CN106986890B - A kind of environment-friendly preparation method of 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane - Google Patents
A kind of environment-friendly preparation method of 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane Download PDFInfo
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- CN106986890B CN106986890B CN201710423632.2A CN201710423632A CN106986890B CN 106986890 B CN106986890 B CN 106986890B CN 201710423632 A CN201710423632 A CN 201710423632A CN 106986890 B CN106986890 B CN 106986890B
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- copyrolysis
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- cyclotrisiloxane
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- QKUBKYWIBHFWCE-UHFFFAOYSA-N 2-ethenyl-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C=C)O1 QKUBKYWIBHFWCE-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 28
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 23
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000001360 synchronised effect Effects 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 51
- 229920002554 vinyl polymer Polymers 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 6
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 9
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PUAIRHYPDYKQCV-UHFFFAOYSA-N 2,4-bis(ethenyl)-2,4,6,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 PUAIRHYPDYKQCV-UHFFFAOYSA-N 0.000 description 3
- LTIUDPOSFOYSKA-UHFFFAOYSA-N 2-ethenyl-2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C=C)O[Si](C)(C)O1 LTIUDPOSFOYSKA-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- -1 Siloxanes Chemical class 0.000 description 2
- QTYCOWZEAOOROO-UHFFFAOYSA-N [O].C[Si]C=C Chemical group [O].C[Si]C=C QTYCOWZEAOOROO-UHFFFAOYSA-N 0.000 description 2
- CNQPFYOBEOUUKV-UHFFFAOYSA-N [SiH4].C=CC Chemical compound [SiH4].C=CC CNQPFYOBEOUUKV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- FBXTUBNFTGCQPZ-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6,8,8-pentamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 FBXTUBNFTGCQPZ-UHFFFAOYSA-N 0.000 description 1
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 description 1
- HJWYBFFQDXNWHV-UHFFFAOYSA-N 2-methylcyclotrisiloxane Chemical compound C[SiH]1O[SiH2]O[SiH2]O1 HJWYBFFQDXNWHV-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBNVNSKOAADSQQ-UHFFFAOYSA-N [O].[Si].CC=C Chemical group [O].[Si].CC=C DBNVNSKOAADSQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical compound Cl[SiH2]C=C DMZWVCJEOLBQCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of environment-friendly preparation methods of 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane.This method comprises: by octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) in molar ratio 2:1 carry out pre- cracking reaction in the presence of copyrolysis catalyst and cocatalyst；Then, copyrolysis catalyst is added in 140-150 DEG C of progress copyrolysis reaction；Normal pressure is changed into negative pressure and collects copyrolysis fraction, it is synchronous while fraction produces that D is added dropwise4And D4 Vi, and keep dropwise addition total amount equal with total amount is produced；Fraction is summarized, rectifying is up to target product.The method of the present invention improves the yield and selectivity of cyclotrisiloxane, it is suppressed that the generation of cyclotetrasiloxane, while the implode of reaction raw materials, crosslinking are also avoided, have the characteristics that simple to operation, at low cost, high-efficient, environmentally friendly, safe.
Description
Technical field
The present invention relates to a kind of 2- vinyl -2,4, the environment-friendly preparation method of 4,6,6- pentamethyl cyclotrisiloxane belongs to
The synthesis field of organo-silicon compound.
Background technique
Cyclosiloxane is very important intermediate feed in organosilicon industry, is widely used in synthesizing silicone oil, silicon tree
Rouge and silicon rubber etc..With its preparation organosilicon material have excellent electric property, physiological inertia, corrosion-resistant, high-low temperature resistant,
The performances such as ageing-resistant, other high-molecular organic materials cannot be compared and be substituted, in aerospace, electric, vapour
Car and boat oceangoing ship, industry light industry textile industry, building, machinery, medicine, communications and transportation etc. are widely used, and have become national economy
In important and indispensable novel high polymer material.
