CN106986890A - A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 - Google Patents
A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 Download PDFInfo
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- CN106986890A CN106986890A CN201710423632.2A CN201710423632A CN106986890A CN 106986890 A CN106986890 A CN 106986890A CN 201710423632 A CN201710423632 A CN 201710423632A CN 106986890 A CN106986890 A CN 106986890A
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- copyrolysis
- vinyl
- reaction
- cyclotrisiloxane
- cut
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title abstract description 16
- SKYKARIMXZGKOD-UHFFFAOYSA-N 2,2,4,4,6-pentamethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[Si](C)(C)O[Si](C)(C)O1 SKYKARIMXZGKOD-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 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 21
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 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 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 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 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 230000001360 synchronised effect Effects 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 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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 class 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 class 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
- 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
- 238000005516 engineering process Methods 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
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- -1 Siloxanes Chemical class 0.000 description 2
- CNQPFYOBEOUUKV-UHFFFAOYSA-N [SiH4].C=CC Chemical compound [SiH4].C=CC CNQPFYOBEOUUKV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 238000003786 synthesis reaction Methods 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 class 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
- 229960000549 4-dimethylaminophenol Drugs 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
- 239000005977 Ethylene Substances 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical class 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
- 238000004891 communication Methods 0.000 description 1
- 238000010924 continuous production Methods 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
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000004519 grease Substances 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
- 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
- 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
- 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 method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6.This method includes：By octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) in molar ratio 2:1 carries out pre- cracking reaction in the presence of copyrolysis catalyst and cocatalyst；Then, add copyrolysis catalyst and carry out copyrolysis reaction at 140 150 DEG C；Normal pressure is changed into negative pressure and collects copyrolysis cut, D is synchronously added dropwise while extraction in cut4And D4 Vi, and keep dropwise addition total amount equal with producing total amount；Cut is collected, rectifying produces target product.The inventive method improves the yield and selectivity of cyclotrisiloxane, it is suppressed that the generation of cyclotetrasiloxane, while it also avoid the implode of reaction raw materials, crosslinking, with simple to operation, cost is low, efficiency high, environmental protection, it is safe the features such as.
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 technology
Cyclosiloxane is very important intermediate feed in organosilicon industry, is widely used in synthesis silicone oil, silicon tree
Fat and silicon rubber etc..With its preparation organosilicon material have excellent electric property, physiological inertia, corrosion-resistant, high-low temperature resistant,
The performance such as ageing-resistant, other high-molecular organic materials can not be compared and substituted, in Aero-Space, electric, vapour
It is widely used in terms of car and boat oceangoing ship, industry light industry textile industry, building, machinery, medical science, communications and transportation, is increasingly becoming 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 comprising only a vinyl in structure, with 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 complete,
Its elasticity also corresponds to only one of which crosslinking points to provide.2- vinyl -2,4,4,6,6- pentamethyls cyclotrisiloxane and other
After organosilicon ring body ring-opening polymerisation, the vinyl methyl silica chain link in strand is between two dimethyl silica chain links,
The appearance of vinyl coherent condition is avoided, during vulcanization, the crosslinking active of vinyl is improved, compared to others
Vinyl ring body, the utilization rate of vinyl is higher, and the effect after solidification is more notable.
The preparation of methyl ethylene silane mixture ring body of current document report, with vinyl methyl dichlorosilane monomer and
Dimethyldichlorosilane monomer is that mixed hydrolysis are prepared for methyl ethylene silane mixture ring body under raw material, acid, cryogenic conditions,
Organosilicon methyl, vinyl ring body in qualitative analysis, product mainly include by gas chromatograph-mass spectrometer (GC-MS)：
D3、D4、D5、D6、V1D3、V2D2、V3D1Deng mixed methylcyclosiloxane, (referring to Hu Wenbin etc., vinyl chlorosilanes and methylchlorosilane are mixed
Hydrolytic Mechanism studies《New Chemical Materials》.2007, volume 35 (the 5th phase), the 30-32 pages).This method is using cohydrolysis
Reaction mechanism, hydrolytic process is difficult to control, and ring body species is complicated in product, it is impossible to effectively prepare the silica of vinyl pentamethyl ring three
Alkane, vinyl pentamethyl cyclotrisiloxane yield is very low, and feed ethylene base chlorosilane and methylchlorosilane stability are very
Difference, in operating process, very easily produces hydrochloric acid steam fog, seriously endangers healthy and Environmental security.
