Hubei Jianghan New Material Co.,Ltd. Address before: 434000 No.2 Road, Shashi District Economic and Technological Development Zone, Jingzhou City, Hubei Province Patentee before: JINGZHOU JIANGHAN FINE CHEMICAL Co.,Ltd. |