CN104292253A - Preparation method of alkyl cyclosiloxane - Google Patents
Preparation method of alkyl cyclosiloxane Download PDFInfo
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- CN104292253A CN104292253A CN201410462781.6A CN201410462781A CN104292253A CN 104292253 A CN104292253 A CN 104292253A CN 201410462781 A CN201410462781 A CN 201410462781A CN 104292253 A CN104292253 A CN 104292253A
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- alkyl
- crown ether
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- halosilanes
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Abstract
The invention discloses a preparation method of alkyl cyclosiloxane. The preparation method is characterized by comprising the following steps: taking alkyl halogenosilane as a raw material, taking crown ether as a solvent and dropping the alkyl halogenosilane in a mixed solution formed by water and the crown ether while continuously stirring the alkyl halogenosilane; carrying out hydrolysis at a certain temperature to carry out condensation polymerization; standing after the reaction to carry out layering; and directly carrying out decompressed rectification on the obtained hydrolyzed oil to separate trialkylcyclotrisiloxane, tetraalkylcyclotetrasiloxane, pentaalkylcyclopentasiloxane and hexaalkylcyclohexasiloxane. The preparation method has the advantages that alcohols and low-boiling point hydrocarbons are not used as solvents, the crown ether is used as solvent and direct rectification is carried out on the prepared hydrolyzed oil to obtain the alkyl cyclosiloxane, so that the processes of washing, neutralization, drying and filtering are saved; and the solvent which undergoes standing and layering after the hydrolysis can be reused or can be cooled to a certain temperature to separate out the crown ether for recovery, so that the production cost is saved.
Description
Technical field
The present invention relates to a kind of preparation method of alkyl cyclosiloxane, particularly relate to a kind of alkyl cyclosiloxane prepared by crown ether method as solvent.
Background technology
Crown ether is the general name that a class contains the macrocylc compound of multiple Sauerstoffatom, is a kind of heterocyclic organic compounds.Common are 15-hat-5,18-hat-6, is the most simply 6-hat-2.
Alkyl cyclosiloxane especially methylhydracyclosiloxane is the good sealing material of electronic industry, also can be used for preparing the containing hydrogen silicone oil with Si-H key function, long-chain alkyl-silicone oil, polyether silicone oil, epoxy silicon oil, silicone oil of carboxyl, amido silicon oil simultaneously.Also for do silicon rubber linking agent, anti-yellowing dose.Methylvinylcyclosiloxane has been the important source material preparing silicon rubber, silicone oil and silicone resin.
The preparation of alkyl cyclosiloxane mainly contains two kinds of methods: the first is with chloric ether silane for raw material, and hydrolysis in organic solvent, stratification, again rectifying obtain.Another kind method gathers organohydrogensiloxanes cracking under alkaline catalysts effect with line style, and rectifying obtains.
James W.Carry etc. describes methyl hydrogen dichlorosilane in the trimethyl carbinol and benzene and is hydrolyzed in USP3484468, and the total recovery of methyl hydrogen ring body is 66.2%, and the yield of simple linear polymer is 33.8%.
USP5395956 describes organic hydrogen dichlorosilane and stoichiometrically water reaction, the hydrolyzate generated carries out rearrangement reaction under an inert solvent neutralizing acid catalyst action, form ring organohydrogensiloxanes, separate from solvent, and line style organohydrogensiloxanes carries out rearrangement reaction in a solvent further with souring agent effect, regenerate ring body.
Xie Mouzheng etc. are added drop-wise in alkane, first alcohol and water adopt methyl hydrogen dichlorosilane and alkane mixing in Chinese patent 2139222.6 after and are hydrolyzed.The total ring yield obtained is up to 88.96%.This technique employs two kinds of solvents, adds separation circuit, improves cost recovery.And normal hexane usage quantity is comparatively large, production efficiency is low, the unsafe factor that used methyl alcohol to environment structure.
Japanese Unexamined Patent Publication 6-80680 describes dimethyl dichlorosilane (DMCS) in tetrahydrofuran (THF) and benzene mixed solvent, is hydrolyzed obtained tetramethyl-ring tetrasiloxane (D
4 h), yield reaches 61.5%.This technique employs two kinds of solvents, adds recovery separation circuit.Improve cost recovery.