2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane is to take a methyl in hexamethyl cyclotrisiloxane
On behalf of the special organosilicon ring body of vinyl.Due to containing only a vinyl in structure, there are many unique functions.Research
It has been shown that, in vulcanizing system, if two vinyl are adjacent in strand or several vinyl are crowded together, even if vulcanization is completely,
Its elasticity also corresponds to only one crosslinking points to provide.2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane and other
After organosilicon ring body ring-opening polymerisation, the vinyl methyl silicon oxygen chain link in strand is between two dimethyl silica chain links,
The appearance for avoiding vinyl coherent condition improves the crosslinking active of vinyl, compared to others during vulcanization
The utilization rate of vinyl ring body, vinyl is higher, and the effect after solidification is more significant.
The document report preparation of methyl ethylene silane mixture ring body at present, with vinyl methyl dichlorosilane monomer and
Dimethyldichlorosilane monomer is raw material, and mixed hydrolysis is prepared for methyl ethylene silane mixture ring body under acid, cryogenic conditions,
Qualitative analysis has been carried out to organosilicon methyl, vinyl ring body by gas chromatograph-mass spectrometer (GC-MS), has been specifically included that in product
D3、D4、D5、D6、V1D3、V2D2、V3D1(referring to Hu Wenbin etc., vinyl chlorosilane and methylchlorosilane mix equal mixed methylcyclosiloxanes
Hydrolytic Mechanism study " New Chemical Materials " .2007, volume 35 (the 5th phase), the 30-32 pages).This method is using cohydrolysis
Reaction mechanism, hydrolytic process are difficult to control, and ring body type is complicated in product, can not effectively prepare three silicon oxygen of vinyl pentamethyl ring
Alkane, vinyl pentamethyl cyclotrisiloxane yield is very low, and feed ethylene base chlorosilane and methylchlorosilane stability are very
Difference in operating process, is extremely easy to produce hydrochloric acid steam fog, seriously endangers health and Environmental security.
In addition, in the prior art also by the pure and mild vinyl methyl dichlorosilane of tetramethyl disiloxane two, in ether
In solvent, under triethylamine and 4-dimethylaminopyridine catalysis, hydrogen chloride is removed, cyclisation obtains three silicon oxygen of vinyl pentamethyl ring
Alkane.This method uses the dichlorosilane of unfavorable environmental protection, and introduces more solvent ether during the reaction, while generating a large amount of
By-product triethylamine hydrochloride, it is unfavorable to environmental protection, and preparation step is complicated, the two silicon oxygen of raw material tetramethyl in this kind of method
Alkane glycol need to be reacted by expensive palladium/carbon catalyst to be made, and cost is excessively high.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of 2- vinyl -2,4 of low cost, 4,6,6- five first
The environment-friendly preparation method of basic ring trisiloxanes.The present invention solves in the prior art using chlorosilane bring environmental issue, keeps away
Exempt from using chlorosilane；On the other hand, the present invention by the effect of technology controlling and process and cocatalyst improve product yield and
Selectivity；Meanwhile the present invention also has many advantages, such as that low in cost, simple to operation, high-efficient, safety is good.
Term is explained:
D4: the abbreviation of octamethylcy-clotetrasiloxane.
D4 Vi: the abbreviation of tetravinyl tetramethyl-ring tetrasiloxane.
GC-MS: Gas chromatographyMass spectrometry.
