CN102372736B - Method for preparing methyl hydrocyclosiloxane - Google Patents
Method for preparing methyl hydrocyclosiloxane Download PDFInfo
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- CN102372736B CN102372736B CN201110350297.0A CN201110350297A CN102372736B CN 102372736 B CN102372736 B CN 102372736B CN 201110350297 A CN201110350297 A CN 201110350297A CN 102372736 B CN102372736 B CN 102372736B
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- hydrogen
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Abstract
The invention provides a method for preparing methyl hydrocyclosiloxane. Methyl hydrochlorosilane is used as a raw material, low-boiling-point hydrocarbon compounds are used as solvents, the hydrolytic polycondensation reaction is carried out under the effect of template agents at the temperature lower than 15 DEG C, organic phases are washed by water and are neutralized after the standing lamination, the solvents are firstly distilled, then, the pressure-reduction rectification is carried out, and trimethyl hydrocyclotrisiloxane (D3H), tetramethyl hydrotetrasiloxane (D4H), pentamethyl hydrocyclopentasiloxane (D5H) and hexamethyl hydrohexasiloxane (D6H) are respectively prepared. The method has the advantages that alcohol is not used as the solvents, the low-boiling-point hydrocarbons are used as the solvents, the template agents with low price are used, the production cost is greatly reduced, and in addition, various products using methyl hydro-ring bodies can be prepared by adopting the solvents and the temperate agents with different properties.
Description
Technical field
The present invention relates to a kind of preparation method of methylhydracyclosiloxane, relate in particular to and a kind ofly with template and low boiling point hydrocarbon, as solvent, prepare the method for methylhydracyclosiloxane.
Background technology
Methylhydracyclosiloxane is widely used for preparing multiple modified silicon oil and high-quality containing hydrogen silicone oil, also can be used as the linking agent of silicon rubber, anti-yellowing dose, it is again the hydrogen-containing siloxane ［ HSi (OSiH that the good sealing material of electronic industry and preparation have Si-H key function simultaneously
2)-O-SiH
3intermediate.
The preparation of alkyl hydrogen cyclosiloxane mainly contains two kinds of methods, a kind of is to take alkyl hydrogen two halosilanes as raw material is at Water in Organic Solvents solution, stratification, redistillation makes, and another kind is that rectifying makes by the poly-alkyl hydrogen siloxanes cracking under alkaline catalysts effect of line style.
James W.Carry etc. are at USP 3,484, have introduced methyl hydrogen dichlorosilane in 468 to be hydrolyzed in triol and benzene, and the total recovery of methyl hydrogen ring body is 66.2%, and the yield of line body reaches 33.8%.
Xie Mouzheng etc. are added drop-wise to after adopting alkane and methyl hydrogen dichlorosilane to mix in Chinese patent 2139222.6 in the mixed solvent of alkane, first alcohol and water and are hydrolyzed, and the total ring yield obtaining is up to 88.96%, tetramethyl-hydrogen cyclotetrasiloxane (D
4 h) yield be up to 52.31%, this technique has been used methyl alcohol and two kinds of mixed solvents of alkane, has increased separation circuit, and use methyl alcohol to environment structure unsafe factor.
USP3714213 has narrated the method that under alkaline catalysts exists Pintsch process linear polysiloxanes is prepared cyclosiloxane, and because this technique will first be produced polysiloxane, step is various, is not widely used.
Zhang Yuanping etc. have introduced methyl hydrogen dichlorosilane in 36 10 phases of volume of New Chemical Materials and have been hydrolyzed in ether solvent, by hydrolyzate cracking under base catalysis, rectifying, obtain D
4 h, productive rate reaches 95% this article and all regards the hydrolyzate of methyl hydrogen dichlorosilane as silicon diol.
Woods money market etc. have been introduced the preparation method of methylhydracyclosiloxane on silicone oil in 2010 and secondary processing product information exchanging meeting (collection of thesis 118-120 page), but the particular content of undeclared its hydrolysis and cracking Preparation Method.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of methylhydracyclosiloxane, the method is made solvent without alcohols, adopt low boiling point hydrocarbon to make solvent, use inexpensive template, reduce production costs greatly, and can make the various products of methyl hydrogen ring body as master of take with template of different nature and solvent.