Describe Pintsch process linear polysiloxanes under alkaline catalysts in Cart J.Miller USP3714213 and prepare the method for cyclosiloxane, this technique first will produce linear polysiloxanes, and process-intensive does not widely use.
Permitted money market in Chinese patent 10170195.9, to describe cracking linear polysiloxanes under catalyst action prepare the method for tetramethyl-ring tetrasiloxane, the preparation process of undeclared linear polysiloxanes.
Describe in Japanese Unexamined Patent Publication 7-242678.1995 patent by the method for line style polymethyl siloxane cracking tetramethyl-ring tetrasiloxane.Its technique is hydrolyzed by allyl chloride to obtain line style polymethyl siloxane and cyclo-methicone mixture.Add atlapulgite and (C again
6h
13si(CH
3)
2si)
2o, at 130 DEG C---at 140 DEG C, drip the tetramethyl-hydrogen cyclotetrasiloxane that certain water gaging obtains 64%.
Lee builds and brave waits that to describe in Chinese patent CN102372736B with methylhydrochlorosilane be raw material, is solvent, is hydrolyzed under temperature is lower than 15 DEG C and template effect with low boiling hydrocarbon compound.Organic phase is carried out wash, neutralize.First steam solvent again rectification under vacuum obtain methylhydracyclosiloxane.This technique still can use low boiling hydrocarbon compound, and production still has hidden danger.
Piao Chaoyang etc. have studied Direct Synthesis of Vinylcyclosiloxanes (fine chemistry industry 20 volume 5 phase 302 pages) and describe 7 kinds of reaction solvents to the impact of product.Accreditation ether is solvent, and productive rate reaches 80.46%, and ether boiling point is low, inflammable brings hidden danger to production.
Summary of the invention
The present invention is a kind of preparation method of alkyl cyclosiloxane, and the method makes solvent without alcohol and hydro carbons, with alkyl halosilanes for raw material, through hydrolysis condensation reaction, and obtained alkyl cyclosiloxane.
The present invention is achieved like this.With alkyl halosilanes for raw material, be solvent with crown ether, by crown ether and water miscible after, under constantly stirring, alkyl halosilanes is instilled wherein uniformly.Be hydrolyzed polycondensation at a certain temperature.Reacted rear stratification, obtained hydrolysing oil, direct rectifying separation goes out trialkyl cyclotrisiloxane, tetraalkyl cyclotetrasiloxane, five alkyl D5s and six alkyl ring six siloxanes.The weight ratio of water and solvent is 1:2, it is best than being 1:0.5-1, the weight ratio of alkyl halosilanes and solvent is 1:3, and its best ratio is add rectifying again in hydrolysing oil after the remaining raffinate of 1:1. rectifying and linear polysiloxanes carry out cracking rearrangement under acid or base catalysis.Halogen in described alkyl halosilanes is chlorine, Ju, iodine, and the best is chlorine.Alkyl in alkyl halosilanes is alkyl, thiazolinyl, alkynyl or alkylalkenyl.With the best of methyl hydrogen dichlorosilane in alkyl halogen silanes.Be the best with methylvinyldichlorosilane in alkylalkenyl halosilanes.Described crown ether is 6-hat-2,9-hat-3,12-crown-4,15-hat-5 and 16-hat-6.
Advantage of the present invention: make solvent without alcohol and low boiling point hydrocarbon, employing crown ether is solvent, the direct rectifying of obtained hydrolysing oil, obtains each alkyl cyclosiloxane, saves the operations such as washing, neutralization, drying, filtration.After hydrolysis, the solvent of stratification can be reused, and also can be cooled to certain temperature and crown ether is separated out, reclaim, and saves production cost.
