CN106349276B - A kind of ester exchange method preparing vinyl three-(2- methoxyethoxy)-silane - Google Patents
A kind of ester exchange method preparing vinyl three-(2- methoxyethoxy)-silane Download PDFInfo
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- CN106349276B CN106349276B CN201610655812.9A CN201610655812A CN106349276B CN 106349276 B CN106349276 B CN 106349276B CN 201610655812 A CN201610655812 A CN 201610655812A CN 106349276 B CN106349276 B CN 106349276B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of ester exchange methods for preparing vinyl three-(2- methoxyethoxy)-silane, belong to technical field of organic chemistry.The present invention carries out ester exchange reaction using glycol monoethyl ether, vinyltrimethoxysilane as raw material, using neutral multiple saline catalyst, generates vinyl three-(2- methoxyethoxy)-silane.Catalyst is recovered by filtration, reusable.Advantage of this method compared with traditional esterifications method is: 1, ester-exchange reaction not will lead to product colour and deepen, and react distillation for removing methanol, directly filtering getting the product.2, catalyst is recyclable, reuses 10 times, activity still maintains.
Description
Technical field
The present invention relates to a kind of ester exchange methods for preparing vinyl three-(2- methoxyethoxy)-silane, belong to organic chemistry
Technical field.
Background technique
The structural formula of vinyl three-(2- methoxyethoxy)-silane is as follows:
The common preparation method of vinyl alkoxy silane is to carry out being esterified instead with vinyl trichlorosilane and alcohols material
Answer, then it is neutralized, filtering, rectifying and (such as Chinese patent CN1320600A) is made.Reaction equation is as follows:
Main reaction:
Side reaction:
The hydrogen chloride gas of feed ethylene base trichlorosilane and by-product that this method uses is big to the corrosivity of equipment, and
The bad processing of the hydrogen chloride of by-product is generally required and is absorbed using the neutralizer of alkalinity, or increases equipment investment, uses drop
The hydrochloric acid that the equipments such as film absorption tower make it be changed into high concentration is externally sold.It is total additionally, due to hydrogen chloride in the reaction system and alcohol
It deposits, so will lead to such as the side reaction in schema, portioned product is caused to polymerize, although using solvent and dry sky in its patent
Gas takes away hydrogen chloride gas in time, but can not be inherently eliminated the generation of side reaction.
Vinyl alkoxy silane can also pass through acetylene and addition under the action of platinum group catalyst of siloxy hydrogen silane
And (such as patent CN102898458A) is obtained, reaction equation is as follows:
Main reaction:
Side reaction:
The disadvantages of the method are as follows the safety cost of raw material acetylene is high, acetylene is a kind of inflammable and explosive gas, is not only met bright
Fire can burn quick-fried work, and operating pressure is excessive will also result in acetylene self-polymerization, and quick-fried work occurs, thus to use acetylene as
Raw materials for production not only need higher equipment investment, but also need lengthy and tedious examination and approval procedures.The method, which has another disadvantage that, to be made
It uses expensive chloroplatinic acid as catalyst, further increases cost, in addition this method also unavoidable acetylene and silane containing hydrogen
Excessive addition, generate ethyl bis-alkoxysilane, cause the yield of principal product to reduce.
A kind of method for the continuous transesterification of alkoxy silane is disclosed in US60272909, this method is contained with one kind
The organo-silicon compound of at least one alkoxy react in the presence of a effective amount of acid or alkaline ester exchange catalyst, and lead to
It crosses control reaction temperature and constantly steams the low-boiling point alcohol that transesterification goes out, realize the continuous separation of product stream.Its reaction equation
It is as follows:
The selection of catalyst is often determined by the alkoxy silane of ester friendship in the ester exchange method, for example, aminoalkyl
Alkoxy silane generallys use basic catalyst such as corresponding sodium alkoxide and carries out transesterification, and non-functional or alkali sensitivity alkyl
Transesterification is carried out with the silane acidic catalyst of alkoxy, such as p-methyl benzenesulfonic acid.
Summary of the invention
It is an object of the invention to: a kind of transesterification side preparing vinyl three-(2- methoxyethoxy)-silane is provided
Method, this method include the multiple saline catalyst that transesterification is added, which is environmental-friendly, to system transesterification catalysis
Ability is strong, and catalyst is small in the solubility of reaction system, recyclable, and activity is unaffected.
The technical scheme is that
A kind of ester exchange method preparing vinyl three-(2- methoxyethoxy)-silane, which is characterized in that it include with
Lower step:
1) vinyltrimethoxysilane, is added into flask, glycol monoethyl ether is as reaction substrate, vinyl three
Methoxy silane and the mass ratio of the material of glycol monoethyl ether are 1:3.