The object of the present invention is achieved like this, the alkyl hydrogen halosilanes of take is raw material, with low boiling hydrocarbon compound, it is solvent, alkyl hydrogen halosilanes is splashed in the mixed solvent being comprised of water, template and low boiling hydrocarbon compound under constantly stirring to the polycondensation that is hydrolyzed at a certain temperature, standing minute water-yielding stratum, organic phase is washed with water to be neutralized to pH be 7 again, first steam solvent, then rectification under vacuum, make respectively trimethylammonium hydrogen cyclotrisiloxane (D
3 h), tetramethyl-hydrogen cyclotetrasiloxane (D
4 h), pentamethyl-hydrogen D5 (D
5 h) and hexamethyl hydrogen ring six siloxanes (D
6 h); The volume ratio of alkyl hydrogen halosilanes and solvent is 1:5, and it is best than being 1:1; The volume ratio of water and solvent is 1:3, and it is best than being 1:1; The mol ratio of alkyl hydrogen halosilanes and template is 1:0.01 to 0.15, and its optimum mole ratio is 1:0.05 to 0.1; The open loop under acid or base catalysis of the remaining raffinate of rectifying and linear polysiloxanes is back to hydrolyzed solution row rectifying again after resetting.Halogen in described alkyl halosilanes is chlorine, bromine, iodine, and the best is chlorine.Alkyl in alkyl halosilanes is alkyl, thiazolinyl, alkynyl and aryl.Its best is alkyl chlorosilane.Wherein take methyl hydrogen dichlorosilane as best.Described low boiling hydrocarbon compound is that boiling range is the sherwood oil of 30-60 ℃; Described template is alkaline earth metal compound BaCl2, CaCl2, Ca (OH), alkali metal compound NaHCO
3, Na
2cO
3, inorganic ammonium salt NH
4cl.
Advantage of the present invention: make solvent without alcohols, adopt low boiling point hydrocarbon to make solvent; Use inexpensive template, reduce production costs greatly; And can make the various products of methyl hydrogen ring body as master of take with template of different nature and solvent.
Concrete embodiment
embodiment 1
The hydrolysising experiment of alkyl hydrogen halosilanes carries out in tri-mouthfuls of beakers of 500ml that thermometer, dropping funnel and reflux condensing tube (HCl gas is derived in one end) is housed.Under fierce magnetic agitation, 72ml methyl hydrogen dichlorosilane is splashed into equably and fills 72ml water, 26.6 grams of CaCl2(template), in the reaction flask of 72ml sherwood oil (boiling range 30-60 ℃), temperature of reaction is by rate of addition and frozen water is cooling controls, and makes it to be no more than 15 ℃.After dripping, continue at the same temperature reaction 1 hour, then pour in separating funnel, stratification, by a small amount of water washing organic phase, then uses saturated NaHCO
3it is 7 that solution is neutralized to pH, finally uses Na
2cO
3dry, steam solvent, then rectification under vacuum, collect each fraction, with gas chromatograph, analyze the composition of each fraction, acquired results is in Table 1.
embodiment 2
Methyl hydrogen dichlorosilane consumption is 72ml, H
2o 72ml, template CaCl
2consumption 7.3g
Solvent C H
2cl
272ml, temperature of reaction 10-12 ℃, experimental installation and operation steps, with embodiment 1, the results are shown in Table 1.
embodiment 3
Methyl hydrogen dichlorosilane, water, sherwood oil (boiling range 30-60 ℃) are respectively 72ml, and template is still CaCl
2, but its consumption is down to 0.6g, temperature of reaction 10-13 ℃, and other the results are shown in Table 1 with embodiment 1.
embodiment 4
Methyl hydrogen dichlorosilane, template, solvent and consumption thereof are all identical with embodiment 3, and water 72ml used is the sour water that after embodiment 3 hydrolysis, stratification is emitted, and reuses in the present embodiment.Discovery is hydrolyzed under acidic conditions, gained D
4 hand D
5 hcontent increase.Other are with embodiment 1, and the results are shown in Table 1.
embodiment 5
Template is NH
4cl, consumption is 12.8g, other,, with embodiment 1, the results are shown in Table 1.
By table, found out gained D
5 hcontent is the highest.
embodiment 6
Template is NaHCO
3, consumption is 8.5g, other,, with embodiment 1, the results are shown in Table 1.
embodiment 7
Template is Ca (OH)
2, consumption is 0.4g, other,, with embodiment 1, the results are shown in Table 1.
embodiment 8
Template is BaCl
2, consumption is 1.04, and solvent is sherwood oil (30-60 ℃) 72ml, and other,, with embodiment 1, the results are shown in Table 1.
embodiment 9
The consumption of methyl hydrogen dichlorosilane, water and template is all identical with embodiment 8, and solvent is CH
2cl
2, its consumption is 72ml, other,, with embodiment 1, the results are shown in Table 1.
embodiment 10
Methyl hydrogen dichlorosilane 216ml, H
2o 216ml, template CaCl
221.9g.