Specific embodiment
Embodiment 1
The hydrolysising experiment of alkyl chlorosilane is being equipped with thermometer, carries out in the 500ml there-necked flask of constant pressure funnel and reflux condensing tube (HCl gas is derived on top).Under magnetic stirring 95 grams of dimethyl dichlorosilane (DMCS)s are instilled uniformly in the there-necked flask filling 95 grams of water and 95 grams of 6-hats-2.Temperature of reaction controls below 20 DEG C, continues reaction at the same temperature 0.5 hour, then reaction solution is transferred to stratification in separating funnel after dripping.Upper liquid is carried out rectification under vacuum, obtains trimethylammonium hydrogen cyclotrisiloxane (D
3 h), tetramethyl-hydrogen cyclotetrasiloxane (D
4 h), pentamethyl-hydrogen D5 (D
5 h), hexamethyl hydrogen ring six siloxanes (D
6 h).With chromatographic each component content, the results are shown in Table 1.The remaining raffinate of rectification under vacuum and linear polysiloxanes after cracking rearrangement, are back to rectifying again in hydrolysing oil under acid or base catalysis.The subnatant of stratification is mainly crown ether and unnecessary moisture content.Can continue for dimethyl dichlorosilane (DMCS) hydrolysis.As moisture content is not enough, moisture content can be supplemented.As acidity is comparatively strong, can add in alkali and rear use.The subnatant be separated also can be cooled to certain temperature, crown ether is separated out, reaches the object of recovery.
Embodiment 2
Solvent 6-in embodiment 1 is preced with-2 and is changed to 9-hat-3(95 gram), other are constant.By the operation of embodiment 1 step, the results are shown in Table 1.
Embodiment 3
Solvent in embodiment 1 is changed to 12-crown-4, and other are constant.Operate, in table 1. by embodiment 1
Embodiment 4
Solvent in embodiment 1 is changed to 15-hat-5, other are constant.Operate by embodiment 1, the results are shown in Table 1.
Embodiment 5
Solvent in embodiment 1 is changed to 18-hat-6, is dissolved in 95 grams of water, by embodiment 1 device by 70 grams of 16-hats-6.Under magnetic stirring 95 grams of dimethyl dichlorosilane (DMCS)s are instilled in there-necked flask uniformly, operate according to embodiment 1, the results are shown in Table 1.
Embodiment 6
600 grams of distilled water and 600 grams of 6-hats-2 are added in the 3000ml there-necked flask that thermometer constant pressure funnel and reflux condensing tube (HCl gas is derived on top) are housed.Instilled uniformly in there-necked flask by dropping funnel by 600 grams of dimethyl dichlorosilane (DMCS)s under magnetic stirring, other operations are with embodiment 1, and acquired results is in table 1.
Table 1, dimethyl dichlorosilane (DMCS) experimental result
Embodiment 7
50 grams of 6-hats-2 and 50 grams of distilled water are added thermometer is housed, in the 250ml there-necked flask of constant pressure funnel and reflux condensing tube (HCl gas is derived on top), under magnetic stirring 50 grams of methylvinyldichlorosilane are instilled in there-necked flask equably by constant pressure funnel, temperature controls below 20 DEG C, and other are with embodiment 1.Rectification under vacuum obtains trimethylammonium trivinyl cyclotrisiloxane (D
3 vi), t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), pentamethyl-five vinyl D5 (D
5 vi), hexamethyl six ethene basic ring six siloxanes (D
6 vi).With the content of chromatographic each component, the results are shown in Table 2.The subnatant of stratification is mainly solvent and unnecessary moisture, can continue for methylvinyldichlorosilane hydrolysis.
Embodiment 8
Solvent in embodiment 7 is changed to 9-hat-3, other are with embodiment 7, operational condition and step with embodiment 1, in the results list 2.
Embodiment 9
Solvent in embodiment 7 is changed to 12-crown-4, and other the results are shown in Table 2. with embodiment 7 and example 1.
Embodiment 10
Solvent in embodiment 7 is changed to 15-hat-5, other the results are shown in Table 2. with embodiment 7 and example 1.
Embodiment 11
Solvent in embodiment 7 is changed to 18-hat-6,35 grams of 18-hats-6 are dissolved in 50 grams of distilled water.By 50 grams of methylvinyldichlorosilane under magnetic stirring, instill in there-necked flask equably, other, with embodiment 7 and example 1, the results are shown in Table 2.