In addition, in the prior art also by tetramethyl disiloxane glycol and vinyl methyl dichlorosilane, in ether
In solvent, under triethylamine and DMAP catalysis, hydrogen chloride is removed, cyclisation obtains the silica of vinyl pentamethyl ring three
Alkane.This method uses unfavorable environmentally friendly dichlorosilane, and introduces more solvent ether during the course of the reaction, while producing a large amount of
Accessory substance triethylamine hydrochloride, it is unfavorable to environmental protection, and preparation process is complicated, the silica of raw material tetramethyl two in this kind of method
Alkane glycol need to be reacted by expensive palladium/carbon catalyst to be made, and cost is too high.
The content of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of inexpensive 2- vinyl -2,4,4,6,6- five first
The environment-friendly preparation method of basic ring trisiloxanes.The present invention solves the environmental issue brought in the prior art using chlorosilane, keeps away
Exempt to use 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 the advantages that with low cost, simple to operation, efficiency high, security are 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, including step：
(1) in the presence of copyrolysis catalyst and cocatalyst, octamethylcy-clotetrasiloxane (D is made4) and tetravinyl
Tetramethyl-ring tetrasiloxane (D4 Vi) in carrying out pre- cracking reaction, reaction time 1-2h under normal pressure, 90-110 DEG C and stirring condition；
Octamethylcy-clotetrasiloxane (the D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to mol ratio 2:1；
Described copyrolysis catalyst is potassium hydroxide, and cocatalyst is triphenylphosphine；
(2) add copyrolysis catalyst into step (1) reaction system, and be warming up to 140-150 DEG C, carry out copyrolysis anti-
Should, the reaction time is 0.5-1h；Then,
(3) 140-150 DEG C of keeping temperature, negative pressure state is changed into by reaction system by atmospheric pressure state, proceeds to split altogether
Solution reaction, while the crude product for reacting generation is produced, that is, collects 70-80 DEG C of cut；
While crude product is produced, by octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane
(D4 Vi) according to mol ratio 2:1 is synchronously added dropwise into reaction system, keeps the D in reaction system4With D4 ViMol ratio be always 2:
1, D4And D4 ViDropwise addition total amount and crude product extraction total amount be maintained at 1:1 mass ratio, is added dropwise temperature and pressure that process maintains copyrolysis
Power is constant；
(4) 70-80 DEG C of cut for collecting step (3) carries out rectifying under vacuum, obtains 2- vinyl -2,4, and 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 atmospheric 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；70-80 DEG C/- 0.092MPa cut 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, step (4) described vacuum condition is that pressure is -0.088MPa to -0.092MPa；The rectifying
Reflux ratio is preferably 7~8:1.
The present invention provides one kind preferred embodiment, including step is as follows：
(1) 592g octamethylcy-clotetrasiloxanes and 344g tetravinyl tetramethyl-ring tetrasiloxanes are added in a kettle.,
It is well mixed, 4.68g solid potassium hydroxides, 56.16g triphenylphosphines are then added thereto, and stirring forms suspension；Open and add
Heat, is to slowly warm up to 95-100 DEG C, carries out sufficiently pre- cracking reaction, reaction time 1.5h；Then,
(2) 4.68g solid potassium hydroxides are added into kettle, 145 DEG C are warming up to, copyrolysis reaction, reaction time is carried out
0.5h；
(3) water-jet pump is used, system is changed into negative pressure state by atmospheric pressure state, pressure maintenance -0.092MPa,
Proceed copyrolysis reaction, collect 70-80 DEG C/- 0.092MPa cut；
While cut is produced, into kettle according to mol ratio 2:1 synchronous dropwise addition octamethylcy-clotetrasiloxane (D4) and four
Vinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMol ratio all the time be in 2:1, keep what is be added dropwise
D4With D4 ViTotal amount with extraction cut total amount be 1:1 mass ratio, whole process keeps 145 DEG C of kettle temperature, pressure -0.092MPa
It is constant；
(4) fraction collection for producing step (3), under -0.090MPa pressure, using 8:1 reflux ratio carries out essence
Purification is evaporated, 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane is obtained.Product purity is more than 99.5%, and total recovery is more than
83%.
What the present invention was not elaborated, by this area routine techniques.
