CN101781328B - Preparation method of cyclosiloxane - Google Patents
Preparation method of cyclosiloxane Download PDFInfo
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- CN101781328B CN101781328B CN2010101015773A CN201010101577A CN101781328B CN 101781328 B CN101781328 B CN 101781328B CN 2010101015773 A CN2010101015773 A CN 2010101015773A CN 201010101577 A CN201010101577 A CN 201010101577A CN 101781328 B CN101781328 B CN 101781328B
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- cyclosiloxane
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- organoalkoxysilane
- aromatic hydrocarbons
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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 through 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; Be used mixed solvent and be hydrolyzed and prepare cyclosiloxane, not only do not have side reaction to take place, and improved the yield of cyclosiloxane greatly.
For realizing above-mentioned purpose, 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 THF obtain mixed solvent, in this mixed solvent, add catalyzer and fully stir, make catalyst dissolution, obtain mixed solvent system;
(3) organoalkoxysilane that under 0-80 ℃, step (1) is obtained and the mixed system of aromatic hydrocarbons are added drop-wise in the mixed solvent system that step (2) obtains, and after dropwising, continue 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, said 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, said 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 Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, cesium hydroxide or rubidium hydroxide, preferred sodium hydroxide.
Described quaternary ammonium hydroxide is TMAH, trimethylammonium ethyl volatile caustic, tetraethyl ammonium hydroxide, TPAOH or TBAH, preferred TMAH 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 said mixed solvent system of step (2), aromatic hydrocarbons: dioxane or 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 said 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, said 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 according to the 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
Through embodiment the present invention is specifically described below, 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, TM and tap 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 the oil reservoir water is washed till 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, fixing its consumption is 2% of organoalkoxysilane quality, gained result such as following table 1.
Table 1
Embodiment 3:
Press the identical method of embodiment 1, selecting TMAH 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, TM and tap 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 the oil reservoir water is washed till neutrality, drying, and steaming desolventizes, and obtains the 157.7g hydrolyzate, and yield is 92%.
Claims (8)
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; Said 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;
(2) aromatic hydrocarbons, water are mixed with dioxane or THF obtain mixed solvent, in this mixed solvent, add catalyzer and fully stir, make catalyst dissolution, obtain mixed solvent system; Described catalyzer is one or more in alkali metal hydroxide, quaternary ammonium hydroxide, the quaternary phosphonium alkali.
(3) organoalkoxysilane that under 0-80 ℃, step (1) is obtained and the mixed system of aromatic hydrocarbons are added drop-wise in the mixed solvent system that step (2) obtains, and after dropwising, continue 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 said aromatic hydrocarbons is benzene, toluene or YLENE.
3. 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.
4. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that described alkali metal hydroxide is Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, cesium hydroxide or rubidium hydroxide; Described quaternary ammonium hydroxide is TMAH, trimethylammonium ethyl volatile caustic, tetraethyl ammonium hydroxide, TPAOH or TBAH; Described quaternary phosphonium alkali is tetrabutylammonium hydroxide phosphorus.
5. according to the preparation method of the described a kind of cyclosiloxane of claim 1; It is characterized in that; In the said mixed solvent system of step (2), aromatic hydrocarbons: dioxane or THF volume ratio are 1: 0.1-1, the volume ratio of the described organoalkoxysilane of aromatic hydrocarbons and step (1) is 0.1-3: 1.
6. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that the mol ratio of water is 1 in described organoalkoxysilane of step (1) and the said mixed solvent system of step (2): 2-30.
7. according to the preparation method of the described a kind of cyclosiloxane of claim 1, it is characterized in that said catalyst consumption is the 0.1%-10% of the quality of organoalkoxysilane.
8. 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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| CN2010101015773A CN101781328B (en) | 2010-01-27 | 2010-01-27 | Preparation method of cyclosiloxane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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 |
| 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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