Technical scheme is as follows:
A kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, comprising steps of
(1) in the presence of copyrolysis catalyst and cocatalyst, make octamethylcy-clotetrasiloxane (D4) and tetravinyl
Tetramethyl-ring tetrasiloxane (D4 Vi) pre- cracking reaction, reaction time 1-2h are carried out under normal pressure, 90-110 DEG C and stirring condition；
Octamethylcy-clotetrasiloxane (the D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to molar ratio 2:1；
The copyrolysis catalyst is potassium hydroxide, and cocatalyst is triphenylphosphine；
(2) copyrolysis catalyst is added into step (1) reaction system, and is warming up to 140-150 DEG C, it is anti-to carry out copyrolysis
It answers, reaction time 0.5-1h；Then,
(3) 140-150 DEG C of temperature is kept, reaction system is changed into negative pressure state by normal pressure state, continues to split altogether
Solution reaction, while the crude product that reaction is generated produces, that is, collects 70-80 DEG C of fraction；
While crude product extraction, by octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane
(D4 Vi) synchronize and be added dropwise into reaction system according to molar ratio 2:1, keep the D in reaction system4With D4 ViMolar ratio be always 2:
1, D4And D4 ViDropwise addition total amount and crude product extraction total amount be maintained at 1:1 mass ratio, temperature and pressure that process maintains copyrolysis is added dropwise
Power is constant；
(4) the 70-80 DEG C of fraction that step (3) are collected is subjected to rectifying under vacuum conditions, obtains 2- vinyl -2,4,4,
6,6- pentamethyl cyclotrisiloxane.
, according to the invention it is preferred to, the copyrolysis catalyst inventory in step (1) is D4And D4 ViGross mass of feeding intake
0.5%-1%.Cocatalyst inventory is D in step (1)4And D4 ViThe 5%-10% of gross mass of feeding intake.
, according to the invention it is preferred to, step (1) the pre- cracking reaction temperature is 90-95 DEG C.
According to the present invention, the inventory that copyrolysis catalyst is added described in step (2) is D4And D4 ViGross mass of feeding intake
0.5%-1%.
, according to the invention it is preferred to, in step (2), 145 DEG C are warming up to, the copyrolysis reaction time is 0.5h.
, according to the invention it is preferred to, it is to be changed reaction system by normal pressure state using water-jet pump in step (3)
For negative pressure state.
, according to the invention it is preferred to, the pressure of negative pressure state described in step (3) is -0.090MPa to -0.095MPa；
It is further preferred that the pressure of negative pressure state is -0.092MPa；The fraction of 70-80 DEG C/- 0.092MPa is collected in crude product extraction.
, according to the invention it is preferred to, D in step (3)4With D4 ViThe copyrolysis temperature of dropwise addition process is kept for 140-150 DEG C,
Copyrolysis pressure holding -0.090MPa to -0.095MPa.
According to the present invention, it is -0.088MPa to -0.092MPa that step (4) described vacuum condition, which is pressure,；The rectifying
Reflux ratio is preferably 7~8:1.
The present invention provides a kind of preferred embodiment, comprises the following steps that
(1) 592g octamethylcy-clotetrasiloxane and 344g tetravinyl tetramethyl-ring tetrasiloxane are added in a kettle,
It is uniformly mixed, 4.68g solid potassium hydroxide, 56.16g triphenylphosphine is then added thereto, stirring forms suspension；It opens and adds
Heat is to slowly warm up to 95-100 DEG C, carries out adequately pre- cracking reaction, reaction time 1.5h；Then,
(2) 4.68g solid potassium hydroxide is added into kettle, is warming up to 145 DEG C, carries out copyrolysis reaction, reaction time
0.5h；
(3) water-jet pump is used, system is changed into negative pressure state by normal pressure state, pressure maintenance -0.092MPa,
Continue copyrolysis reaction, collects the fraction of 70-80 DEG C/- 0.092MPa；
While producing fraction, octamethylcy-clotetrasiloxane (D is added dropwise according to molar ratio 2:1 is synchronous into kettle4) and four
Vinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMolar ratio be in 2:1 always, keep be added dropwise
D4With D4 ViTotal amount and extraction fraction total amount be 1:1 mass ratio, whole process keep 145 DEG C of kettle temperature, pressure -0.092MPa
It is constant；
(4) fraction collection for producing step (3) carries out essence using the reflux ratio of 8:1 under the pressure of -0.090MPa
Purification is evaporated, 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane are obtained.Product purity is greater than 99.5%, and total recovery is greater than
83%.
What the present invention did not elaborate, press this field routine techniques.