Compared with prior art, technical characterstic of the invention and have the beneficial effect that：
1st, 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 utilizes D4And D4 ViCracking prepares 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane；Step (1)
Middle D4And D4 ViInitial stage, molar ratio was 2:1, D in step (3)4And D4 ViThe synchronous mol ratio that is added dropwise be 2:1, copyrolysis reaction
When 70-80 DEG C of cut in dimethyl silica chain link total moles and vinyl methyl silica chain link total moles be 2:1, pass through
The synchronous technology controlling and process being added dropwise with extraction, it is ensured that the D in system4With D4 ViMol ratio substantially constant, all the time in 2:1, auxiliary
In the presence of co-catalyst triphenylphosphine, the continuous process inhibits the generation of cyclotetrasiloxane, while greatly improving ring
The cyclization selectivity of trisiloxanes.
2nd, 2- vinyl -2,4 prepared by method of the invention, 4,6,6- pentamethyl cyclotrisiloxane high incomes, raw material is easy
, product purity is high, and wastewater flow rate is few.It is with low cost.
3rd, the present invention is solved the environmental pollution brought in the prior art using chlorosilane and asked without using chlorosilane raw material
Topic；Meanwhile, the present invention is also without using solvent ether and Triethylamine catalyst, it is to avoid course of reaction produces the substantial amounts of second of accessory substance three
Amine hydrochlorate.
4th, the generation of cyclotetrasiloxane is inhibited during method copyrolysis of the invention, cyclotrisiloxane is being improved
Implode, the crosslinking of reaction raw materials are it also avoid while cyclic selectivity, it is good etc. excellent with simple to operation, efficiency high, security
Point.
Brief description of the drawings
Fig. 1 is the gas chromatogram of the cut of the copyrolysis of the embodiment of the present invention 1 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.
Embodiment
With reference to following examples, the invention will be further described, can not limit present disclosure.
Raw material described in embodiment is convenient source, can market buy or prepared according to prior art.
Embodiment 1, a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, including step：
(1) in the 2L four-hole boiling flasks equipped with mechanical agitation, 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 well mixed,
Then 4.68g solid potassium hydroxides, 56.16g triphenylphosphines are added thereto, and stirring forms suspension；Heating is opened, it is slow to rise
Material gradually becomes thick in temperature, kettle, and with white solid suspension, when being warming up to 95-100 DEG C, system is gradually by sticking
It is thick thinning, carry out sufficiently pre- cracking reaction, reaction time 1.5h；Then,
(2) 4.68g solid potassium hydroxides are added into kettle, 145 DEG C are warming up to, copyrolysis reaction, reaction time is carried out
0.5h；
(3) water-jet pump is used, system is changed into negative pressure state by atmospheric pressure state, pressure maintenance -0.092MPa,
Proceed copyrolysis reaction, the cut that now copyrolysis is produced is produced by overhead, collects 70-80 DEG C/- 0.092MPa
Cut；
Produce cut while, from two constant pressure funnels into kettle according to mol ratio 2:1 synchronous dropwise addition prestox
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMol ratio all the time
In 2:1, and according to being added dropwise and producing speed, keep the D being added dropwise4With D4 ViGross mass with extraction cut quality be 1:1,
Whole process keeps 145 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) fraction collection for producing step (3), under -0.090MPa pressure, using 8:1 reflux ratio carries out essence
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.55%, total recovery 83.4% is obtained.
The cut 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 that hydrogen is composed, integrates face
Product is 15, five methyl of correspondence, should be five Si-CH in 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane3,
It is typical vinyl peak type at 5.9ppm, integral area is respectively 1 and 2, correspondence Si-CH=CH2In three hydrogen atoms.
Embodiment 2, a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, including step：
(1) in the 2L reactors equipped with mechanical agitation, 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 well mixed,
Then 4.68g solid potassium hydroxides, 74.88g triphenylphosphines are added thereto, and stirring forms suspension；Heating is opened, it is slow to rise
Material gradually becomes thick in temperature, kettle, and with white solid suspension, when being warming up to 100 DEG C, system is gradually become by sticky
It is dilute, 1-2h is maintained, sufficiently pre- cracking reaction is carried out；Then,
(2) 5.62g solid potassium hydroxides are added into kettle, 143-147 DEG C is warming up to, 40min is maintained, copyrolysis is carried out
Reaction；
(3) water-jet pump is used, system is changed into negative pressure state, pressure maintenance -0.092MPa by atmospheric pressure state
Proceed copyrolysis reaction, the cut that now copyrolysis is produced is produced by overhead, collects 70-80 DEG C/- 0.092MPa
Cut；
Produce cut while, from two constant pressure funnels into kettle according to mol ratio 2:1 synchronous dropwise addition prestox
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMol ratio all the time
In 2:1, and according to being added dropwise and producing speed, keep the D being added dropwise4With D4 ViGross mass with extraction cut quality be 1:1,
Whole process keeps 143-147 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) cut for producing step (3) collects, under -0.090MPa pressure, using 8:1 reflux ratio carries out essence
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.74%, total recovery 81.3% is obtained.
