CN101781328A - Preparation method of cyclosiloxane - Google Patents
Preparation method of cyclosiloxane Download PDFInfo
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- CN101781328A CN101781328A CN201010101577A CN201010101577A CN101781328A CN 101781328 A CN101781328 A CN 101781328A CN 201010101577 A CN201010101577 A CN 201010101577A CN 201010101577 A CN201010101577 A CN 201010101577A CN 101781328 A CN101781328 A CN 101781328A
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- cyclosiloxane
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- organoalkoxysilane
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Abstract
The invention discloses a preparation method of cyclosiloxane. The method comprises the following steps: evenly mixing bifunctional alkoxy silane and aromatic hydrocarbon; dropwise adding the mixture into a mixed solvent system containing basic catalyst, the aromatic hydrocarbon, water and dioxane or tetrahydrofuran for reacting for a while at a certain temperature; and then separating to obtain the cyclosiloxane. The invention has the best advantages of greatly improving the yield of products, reducing by-products, and being widely applied to the production field of preparing the cyclosiloxane by utilizing the bifunctional alkoxy silane.
Description
Technical field
The present invention relates to a kind of preparation method of cyclosiloxane, belong to the organosilicon synthesis technical field.
Background technology
Cyclosiloxane is an intermediate feed important in the organosilicon industry, is widely used in synthetic silicone oil, silicone resin and raw-silastic continuously etc.About the preparation of cyclosiloxane, mainly contain three kinds of methods: hydrolysis method, pyrolysis method and dechlorinating process.Wherein traditional preparation method is the hydrolytic rupture method of chlorosilane or organoalkoxysilane, be about to the hydrolyzate that silane elder generation hydrolysis generation mixed methylcyclosiloxane and siloxanes linear body are formed, hydrolyzate can obtain mixed methylcyclosiloxane through vacuum catalytic cracking under catalyst action then.But there is the problem of following several respects in it: (1) chlorosilane purity is not high, and hydrolysis rate is very fast, is difficult to control, and the cyclosiloxane purity that makes can not satisfy the requirement of high purity ring body; (2) higher owing to temperature of reaction in hydrolyzate vacuum cracking process, the part side reaction can take place, cause the product purity drop of cyclosiloxane.
The research worker finds to adopt the hydrolysis of organoalkoxysilane substituted chlorosilane can improve the productive rate and the purity of cyclosiloxane, the patent No. is that 200910096804.5 patents have proposed to be raw material with high-purity methyl phenyl dialkoxy silicane, not contain the method for the aminomethyl phenyl mixed methylcyclosiloxane of trifunctional impurity by hydrolytic condensation and cracking technology preparation a kind of: with aminomethyl phenyl dialkoxy silicane replacement dichloromethyl phenylsilane is the aminomethyl phenyl mixed methylcyclosiloxane that feedstock production does not contain trifunctional impurity.But use solvent in the not mentioned hydrolytic process of patent.The patent No. be 200810120384.5 patents with acid as hydrolyst, the p-methylphenyl organoalkoxysilane is hydrolyzed and has prepared the methyl phenyl ring siloxane of higher yields.But under an acidic catalyst certain condition silicon-carbon bonds there is destruction, can brings some side reactions to system.
Summary of the invention
The present invention is directed to deficiency of the prior art, a kind of preparation method of cyclosiloxane is provided, this kind method adopts the catalyzer of alkaloids as difunctionality organoalkoxysilane hydrolysis reaction, being used mixed solvent is hydrolyzed and prepares cyclosiloxane, not only do not have side reaction to take place, and improved the yield of cyclosiloxane greatly.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of cyclosiloxane comprises the steps:
(1) organoalkoxysilane and aromatic hydrocarbons are mixed, obtain the mixed system of organoalkoxysilane and aromatic hydrocarbons;
(2) aromatic hydrocarbons, water are mixed with dioxane or tetrahydrofuran (THF) obtain mixed solvent, in this mixed solvent, add catalyzer and fully stir, make catalyst dissolution, obtain mixed solvent system;
(3) mixed system of organoalkoxysilane that under 0-80 ℃ step (1) is obtained and aromatic hydrocarbons is added drop-wise in the mixed solvent system that step (2) obtains, and after dropwising, continues reaction 60-150min;
(4) will react the back mixture heating up to 60-80 ℃, steam the alcohols material that reaction generates;
(5) static layering is taken out organic phase, after steaming desolventizes, obtains cyclosiloxane.