Compared with prior art, it technical characterstic of the invention and has the beneficial effect that:
1, the present invention is a kind of environmental protection preparation of new easy 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane
Method, this method directly utilize D4And D4 ViCracking preparation 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane；Step (1)
Middle D4And D4 ViInitial stage molar ratio is 2:1, D in step (3)4And D4 ViThe synchronous molar ratio that is added dropwise be 2:1, copyrolysis reaction
When 70-80 DEG C of fraction in dimethyl silica chain link total moles and vinyl methyl silicon oxygen chain link total moles be 2:1, pass through
Synchronize the technology controlling and process being added dropwise with extraction, the D in guarantee system4With D4 ViMolar ratio substantially constant, always be in 2:1, auxiliary
Under the action of co-catalyst triphenylphosphine, which inhibits the generation of cyclotetrasiloxane, while greatly improving ring
The cyclization selectivity of trisiloxanes.
2,2- vinyl -2,4 of method of the invention preparation, 4,6,6- pentamethyl cyclotrisiloxane high incomes, raw material are easy
, product purity is high, and wastewater flow rate is few.It is low in cost.
3, the present invention does not use chlorosilane raw material, solves and is asked in the prior art using chlorosilane bring environmental pollution
Topic；Meanwhile the present invention does not use solvent ether and Triethylamine catalyst yet, and reaction process is avoided to generate a large amount of three second of by-product
Amine hydrochlorate.
4, the generation that cyclotetrasiloxane is inhibited during method copyrolysis of the invention, is improving cyclotrisiloxane
Implode, the crosslinking that reaction raw materials are also avoided while cyclic selectivity, it is excellent to have that simple to operation, high-efficient, safety is good etc.
Point.
Detailed description of the invention
Fig. 1 is the gas chromatogram of the fraction of 1 copyrolysis of embodiment of the present invention extraction.
Fig. 2 is product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane prepared by the embodiment of the present invention 11H-
NMR spectra.
Specific embodiment
Below with reference to following embodiment, the invention will be further described, can not limit the contents of the present invention.
Raw material as described in the examples is conventional raw material, can market buy or obtained according to prior art preparation.
Embodiment 1, a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, comprising steps of
(1) in the 2L four-hole boiling flask equipped with mechanical stirring, constant pressure funnel, thermometer and destilling tower, 592g is added
(2mol) octamethylcy-clotetrasiloxane (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is uniformly mixed,
Then 4.68g solid potassium hydroxide, 56.16g triphenylphosphine are added thereto, stirring forms suspension；Heating is opened, is slowly risen
Temperature, material gradually becomes thick in kettle, and with white solid suspended matter, when being warming up to 95-100 DEG C, system is gradually by sticking
It is thick thinning, carry out adequately pre- cracking reaction, reaction time 1.5h；Then,
(2) 4.68g solid potassium hydroxide is added into kettle, is warming up to 145 DEG C, carries out copyrolysis reaction, reaction time
0.5h；
(3) water-jet pump is used, system is changed into negative pressure state by normal pressure state, pressure maintenance -0.092MPa,
Continue copyrolysis reaction, the fraction that copyrolysis generates at this time is produced by overhead, collects 70-80 DEG C/- 0.092MPa
Fraction；
While producing fraction, prestox is added dropwise according to molar ratio 2:1 is synchronous into kettle in You Liangzhi constant pressure funnel
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMolar ratio always
In 2:1, and according to being added dropwise and producing rate, the D being added dropwise is kept4With D4 ViGross mass and extraction fraction quality be 1:1,
Whole process keeps 145 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) fraction collection for producing step (3) carries out essence using the reflux ratio of 8:1 under the pressure of -0.090MPa
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.55%, total recovery 83.4% are obtained.