The cut sampling produced from step (3) copyrolysis, the content of each component is analyzed using GC-MS, as a result such as table 2 below 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, including step：
(1) in the 2L reactors equipped with mechanical agitation, 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 well mixed,
Then 5.62g solid potassium hydroxides, 84.24g triphenylphosphines are added thereto, and stirring forms suspension；Heating is opened, it is slow to rise
Material gradually becomes thick in temperature, kettle, and with white solid suspension, when being warming up to 90-110 DEG C, system is gradually by sticking
It is thick thinning, 1-2h is maintained, sufficiently pre- cracking reaction is carried out；Then,
(2) 5.62g solid potassium hydroxides are added into kettle, 140-150 DEG C is warming up to, 0.5h is maintained, copyrolysis is carried out
Reaction；
(3) water-jet pump is used, system is changed into negative pressure state, pressure maintenance -0.092MPa by atmospheric pressure state
Proceed the reaction of step (2) copyrolysis, the cut that now copyrolysis is produced is produced by overhead, 70-80 DEG C of collection/-
0.092MPa cut；
Produce cut while, from two constant pressure funnels into kettle according to mol ratio 2:1 synchronous dropwise addition prestox
Cyclotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMol ratio all the time
In 2:1, and according to being added dropwise and producing speed, keep the D being added dropwise4With D4 ViGross mass with extraction cut quality be 1:1,
Whole process keeps 140-150 DEG C of kettle temperature, pressure -0.092MPa constant；
(4) cut for producing step (3) collects, under -0.090MPa pressure, using 8:1 reflux ratio carries out essence
Purification is evaporated, product 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane, purity 99.53%, total recovery 82.9% is obtained.
The cut sampling produced from step (3) copyrolysis, the content of each component is analyzed using GC-MS, as a result such as table 3 below 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 reactors equipped with mechanical agitation, thermometer and destilling tower, 592g (2mol) prestoxs ring four is added
Siloxanes (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is well mixed, then adds thereto
4.68g solid potassium hydroxides, stirring forms suspension；Open material in heating, slow heating, kettle and gradually become thick, and
With white solid suspension, when being warming up to 90-110 DEG C, system is very sticky, maintains 1-2h；
(2) 4.68g solid potassium hydroxides are added into kettle, 140-150 DEG C are warming up to, system still presents obvious 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 has a small amount of cut and occurred；
(4) during collecting fractions, material is changed into crineous in kettle, and viscosity further increases, and crosslinking phenomenon is sent out
Raw, as reaction is carried out, system crosslinking is obvious, and material lumps in kettle, and stirring is difficult, and tower top is almost without cut.
The cut of extraction is cracked, the content of each component is analyzed using GC-MS, it is 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- heptamethylcyclotetrasiloxanes | 11.21 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxanes | 5.67 |
| 2,4,6,8- tetravinyl -2,4,6,8- tetramethyl-ring tetrasiloxanes | 1.46 |
Although comparative example 1 is according to octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi)
Mol ratio 2:1 feeds intake, but does not add cocatalyst triphenylphosphine.During copyrolysis, material is very sticky in kettle, knot
Glue substantially, only cracks out minimal amount of cut, yield is very low；And the component (such as table 4) of cut is sufficiently complex, 2- ethene
Base -2,4, the selectivity of 4,6,6- pentamethyl cyclotrisiloxane is very low, it is impossible to efficient sintetics.
Comparative example 2
(1) in the 2L four-hole boiling flasks equipped with mechanical agitation, thermometer and destilling tower, 296g (1mol) prestox ring is added
Tetrasiloxane (D4) and 344g (1mol) tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi), it is well mixed, then adds thereto
3.4g solid potassium hydroxides, 470.4g diphenyl ether and 169.6g biphenyl, stirring form suspension；
(2) heating, slow heating are opened, while carry out vacuumize process to system, 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), gather the cut of 80-100 DEG C of tower top.