Solvent C H
2cl
2216ml, the reaction that is hydrolyzed in 2000ml reaction flask, other,, with embodiment 1, the results are shown in Table 1.
embodiment 11
Methyl hydrogen dichlorosilane 216ml, H
2o 216ml, template BaCl
212g and NH
4cl 6g, solvent C H
2cl
2216ml, the reaction that is hydrolyzed in 2000ml reaction flask, other,, with embodiment 1, the results are shown in Table 1.
embodiment 12
Methyl hydrogen dichlorosilane 144ml, H
2o 144ml, template NaHCO
38.5g and NH
4cl 12g, solvent C H
2cl 144ml, the reaction that is hydrolyzed in 1000ml reaction flask, other,, with embodiment 1, the results are shown in Table 1.
Table 1
Claims (3)
1. the preparation method of a methylhydracyclosiloxane, it is characterized in that take that alkyl hydrogen halosilanes is raw material, with low boiling hydrocarbon compound, it is solvent, alkyl hydrogen halosilanes is splashed in the mixed solvent being comprised of water, template and low boiling hydrocarbon compound under constantly stirring to the polycondensation that is hydrolyzed at a certain temperature, standing minute water-yielding stratum, organic phase is washed with water to be neutralized to pH be 7 again, first steam solvent, then rectification under vacuum, make respectively trimethylammonium hydrogen cyclotrisiloxane (D
3 h), tetramethyl-hydrogen cyclotetrasiloxane (D
4 h), pentamethyl-hydrogen D5 (D
5 h) and hexamethyl hydrogen ring six siloxanes (D
6 h); The volume ratio of alkyl hydrogen halosilanes and solvent is 1:5; The volume ratio of water and solvent is 1:3; The mol ratio of alkyl hydrogen halosilanes and template is 1:0.01 to 0.15; The open loop under acid or base catalysis of the remaining raffinate of rectifying and linear polysiloxanes is back to hydrolyzed solution row rectifying again after resetting, and described low boiling hydrocarbon compound is that boiling range is the sherwood oil of 30-60 ℃.
2. the preparation method of methylhydracyclosiloxane according to claim 1, is characterized in that described alkyl hydrogen halosilanes is methyl hydrogen dichlorosilane.
3. the preparation method of methylhydracyclosiloxane according to claim 1, is characterized in that described template is alkaline earth metal compound
,
,
, alkali metal compound NaHCO
3, Na
2cO
3, inorganic ammonium salt NH
4cl.
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|---|---|---|---|
| CN201110350297.0A CN102372736B (en) | 2011-11-09 | 2011-11-09 | Method for preparing methyl hydrocyclosiloxane |
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| CN201110350297.0A CN102372736B (en) | 2011-11-09 | 2011-11-09 | Method for preparing methyl hydrocyclosiloxane |
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| CN102372736B true CN102372736B (en) | 2014-05-07 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349846B (en) * | 2013-07-09 | 2015-04-01 | 浙江合盛硅业有限公司 | Device for rectifying and purifying decamethyl cyclopenta siloxane through organosilicon high boiling point compound and purifying process |
| CN103924259A (en) * | 2014-04-22 | 2014-07-16 | 浙江合盛硅业有限公司 | Method for preparing poly(dialkyl cyclosiloxane) at room temperature |
| CN104292253B (en) * | 2014-09-12 | 2016-08-24 | 江西多林科技发展有限公司 | The preparation method of alkyl cyclosiloxane |
| CN110093782B (en) * | 2019-05-29 | 2021-05-18 | 杭州美高华颐化工有限公司 | Preparation method of low-foam silicon-containing degreasing agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3484468A (en) * | 1967-06-16 | 1969-12-16 | Texas Instruments Inc | Method for preparation of cyclic organohydrosiloxanes |
| US3714213A (en) * | 1971-01-06 | 1973-01-30 | Gen Electric | Method of making cyclopolysiloxanes containing silanic hydrogen |
| CN1410430A (en) * | 2002-10-28 | 2003-04-16 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Synthesis method of methylhydro cyclo siloxane |
-
2011
- 2011-11-09 CN CN201110350297.0A patent/CN102372736B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3484468A (en) * | 1967-06-16 | 1969-12-16 | Texas Instruments Inc | Method for preparation of cyclic organohydrosiloxanes |
| US3714213A (en) * | 1971-01-06 | 1973-01-30 | Gen Electric | Method of making cyclopolysiloxanes containing silanic hydrogen |
| CN1410430A (en) * | 2002-10-28 | 2003-04-16 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Synthesis method of methylhydro cyclo siloxane |
Non-Patent Citations (1)
| Title |
|---|
| 张院萍等，.四甲基氢环四硅氧烷(D4H)的合成与表征.《化工新型材料》.2010,第38卷(第10期),第88-90页. * |
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