The fraction sampling produced from step (3) copyrolysis, is analyzed, gas chromatogram is as shown in Figure 1, each group using GC-MS
The content divided is as shown in table 1 below:
Table 1
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 5.94 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 84.66 |
| 2,4- divinyl -2,4,6,6- tetramethyl-ring trisiloxanes | 8.18 |
| Octamethylcy-clotetrasiloxane | 1.22 |
Step (4) product1H-NMR spectrum, as shown in Fig. 2, the peak group at the most High-Field 0.2ppm of hydrogen spectrum, integrates face
Product is 15, and corresponding five methyl should be 2- vinyl -2,4, five Si-CH in 4,6,6- pentamethyl cyclotrisiloxane3,
It is typical vinyl peak type at 5.9ppm, integral area is respectively 1 and 2, corresponding Si-CH=CH2In three hydrogen atoms.
Embodiment 2, a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, comprising steps of
(1) in the 2L reaction kettle equipped with mechanical stirring, constant pressure funnel, thermometer and destilling tower, 592g is added
(2mol) octamethylcy-clotetrasiloxane (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is uniformly mixed,
Then 4.68g solid potassium hydroxide, 74.88g triphenylphosphine are added thereto, stirring forms suspension；Heating is opened, is slowly risen
Temperature, material gradually becomes thick in kettle, and with white solid suspended matter, when being warming up to 100 DEG C, system is gradually by sticky change
It is dilute, 1-2h is maintained, adequately pre- cracking reaction is carried out；Then,
(2) 5.62g solid potassium hydroxide is added into kettle, is warming up to 143-147 DEG C, maintains 40min, carries out copyrolysis
Reaction；
(3) water-jet pump is used, system is changed into negative pressure state, pressure maintenance -0.092MPa by normal pressure state
Continue copyrolysis reaction, the fraction that copyrolysis generates at this time is produced by overhead, collects 70-80 DEG C/- 0.092MPa
Fraction；
While producing fraction, prestox is added dropwise according to molar ratio 2:1 is synchronous into kettle in You Liangzhi constant pressure funnel
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMolar ratio always
In 2:1, and according to being added dropwise and producing rate, the D being added dropwise is kept4With D4 ViGross mass and extraction fraction quality be 1:1,
Whole process keeps 143-147 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) fraction that step (3) produce is summarized, under the pressure of -0.090MPa, essence is carried out using the reflux ratio of 8:1
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.74%, total recovery 81.3% are obtained.
The fraction sampling produced from step (3) copyrolysis, using the content of GC-MS analysis each component, as a result such as the following table 2 institute
Show:
Table 2
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 7.23 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 83.78 |
| 2,4- divinyl -2,4,6,6- tetramethyl-ring trisiloxanes | 8.03 |
| Octamethylcy-clotetrasiloxane | 0.96 |
Embodiment 3, a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, comprising steps of
(1) in the 2L reaction kettle equipped with mechanical stirring, constant pressure funnel, thermometer and destilling tower, 592g is added
(2mol) octamethylcy-clotetrasiloxane (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is uniformly mixed,
Then 5.62g solid potassium hydroxide, 84.24g triphenylphosphine are added thereto, stirring forms suspension；Heating is opened, is slowly risen
Temperature, material gradually becomes thick in kettle, and with white solid suspended matter, when being warming up to 90-110 DEG C, system is gradually by sticking
It is thick thinning, 1-2h is maintained, adequately pre- cracking reaction is carried out；Then,
(2) 5.62g solid potassium hydroxide is added into kettle, is warming up to 140-150 DEG C, maintains 0.5h, carries out copyrolysis
Reaction；
(3) water-jet pump is used, system is changed into negative pressure state, pressure maintenance -0.092MPa by normal pressure state
Continuing the reaction of step (2) copyrolysis, the fraction that copyrolysis generates at this time is produced by overhead, 70-80 DEG C of collection/-
The fraction of 0.092MPa；
While producing fraction, prestox is added dropwise according to molar ratio 2:1 is synchronous into kettle in You Liangzhi constant pressure funnel
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMolar ratio always
In 2:1, and according to being added dropwise and producing rate, the D being added dropwise is kept4With D4 ViGross mass and extraction fraction quality be 1:1,
Whole process keeps 140-150 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) fraction that step (3) produce is summarized, under the pressure of -0.090MPa, essence is carried out using the reflux ratio of 8:1
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.53%, total recovery 82.9% are obtained.