The cut of extraction is cracked, the content of each component is analyzed using GC-MS, it is 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- heptamethylcyclotetrasiloxanes | 28.25 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxanes | 53.86 |
Comparative example 2 is according to octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) mole
Than 1:1 is fed intake, and heat-conducting medium, progress copyrolysis reaction are used as from the mixture of diphenyl ether and biphenyl.In change ingredient proportion
And in the case of lacking cocatalyst of the present invention, as shown in table 5, the cut that copyrolysis is produced is mainly cyclotetrasiloxane, 2-
Vinyl -2,4, the content of 4,6,6- pentamethyl cyclotrisiloxane is very low, and selectivity is very poor.
Comparative example 3
(1) in the 2L four-hole boiling flasks equipped with mechanical agitation, 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), mix
Close uniform, 16.36g solid potassium hydroxides, 164g mineral oil are then added thereto, stirring forms suspension；
(2) heating, slow heating are opened, while carry out vacuumize process to system, pressure maintain -0.097MPa to -
0.099MPa, is warming up to 150-160 DEG C, carries out cracking reaction；
(3) cut that collection step (2) cracking reaction is produced.
The cut of extraction is cracked, the content of each component is analyzed using GC-MS, it is 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- heptamethylcyclotetrasiloxanes | 26.34 |
| 2,4- divinyl -2,4,6,6,8,8- hexamethyl cyclotetrasiloxanes | 35.78 |
| 2,4,6- trivinyl -2,4,6,8,8- pentamethyl cyclotetrasiloxanes | 13.44 |
Comparative example 3 is as cracking stock, wherein dimethyl silica chain using dimethicone and methyl vinyl silicon oil
The mol ratio of section and methyl ethylene silica chain link is 1:1, replace the cocatalyst of the present invention, use mineral oil instead, be total to
Cracking reaction.As shown in table 6, pyrolysis product is mainly various cyclotetrasiloxanes, 2- vinyl -2,4,4,6,6- five to cut result
The yield of methyl cyclotrisiloxane and selectivity are very low, it is impossible to effectively obtain.
Comparative example 4
(1) 1000g 20% hydrochloric acid is added into 2L four-hole boiling flasks, is stirred vigorously, then by two constant pressure funnels
It is synchronous that 258g (2mol) dimethyldichlorosilanes and 141g (1mol) methylvinyldichlorosilane is added dropwise, carry out cohydrolysis anti-
Should.The temperature of cohydrolysis maintains 10-50 DEG C, after being added dropwise to complete, and continues to stir 2h, then stands, is layered, organic phase is washed to
Neutrality, cohydrolysis thing is obtained after drying；
(2) in another 2L four-hole boiling flasks equipped with mechanical agitation, thermometer and destilling tower, the above-mentioned common water of 180g is added
Thing, 1.8g solid potassium hydroxides, 20g octadecyl alcolols are solved, is stirred；
(3) heating, slow heating are opened, while carry out vacuumize process to system, 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 changed into from grease, it is impossible to crack, no cut extraction.
Comparative example 4 is according to dimethyldichlorosilane and methylvinyldichlorosilane mol ratio 2:1 progress cohydrolysis is anti-
Should, it is intended to synthesize mol ratio 2:1 cohydrolysis thing, then carries out cracking processing by cohydrolysis thing.In course of reaction, system is quick-fried
Poly-, material crosslinking is violent.The appearance of the situation, illustrates that composition component is complicated in cohydrolysis thing, poly- containing various ring bodies and straight chain
Siloxanes, in the presence of highly basic, ring body ring-opening polymerisation reacts highly exothermic, and causes the crosslinking of vinyl to occur, and heat enters
One step is superimposed, and finally causes whole system implode, it is impossible to crack.