Among the preparation method of above-mentioned a kind of cyclosiloxane, described organoalkoxysilane be in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl hydrogen dimethoxy silane, methyl ethylene dimethoxy silane, the methyl trifluoro propyl dimethoxy silane any one or more.
Among the preparation method of above-mentioned a kind of cyclosiloxane, described aromatic hydrocarbons is benzene,toluene,xylene, preferred toluene.
Among the preparation method of above-mentioned a kind of cyclosiloxane, the organoalkoxysilane described in the step (1) and aromatic hydrocarbons can arbitrary volume than mixing, preferred organoalkoxysilane and aromatic hydrocarbons volume ratio are 1: 1.
Among the preparation method of above-mentioned a kind of cyclosiloxane, described catalyzer is one or more in alkali metal hydroxide, quaternary ammonium hydroxide, the quaternary phosphonium alkali.
Described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide or rubidium hydroxide, preferred sodium hydroxide.
Described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, trimethylammonium ethyl ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH, preferred Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
Described quaternary phosphonium alkali is tetrabutylammonium hydroxide phosphorus.
Among the preparation method of above-mentioned a kind of cyclosiloxane, in the described mixed solvent system of step (2), aromatic hydrocarbons: dioxane or tetrahydrofuran (THF) volume ratio are 1: 0.1-1, preferred 1: 0.2; Aromatic hydrocarbons: the volume ratio of organoalkoxysilane is 0.1-3: 1.
Among the preparation method of above-mentioned a kind of cyclosiloxane, in the described mixed solvent system, the consumption of water is with reference to organoalkoxysilane, and wherein the mol ratio of organoalkoxysilane and water is 1: 2-30, preferred 1: 15.
Among the preparation method of above-mentioned a kind of cyclosiloxane, described catalyst consumption is with reference to organoalkoxysilane, and its consumption is the 0.1%-10% of the quality of organoalkoxysilane, is preferably 2%.
Among the preparation method of above-mentioned a kind of cyclosiloxane, the described rate of addition of step (3) is that 1-3 drips/second, oyster white do not occur with system and is advisable; The preferred 60-70 of temperature ℃.
The preparation method of a kind of cyclosiloxane of the present invention has following effect or advantage:
Adopt specific mixed solvent system, controlled the hydrolysis rate of difunctionality organoalkoxysilane effectively, promote the low molecular weight polysiloxane cyclization, obtained the organo-siloxane ring body of high yield.Compare effective hydrolysis reaction speed of having controlled with background technology, help the generation of cyclosiloxane, reduced the generation of linear polysiloxanes, effectively improved the productive rate of cyclosiloxane.Solvent can repeatedly recycle in the preparation process, has reduced environmental pollution, is suitable for industrialization production.
Embodiment
Below by embodiment the present invention is specifically described, be necessary to be pointed out that at this: present embodiment only is used for the present invention is further specified, but does not limit to its scope.
Embodiment 1:
In the 1000ml there-necked flask of stirring, thermometer and dropping funnel is housed, add 40ml dioxane, 200ml toluene, 200ml deionized water, 4gNaOH, stir, system temperature is controlled at 60 ℃.Slowly splash into the mixed solution of 200ml aminomethyl phenyl dimethoxy silane and 200ml toluene, after dropwising, continue reaction 2h.Progressively be warming up to 80 ℃ then, the methyl alcohol that reaction is generated steams.Stopped reaction leaves standstill the branch water-yielding stratum, and oil reservoir washes with water to neutrality, drying, and steaming desolventizes, and obtains the 134.6g hydrolyzate, and yield is 90%.