The fraction sampling produced from step (3) copyrolysis, using the content of GC-MS analysis each component, as a result such as the following table 3 institute
Show:
Table 3
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 7.05 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 84.01 |
| 2,4- divinyl -2,4,6,6- tetramethyl-ring trisiloxanes | 7.85 |
| Octamethylcy-clotetrasiloxane | 1.09 |
Comparative example 1
(1) in the 2L reaction kettle equipped with mechanical stirring, thermometer and destilling tower, 592g (2mol) prestox ring four is added
Siloxanes (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is uniformly mixed, is then added thereto
4.68g solid potassium hydroxide, stirring form suspension；Heating to be opened, is slowly heated up, material gradually becomes thick in kettle, and
With white solid suspended matter, when being warming up to 90-110 DEG C, system is very sticky, maintains 1-2h；
(2) 4.68g solid potassium hydroxide is added into kettle, is warming up to 140-150 DEG C, system still presents apparent viscous
Stagnant state；
(3) use water-jet pump, system be evacuated to negative pressure, pressure maintenance -0.090MPa to -0.095MPa continue into
Row reaction, tower top only have a small amount of fraction and occur；
(4) during collecting fractions, material becomes crineous in kettle, and viscosity further increases, and crosslinking phenomenon is sent out
Raw, as reaction carries out, system crosslinking is obvious, and material agglomerates in kettle, and stirring is difficult, and tower top is almost without fraction.
The fraction for cracking extraction, using the content of GC-MS analysis each component, as a result as shown in table 4 below:
Table 4
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 21.85 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 10.62 |
| 2,4- divinyl -2,4,6,6- tetramethyl-ring trisiloxanes | 7.91 |
| Octamethylcy-clotetrasiloxane | 30.76 |
| 2,4,6- trivinyl -2,4,6- trimethyl cyclotrisiloxane | 8.66 |
| 2- vinyl -2,4,4,6,6,8,8- heptamethylcyclotetrasiloxane | 11.21 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxane | 5.67 |
| 2,4,6,8- tetravinyl -2,4,6,8- tetramethyl-ring tetrasiloxane | 1.46 |
Although comparative example 1 is according to octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi)
Molar ratio 2:1 feeds intake, but does not add cocatalyst triphenylphosphine.During copyrolysis, material is very sticky in kettle, knot
Glue is obvious, only cracks out minimal amount of fraction, and yield is very low；And the component (such as table 4) of fraction is sufficiently complex, 2- ethylene
The selectivity of base -2,4,4,6,6- pentamethyl cyclotrisiloxane is very low, can not efficient sintetics.
Comparative example 2
(1) in the 2L four-hole boiling flask equipped with mechanical stirring, thermometer and destilling tower, 296g (1mol) prestox ring is added
Tetrasiloxane (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is uniformly mixed, is then added thereto
3.4g solid potassium hydroxide, 470.4g diphenyl ether and 169.6g biphenyl, stirring form suspension；
(2) open heating, slowly heat up, while to system carry out vacuumize process, pressure maintain -0.097MPa to -
0.099MPa is warming up to 130 DEG C, carries out cracking reaction；
(3) continue the cracking reaction of step (2), the fraction of 80-100 DEG C of tower top of acquisition.
The fraction for cracking extraction, using the content of GC-MS analysis each component, as a result as shown in table 5 below:
Table 5
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 1.85 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 3.66 |
| Octamethylcy-clotetrasiloxane | 10.76 |
| 2- vinyl -2,4,4,6,6,8,8- heptamethylcyclotetrasiloxane | 28.25 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxane | 53.86 |
Comparative example 2 is according to octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) mole
It feeds intake than 1:1, selects the mixture of diphenyl ether and biphenyl as heat-conducting medium, carry out copyrolysis reaction.In change ingredient proportion
And in the case where lacking cocatalyst of the present invention, as shown in table 5, the fraction that copyrolysis generates is mainly cyclotetrasiloxane, 2-
The content of vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane is very low, and selectivity is very poor.