Claims (10)
1. a kind of 2- vinyl -2,4, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, including step：
(1) in the presence of copyrolysis catalyst and cocatalyst, octamethylcy-clotetrasiloxane (D is made4) and tetravinyl tetramethyl
Cyclotetrasiloxane (D4 Vi) in carrying out pre- cracking reaction, reaction time 1-2h under normal pressure, 90-110 DEG C and stirring condition；
Octamethylcy-clotetrasiloxane (the D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to mol ratio 2:1；
Described copyrolysis catalyst is potassium hydroxide, and cocatalyst is triphenylphosphine；
(2) add copyrolysis catalyst into step (1) reaction system, and be warming up to 140-150 DEG C, carry out copyrolysis reaction,
Reaction time is 0.5-1h；Then,
(3) 140-150 DEG C of keeping temperature, is changed into negative pressure state by atmospheric pressure state by reaction system, proceeds copyrolysis anti-
Should, while the crude product for reacting generation is produced, that is, collect 70-80 DEG C of cut；
While crude product is produced, by octamethylcy-clotetrasiloxane (D4) and tetravinyl tetramethyl-ring tetrasiloxane (D4 Vi) according to
Mol ratio 2:1 is synchronously added dropwise into reaction system, keeps the D in reaction system4With D4 ViMol ratio be always 2:1, D4And D4 Vi's
Total amount is added dropwise and is maintained at 1 with crude product extraction total amount:1 mass ratio, the process that is added dropwise maintains the temperature and pressure of copyrolysis constant；
(4) 70-80 DEG C of cut for collecting step (3) carries out rectifying under vacuum, obtains 2- vinyl -2,4,4,6,6-
Pentamethyl cyclotrisiloxane.
2. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
Copyrolysis catalyst inventory in step (1) is D4And D4 ViAuxiliary is urged in the 0.5%-1% of gross mass of feeding intake, step (1)
Agent inventory is D4And D4 ViThe 5%-10% of gross mass of feeding intake.
3. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
In step (1) the pre- reaction temperature that cracks for 90-95 DEG C.
4. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
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 claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
In step (2), 145 DEG C are warming up to, the copyrolysis reaction time is 0.5h.
6. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
It is that reaction system is changed into by negative pressure state by atmospheric pressure state using water-jet pump in step (3).
7. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
The pressure of negative pressure state described in step (3) is -0.090MPa to -0.095MPa；It is preferred that, the pressure of negative pressure state for-
0.092MPa。
8. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
The D in step (3)4With D4 ViThe copyrolysis temperature of dropwise addition process keeps 140-150 DEG C, copyrolysis pressure holding -0.090MPa
To -0.095MPa.
9. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature exists
It is that pressure is -0.088MPa to -0.092MPa in step (4) described vacuum condition；The reflux ratio of the rectifying is preferably 7~8:
1。
10. 2- vinyl -2,4 as claimed in claim 1, the preparation method of 4,6,6- pentamethyl cyclotrisiloxane, its feature
It is, including step：
(1) 592g octamethylcy-clotetrasiloxanes and 344g tetravinyl tetramethyl-ring tetrasiloxanes, mixing are added in a kettle.
Uniformly, 4.68g solid potassium hydroxides, 56.16g triphenylphosphines are then added thereto, and stirring forms suspension；Open heating,
95-100 DEG C is to slowly warm up to, sufficiently pre- cracking reaction, reaction time 1.5h is carried out；Then,
(2) 4.68g solid potassium hydroxides are added into kettle, 145 DEG C are warming up to, copyrolysis reaction, reaction time 0.5h is carried out；
(3) water-jet pump is used, system negative pressure state is changed into by atmospheric pressure state, pressure maintenance -0.092MPa continues
Copyrolysis reaction is carried out, 70-80 DEG C/- 0.092MPa cut is collected；
While cut is produced, into kettle according to mol ratio 2:1 synchronous dropwise addition octamethylcy-clotetrasiloxane (D4) and tetravinyl
Tetramethyl-ring tetrasiloxane (D4 Vi), the D in holding system4With D4 ViMol ratio all the time be in 2:1, keep the D being added dropwise4With D4 Vi
Total amount with extraction cut total amount 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), under -0.090MPa pressure, using 8:1 reflux ratio carries out rectifying and carried
It is pure, obtain 2- vinyl -2,4,4,6,6- pentamethyl cyclotrisiloxane.
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| CN108409775A (en) * | 2018-03-23 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of 1- vinyl -1,1,3,3,3- pentamethyl disiloxanes |
| CN108409775B (en) * | 2018-03-23 | 2020-09-04 | 威海新元化工有限公司 | Preparation method of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane |
| CN110156826A (en) * | 2019-06-20 | 2019-08-23 | 威海新元化工有限公司 | Diphenyl cyclotrisiloxane and the preparation method and application thereof |
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