2) double salt ester exchange catalyst, is added into the mixture, double salt ester exchange catalyst is anhydrous potassium aluminium sulfate, sulphur
Any one of sour ferripotassium, iron ammonium sulfate, double salt ester exchange catalyst dosage account for the 0.1-0.5% of reactant gross mass.
3) reaction system, is heated, reaction temperature is made to rise to 70-80 DEG C, vinyltrimethoxysilane and ethylene glycol list
Ester exchange reaction occurs for methyl ether.
4) it after, reacting 2h, starts to warm up and methanol is evaporated off, when temperature in the kettle rises to 100 DEG C, recycling obtains theoretical amount
Methanol, while most double salt catalyst also evolution reaction system therewith.
5) 50 DEG C, are cooled to hereinafter, filtering, obtains double salt ester exchange catalyst and give over to next pot of use, and obtain colourless
Transparent vinyl three-(2- methoxyethoxy)-silane, yield 98.5-99.5%, through gas chromatographic detection, content is
99.2-99.5% can be used directly as product.
Step 5) is recycled into gained double salt catalyst collection, instead of raw catelyst for reacting, is reused 10 times, catalysis
The activity of agent still maintains.
During the experiment it was found that after multiple saline catalyst is added, without the temperature of stringent control reaction, instead
Not phenomena such as crude product color does not occur intensification during answering, blackening, it means that catalyst stability is good, strong compared to traditional
Acid, strong alkali catalyst, caused side reaction are less.Based on this, transesterification production need to be only evaporated off after the completion of transesterification in we
Raw methanol directly filters, the product of coloration compliance can be obtained, and the step for eliminating product distillation is poly-.In addition, we are testing
In it has also been found that, for containing ethylene linkage substance carry out distilation when, traditional catalyst, such as lithium hydroxide of strong basicity,
Such as p-methyl benzenesulfonic acid of highly acid all easily leads to ethylene linkage polymerization, and influences product yield.And double salt class used in the present invention
Catalyst not will lead to the polymerization of ethylene linkage then, even under the conditions of vapo(u)rizing temperature is higher.
The present invention has the advantages that
The present invention uses neutral multiple saline catalyst using glycol monoethyl ether, vinyltrimethoxysilane as raw material
Ester exchange reaction is carried out, vinyl three-(2- methoxyethoxy)-silane is generated.Catalyst is recovered by filtration, repeatable to make
With.Advantage of this method compared with traditional esterifications method is: 1, ester-exchange reaction not will lead to product colour and deepen, and react
Distillation for removing methanol, directly filtering getting the product.2, catalyst is recyclable, reuses 10 times, activity still maintains.
Specific embodiment
Embodiment 1
Equipped with magnetic agitation, thermometer, spherical condensation tube 1000ml four-hole boiling flask in vinyl trimethoxy is added
Silane 148g, glycol monoethyl ether 228g, 1g anhydrous potassium aluminium sulfate.It is warming up to 70-80 DEG C, reacts 2h.Then heating starts to steam
Except methanol, when kettle temperature rises to 100 DEG C, Methanol Recovery is finished, and methanol 94g is obtained.Then cool down, when being cooled under 50 DEG C
Afterwards, it filters, recycling obtains anhydrous potassium aluminium sulfate 0.96g, obtains colorless and transparent vinyl three-(2- methoxyethoxy)-silane
Product 278g, yield 99.5%.It is 99.5% using its content of gas chromatographic detection.
Embodiment 2
Equipped with magnetic agitation, thermometer, spherical condensation tube 1000ml four-hole boiling flask in vinyl trimethoxy is added
Silane 148g, glycol monoethyl ether 228g, 1g anhydrous slufuric acid ferripotassium.It is warming up to 70-80 DEG C, reacts 4h.Then heating starts to steam
Except methanol, when kettle temperature rises to 100 DEG C, Methanol Recovery is finished, and it is 90g that quantity of methyl alcohol, which is obtained,.Then cool down, when being cooled to 50 DEG C
Under after, filtering, recycling obtain double salt ester exchange catalyst 0.96g, obtain vinyl three-(2- methoxyethoxy)-silane production
Product 277g, yield 99.0%.It is 99.3% using its content of gas chromatographic detection.
Embodiment 3
Equipped with magnetic agitation, thermometer, spherical condensation tube 1000ml four-hole boiling flask in vinyl trimethoxy is added
Silane 148g, glycol monoethyl ether 228g, 1g anhydrous slufuric acid ferrous ammonium.It is warming up to 70-80 DEG C, reacts 4h.Then heating starts
Methanol is evaporated off, when temperature rises to 100 DEG C, Methanol Recovery is finished, and it is 90g that quantity of methyl alcohol, which is obtained,.Then cool down, when being cooled to 50
After under DEG C, filtering, recycling obtains double salt ester exchange catalyst 0.96g, obtains vinyl three-(2- methoxyethoxy)-silane
Product 276g, yield 98.5%.It is 99.3% using its content of gas chromatographic detection.