Embodiment 12
By 400 grams of distilled water and 400 grams of 6-hat-2 miscible after add in the 200ml there-necked flask that thermometer, constant pressure funnel and reflux condensing tube (HCl gas is derived on top) are housed.Under magnetic stirring, instilled equably in there-necked flask by 400 grams of methylvinyldichlorosilane by constant pressure funnel, other are with embodiment 7 and example 1, and acquired results is in table 2.
Table 2 methylvinyldichlorosilane
Claims (6)
1. the preparation method of an alkyl cyclosiloxane, it is characterized in that with alkyl halosilanes for raw material, be solvent with crown ether, alkyl halosilanes is instilled in the mixed solution be made up of water and crown ether under constantly stirring, be hydrolyzed at a certain temperature, polycondensation, stratification, oil reservoir in hydrolyzed solution is directly carried out rectification under vacuum, obtained trialkyl cyclotrisiloxane respectively, tetraalkyl cyclotetrasiloxane, five alkyl D5s and six alkyl ring six siloxanes, the weight ratio of alkyl halosilanes and crown ether is 1:3, the weight ratio of water and crown ether is 1:2, after the remaining raffinate of rectifying and linear polysiloxanes are reset under acid or base catalysis, be back to hydrolyzed solution and carry out rectifying again.
2. the preparation method of alkyl cyclosiloxane according to claim 1, it is characterized in that the alkyl in described alkyl halosilanes is alkyl, thiazolinyl, alkynyl, the halogen in alkylalkenyl halosilanes is chlorine, bromine, iodine, and the best is chlorine.
3. alkyl halogen silanes in alkyl halosilanes according to claim 1 and 2, take dimethyl dichlorosilane (DMCS) as the best, is the best in alkylalkenyl halosilanes with methylvinyldichlorosilane.
4. the preparation method of alkyl cyclosiloxane according to claim 1, is characterized in that the weight ratio of described alkyl halosilanes and crown ether is 1:3, and the best is 1:1.
5. the preparation method of alkyl cyclosiloxane according to claim 1, is characterized in that the weight ratio of described water and crown ether is 1:2, and the best is 1:0.5-1.
6. the preparation method of alkyl siloxanes according to claim 1, is characterized in that described crown ether is 6-hat-2,9-hat-3,12-crown-4,15-hat-5 and 16-hat-6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072716A (en) * | 2020-01-06 | 2020-04-28 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN117306263A (en) * | 2023-10-18 | 2023-12-29 | 广州蓝博纺织品有限公司 | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| DE102010028170A1 (en) * | 2010-04-26 | 2011-10-27 | Evonik Degussa Gmbh | Preparing metallated hydridosilane compounds, useful for reacting with metal compounds, comprises reacting hydridosilane compound comprising a silicon group with a metallic base under the abstraction of the silicon group |
| CN102372736A (en) * | 2011-11-09 | 2012-03-14 | 江西多林科技发展有限公司 | Method for preparing methyl hydrocyclosiloxane |
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2014
- 2014-09-12 CN CN201410462781.6A patent/CN104292253B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010028170A1 (en) * | 2010-04-26 | 2011-10-27 | Evonik Degussa Gmbh | Preparing metallated hydridosilane compounds, useful for reacting with metal compounds, comprises reacting hydridosilane compound comprising a silicon group with a metallic base under the abstraction of the silicon group |
| CN102372736A (en) * | 2011-11-09 | 2012-03-14 | 江西多林科技发展有限公司 | Method for preparing methyl hydrocyclosiloxane |
Non-Patent Citations (1)
| Title |
|---|
| 补朝阳等: "直接法合成乙烯基环硅氧烷", 《精细化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072716A (en) * | 2020-01-06 | 2020-04-28 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN111072716B (en) * | 2020-01-06 | 2022-08-30 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN117306263A (en) * | 2023-10-18 | 2023-12-29 | 广州蓝博纺织品有限公司 | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
| CN117306263B (en) * | 2023-10-18 | 2024-04-30 | 广州蓝博纺织品有限公司 | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
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