Embodiment 2:
Press the identical method of embodiment 1, change catalyst type, fix its consumption and be 2% of organoalkoxysilane quality, gained result such as following table 1.
Table 1
Embodiment 3:
Press the identical method of embodiment 1, selecting Tetramethylammonium hydroxide is that catalyzer changes catalyst levels, gained result such as following table 2.
Table 2
Embodiment 4:
Press the identical method of embodiment 1, change proportioning raw materials, gained result such as following table 3.
Table 3
Embodiment 5:
Press the identical method of embodiment 1, change the system hydrolysis temperature, gained result such as following table 4.
Table 4
Embodiment 6:
In the 1000ml there-necked flask of stirring, thermometer and dropping funnel is housed, add 40ml dioxane, 200ml toluene, 100ml deionized water, 4gNaOH, stir, system temperature is controlled at 60 ℃.Slowly splash into the mixed solution of 200ml methyl trifluoro propyl dimethoxy silane and 200ml toluene, after dropwising, continue reaction 2h.Progressively be warming up to 80 ℃ then, the methyl alcohol that reaction is generated steams.Stopped reaction leaves standstill the branch water-yielding stratum, and oil reservoir washes with water to neutrality, drying, and steaming desolventizes, and obtains the 157.7g hydrolyzate, and yield is 92%.
Claims (10)
1. the preparation method of a cyclosiloxane is characterized in that comprising the steps:
(1) organoalkoxysilane and aromatic hydrocarbons are mixed, obtain the mixed system of organoalkoxysilane and aromatic hydrocarbons;
(2) aromatic hydrocarbons, water are mixed with dioxane or tetrahydrofuran (THF) obtain mixed solvent, in this mixed solvent, add catalyzer and fully stir, make catalyst dissolution, obtain mixed solvent system;
(3) mixed system of organoalkoxysilane that under 0-80 ℃ step (1) is obtained and aromatic hydrocarbons is added drop-wise in the mixed solvent system that step (2) obtains, and after dropwising, continues reaction 60-150min;
(4) will react the back mixture heating up to 60-80 ℃, steam the alcohols material that reaction generates;
(5) static layering is taken out organic phase, after steaming desolventizes, obtains cyclosiloxane.
2. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that, described organoalkoxysilane be in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl hydrogen dimethoxy silane, methyl ethylene dimethoxy silane, the methyl trifluoro propyl dimethoxy silane any one or more.
3. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that described aromatic hydrocarbons is benzene, toluene or dimethylbenzene.
4. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that, the organoalkoxysilane described in the step (1) and aromatic hydrocarbons can arbitrary volume than mixing.
5. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that the described catalyzer of step (2) is one or more in alkali metal hydroxide, quaternary ammonium hydroxide, the quaternary phosphonium alkali.
6. according to the preparation method of the described a kind of cyclosiloxane of claim 5, it is characterized in that described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide or rubidium hydroxide; Described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, trimethylammonium ethyl ammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH or TBAH; Described quaternary phosphonium alkali is tetrabutylammonium hydroxide phosphorus.
7. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that in the described mixed solvent system of step (2), aromatic hydrocarbons: dioxane or tetrahydrofuran (THF) volume ratio are 1: 0.1-1, aromatic hydrocarbons: the volume ratio of organoalkoxysilane is 0.1-3: 1.
8. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that in the described mixed solvent system of step (2), the mol ratio of organoalkoxysilane and water is 1: 2-30.
9. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that described catalyst consumption is the 0.1%-10% of the quality of organoalkoxysilane.
10. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that the described rate of addition of step (3) is that 1-3 drips/second; Temperature is 60-70 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626798A (en) * | 2013-12-12 | 2014-03-12 | 中蓝晨光化工研究设计院有限公司 | Preparation method of methylphenyl cyclosiloxane without containing polyfunctional impurities |
| CN103881094A (en) * | 2014-01-14 | 2014-06-25 | 杭州师范大学 | Synthetic method of large cyclosiloxane |
| CN105085567A (en) * | 2015-08-25 | 2015-11-25 | 浙江大学 | Multiple functional groups co-substituted cyclosiloxane, cyclosiloxane mixture, and preparation method and application of cyclosiloxane mixture |
| CN105622663A (en) * | 2016-02-29 | 2016-06-01 | 山东东岳有机硅材料有限公司 | Preparation method of methylphenylcyclosiloxane |
| CN109355009A (en) * | 2018-09-30 | 2019-02-19 | 浙江凌志新材料有限公司 | A kind of organosilicon static conductive coating based on silicon substrate glyoxaline ion liquid |
| CN110128464A (en) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | A kind of preparation method of methyl dimethoxysilane |
| CN113773499A (en) * | 2021-09-29 | 2021-12-10 | 安徽硅宝有机硅新材料有限公司 | Functional silane macromolecular polymer, preparation method, additive and application |
| WO2022047778A1 (en) * | 2020-09-07 | 2022-03-10 | Wacker Chemie Ag | Method of preparing alkyl functionalized polysiloxane |
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2010
- 2010-01-27 CN CN2010101015773A patent/CN101781328B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626798A (en) * | 2013-12-12 | 2014-03-12 | 中蓝晨光化工研究设计院有限公司 | Preparation method of methylphenyl cyclosiloxane without containing polyfunctional impurities |
| CN103626798B (en) * | 2013-12-12 | 2016-01-20 | 中蓝晨光化工研究设计院有限公司 | A kind of not containing the preparation method of polyfunctionality impurity methyl phenyl ring siloxane |
| CN103881094B (en) * | 2014-01-14 | 2016-03-30 | 杭州师范大学 | A kind of synthetic method of large annular siloxane |
| CN103881094A (en) * | 2014-01-14 | 2014-06-25 | 杭州师范大学 | Synthetic method of large cyclosiloxane |
| CN105085567B (en) * | 2015-08-25 | 2018-04-20 | 浙江大学 | Cyclosiloxane that polyfunctional group substitutes altogether, ring siloxane mixture and its preparation method and application |
| CN105085567A (en) * | 2015-08-25 | 2015-11-25 | 浙江大学 | Multiple functional groups co-substituted cyclosiloxane, cyclosiloxane mixture, and preparation method and application of cyclosiloxane mixture |
| CN105622663A (en) * | 2016-02-29 | 2016-06-01 | 山东东岳有机硅材料有限公司 | Preparation method of methylphenylcyclosiloxane |
| CN109355009A (en) * | 2018-09-30 | 2019-02-19 | 浙江凌志新材料有限公司 | A kind of organosilicon static conductive coating based on silicon substrate glyoxaline ion liquid |
| CN109355009B (en) * | 2018-09-30 | 2021-02-19 | 浙江凌志新材料有限公司 | Organosilicon static conductive coating based on silicon-based imidazole ionic liquid |
| CN110128464A (en) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | A kind of preparation method of methyl dimethoxysilane |
| CN110128464B (en) * | 2019-06-25 | 2022-01-11 | 湖北江瀚新材料股份有限公司 | Preparation method of methyldimethoxysilane |
| WO2022047778A1 (en) * | 2020-09-07 | 2022-03-10 | Wacker Chemie Ag | Method of preparing alkyl functionalized polysiloxane |
| CN113773499A (en) * | 2021-09-29 | 2021-12-10 | 安徽硅宝有机硅新材料有限公司 | Functional silane macromolecular polymer, preparation method, additive and application |
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| CN101781328B (en) | 2012-07-11 |
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