By example 1-3 it can be found that catalytic effect is more preferable, the reaction time when ester exchange catalyst selects aluminum aluminum sulfate
It is short, and product content is high.So selecting aluminum aluminum sulfate to carry out recycling reuses experiment.
The catalyst 1g of every pot of investment in embodiment 1-3, but the catalyst that recycling obtains is 0.96g, in order to keep urging
The amount of agent is constant, so the new catalyst of 0.04g is added in each pot of meeting when the reply for making catalyst is using experiment.It is other
Reaction condition is identical as example 1, so repeats reaction 10 times, the yield and content results of product are as follows:
Quality/product theory the quality of product yield=vinyl three-(2- methoxyethoxy)-silane
Claims (1)
1. a kind of ester exchange method for preparing vinyl three-(2- methoxyethoxy)-silane, which is characterized in that it includes following
Step:
1) vinyltrimethoxysilane, is added into flask, glycol monoethyl ether is as reaction substrate, vinyl trimethoxy
The mass ratio of the material of silane and glycol monoethyl ether is 1:3；
2) double salt ester exchange catalyst, is added into the mixture, double salt ester exchange catalyst is anhydrous potassium aluminium sulfate, anhydrous sulphur
Any one of sour ferripotassium, anhydrous slufuric acid ferrous ammonium, double salt ester exchange catalyst dosage account for the 0.1-0.5% of reactant gross mass；
3) reaction system, is heated, reaction temperature is made to rise to 70-80 DEG C, vinyltrimethoxysilane and glycol monoethyl ether
Ester exchange reaction occurs；
4) it after, reacting 2h, starts to warm up and methanol is evaporated off, when temperature in the kettle rises to 100 DEG C, recycling obtains the first of theoretical amount
Alcohol, while most double salt catalyst also evolution reaction system therewith；
5) 50 DEG C, are cooled to hereinafter, filtering, obtains double salt ester exchange catalyst and give over to next pot of use, and obtain colorless and transparent
Vinyl three-(2- methoxyethoxy)-silane, yield 98.5-99.5%, through gas chromatographic detection, content is
99.2-99.5% can be used directly as product；
Step 5) is recycled into gained double salt catalyst collection, instead of raw catelyst for reacting, reuse 10 times, catalyst
Activity still maintains.
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| CN110591106B (en) * | 2019-09-11 | 2022-03-15 | 西北工业大学 | Phosphorus-silicon synergistic flame retardant with hyperbranched structure and preparation method thereof |
| CN112708135B (en) * | 2020-12-29 | 2022-10-21 | 江西晨光新材料股份有限公司 | Degradable organic silicon elastomer and synthesis method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085220A (en) * | 1992-09-30 | 1994-04-13 | 哈尔滨化工研究所 | Production method of pollution-free organo-silicon coupling agent and products thereof |
| CN1489593A (en) * | 2001-03-02 | 2004-04-14 | ��³�նٹ�˾ | Continuous transesterification process for alkoxyorganosilicon compounds |
| CN105273851A (en) * | 2014-06-17 | 2016-01-27 | 中国石油化工股份有限公司 | Method for preparing fatty acid ester |
| JP2016053021A (en) * | 2014-09-03 | 2016-04-14 | 国立研究開発法人産業技術総合研究所 | Alkoxysilanes, and oligosiloxanes and method for producing the same |
-
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- 2016-08-12 CN CN201610655812.9A patent/CN106349276B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085220A (en) * | 1992-09-30 | 1994-04-13 | 哈尔滨化工研究所 | Production method of pollution-free organo-silicon coupling agent and products thereof |
| CN1489593A (en) * | 2001-03-02 | 2004-04-14 | ��³�նٹ�˾ | Continuous transesterification process for alkoxyorganosilicon compounds |
| CN105273851A (en) * | 2014-06-17 | 2016-01-27 | 中国石油化工股份有限公司 | Method for preparing fatty acid ester |
| JP2016053021A (en) * | 2014-09-03 | 2016-04-14 | 国立研究開発法人産業技術総合研究所 | Alkoxysilanes, and oligosiloxanes and method for producing the same |
Non-Patent Citations (3)
| Title |
|---|
| 乙烯基三(β-甲氧乙氧基)硅烷的合成及其偶联效果;林开涵等;《福州大学学报》;19821231;83-88页 |
| 乙烯基三(β-甲氧基乙氧基)硅烷的合成工艺研究;马梅红等,;《精细与专用化学品》;20110731;12-15页 |
| 新型功能硅烷偶联剂的催化合成、表征新型功能硅烷偶联剂的催化合成、表征新型功能硅烷偶联剂的催化合成、表征与研究;王珊珊;《曲阜师范大学硕士学位论文》;20121128;第五章 |
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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. |