Comparative example 3
(1) in the 2L four-hole boiling flask equipped with mechanical stirring, thermometer and destilling tower, 758g (1mol) dimethyl-silicon is added
Oil (HO- [Si (CH3)2O]10- H) and 878g (1mol) methyl vinyl silicon oil (HO- [Si (CH3) (CH=CH2)O]10- H), it mixes
It closes uniformly, 16.36g solid potassium hydroxide, 164g mineral oil is then added thereto, stirring forms suspension；
(2) open heating, slowly heat up, while to system carry out vacuumize process, pressure maintain -0.097MPa to -
0.099MPa is warming up to 150-160 DEG C, carries out cracking reaction；
(3) fraction that collection step (2) cracking reaction generates.
The fraction for cracking extraction, using the content of GC-MS analysis each component, as a result as shown in table 6 below:
Table 6
| Ingredient names | Constituent content/% |
| Hexamethyl cyclotrisiloxane | 3.06 |
| 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane | 1.22 |
| Octamethylcy-clotetrasiloxane | 17.63 |
| 2- vinyl -2,4,4,6,6,8,8- heptamethylcyclotetrasiloxane | 26.34 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxane | 35.78 |
| 2,4,6- trivinyl -2,4,6,8,8- pentamethyl cyclotetrasiloxane | 13.44 |
Comparative example 3 is using dimethicone and methyl vinyl silicon oil as cracking stock, wherein dimethyl silica chain
The molar ratio of section and methyl ethylene silicon oxygen chain link is 1:1, replaces cocatalyst of the invention, uses mineral oil instead, is total to
Cracking reaction.The results are shown in Table 6 for fraction, and pyrolysis product is mainly various cyclotetrasiloxanes, 2- vinyl -2,4, and 4,6,6- five
The yield of methyl cyclotrisiloxane and selectivity are very low, can not effectively obtain.
Comparative example 4
(1) hydrochloric acid of 1000g 20% is added into 2L four-hole boiling flask, is vigorously stirred, then by two constant pressure funnels
It is synchronous that 258g (2mol) dimethyldichlorosilane and 141g (1mol) methylvinyldichlorosilane is added dropwise, it is anti-to carry out cohydrolysis
It answers.The temperature of cohydrolysis maintains 10-50 DEG C, after being added dropwise to complete, and continues to stir 2h, is then allowed to stand, is layered, organic phase is washed to
Neutrality obtains cohydrolysis object after dry；
(2) in another 2L four-hole boiling flask equipped with mechanical stirring, thermometer and destilling tower, the above-mentioned total water of 180g is added
Object, 1.8g solid potassium hydroxide, 20g octadecyl alcolol are solved, is stirred evenly；
(3) open heating, slowly heat up, while to system carry out vacuumize process, pressure maintain -0.090MPa to -
0.095MPa；
(4) when being warming up to 55 DEG C, system implode, kettle temperature is i.e. by 55 DEG C of rapid blunt temperatures to 102 DEG C, and material crosslinking is bright in kettle
It is aobvious, solid glue residue is become from grease, can not be cracked, no fraction extraction.
Comparative example 4 is anti-according to dimethyldichlorosilane and methylvinyldichlorosilane molar ratio 2:1 progress cohydrolysis
It answers, it is intended to which then cohydrolysis object is carried out cracking processing by the cohydrolysis object for synthesizing molar ratio 2:1.In reaction process, system is quick-fried
Poly-, material crosslinking is violent.The appearance of the situation illustrates that composition component is complicated in cohydrolysis object, poly- containing various ring bodies and straight chain
Siloxanes, under the action of highly basic, ring body ring-opening polymerisation reacts highly exothermic, and the crosslinking of vinyl is caused to occur, heat into
The superposition of one step, finally causes whole system implode, can not crack.
Claims (10)
1. a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, comprising steps of
(1) in the presence of copyrolysis catalyst and cocatalyst, make octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl
Cyclotetrasiloxane (D4 Vi) pre- cracking reaction, reaction time 1-2h are carried out under normal pressure, 90-110 DEG C and stirring condition；
Octamethylcy-clotetrasiloxane (the D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to molar ratio 2:1；
The copyrolysis catalyst is potassium hydroxide, and cocatalyst is triphenylphosphine；
(2) copyrolysis catalyst is added into step (1) reaction system, and is warming up to 140-150 DEG C, carry out copyrolysis reaction,
Reaction time is 0.5-1h；Then,
(3) 140-150 DEG C of temperature is kept, reaction system is changed into negative pressure state by normal pressure state, it is anti-to continue copyrolysis
The crude product answered, while reaction being generated produces, that is, collects 70-80 DEG C of fraction；
While crude product extraction, by octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to
Molar ratio 2:1, which is synchronized, to be added dropwise into reaction system, and the D in reaction system is kept4With D4 ViMolar ratio be always 2:1, D4And D4 Vi's
Total amount is added dropwise and crude product extraction total amount is maintained at 1:1 mass ratio, process is added dropwise and maintains the temperature of copyrolysis and pressure constant；
(4) the 70-80 DEG C of fraction that step (3) are collected is subjected to rectifying under vacuum conditions, obtains 2- vinyl -2,4,4,6,6-
Pentamethyl cyclotrisiloxane.
2. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
Copyrolysis catalyst inventory in step (1) is D4And D4 ViThe 0.5%-1% of gross mass of feeding intake, the middle auxiliary of step (1) are urged
Agent inventory is D4And D4 ViThe 5%-10% of gross mass of feeding intake.
3. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
In step (1) the pre- cracking reaction temperature be 90-95 DEG C.
4. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
The inventory that copyrolysis catalyst is added described in step (2) is D4And D4 ViThe 0.5%-1% of gross mass of feeding intake.
5. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
In step (2), 145 DEG C are warming up to, the copyrolysis reaction time is 0.5h.
6. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
It is that reaction system is changed by normal pressure state by negative pressure state using water-jet pump in step (3).
7. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
The pressure of the negative pressure state described in step (3) is -0.090MPa to -0.095MPa.
8. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
The D in step (3)4With D4 ViThe copyrolysis temperature of dropwise addition process is kept for 140-150 DEG C, copyrolysis pressure holding -0.090MPa
To -0.095MPa.
9. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature exist
It is pressure in step (4) described vacuum condition is -0.088MPa to -0.092MPa；The reflux ratio of the rectifying is preferably 7~8:
1。
10. 2- vinyl -2,4 as described in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, feature
It is, comprising steps of
(1) 592g octamethylcy-clotetrasiloxane and 344g tetravinyl tetramethyl-ring tetrasiloxane, mixing are added in a kettle
Uniformly, 4.68g solid potassium hydroxide, 56.16g triphenylphosphine are then added thereto, stirring forms suspension；Heating is opened,
It is to slowly warm up to 95-100 DEG C, carries out adequately pre- cracking reaction, reaction time 1.5h；Then,
(2) 4.68g solid potassium hydroxide is added into kettle, is warming up to 145 DEG C, carries out copyrolysis reaction, reaction time 0.5h；
(3) water-jet pump is used, system is changed into negative pressure state by normal pressure state, pressure maintenance -0.092MPa continues
Copyrolysis reaction is carried out, the fraction of 70-80 DEG C/- 0.092MPa is collected；
While producing fraction, octamethylcy-clotetrasiloxane (D is added dropwise according to molar ratio 2:1 is synchronous into kettle4) and tetravinyl
Tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMolar ratio be in 2:1 always, keep be added dropwise D4With D4 Vi
Total amount and the fraction total amount of extraction be 1:1 mass ratio, whole process keeps 145 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) fraction collection for producing step (3) carries out rectifying using the reflux ratio of 8:1 and mentions under the pressure of -0.090MPa
It is pure, obtain 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane.
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