CN110105384A - A method of preparing methyl three (trimethylsiloxane group) silane - Google Patents
A method of preparing methyl three (trimethylsiloxane group) silane Download PDFInfo
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- CN110105384A CN110105384A CN201910438241.7A CN201910438241A CN110105384A CN 110105384 A CN110105384 A CN 110105384A CN 201910438241 A CN201910438241 A CN 201910438241A CN 110105384 A CN110105384 A CN 110105384A
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 63
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012044 organic layer Substances 0.000 claims abstract description 6
- 238000013517 stratification Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- -1 silicane alkane Chemical class 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 10
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 231100000252 nontoxic Toxicity 0.000 description 7
- 230000003000 nontoxic effect Effects 0.000 description 7
- 230000009967 tasteless effect Effects 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- ZPCHCIABIAQKQB-UHFFFAOYSA-M [OH-].C(CCC)[N+](CCCC)(CCCC)CCCC.[P] Chemical compound [OH-].C(CCC)[N+](CCCC)(CCCC)CCCC.[P] ZPCHCIABIAQKQB-UHFFFAOYSA-M 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005108 dry cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000001166 anti-perspirative effect Effects 0.000 description 2
- 239000003213 antiperspirant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BBLQQYUOIZZLQW-UHFFFAOYSA-N bis(ethenyl)-methyl-[methyl(diphenyl)silyl]oxysilane Chemical compound C=1C=CC=CC=1[Si](C)(O[Si](C)(C=C)C=C)C1=CC=CC=C1 BBLQQYUOIZZLQW-UHFFFAOYSA-N 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Polymers (AREA)
Abstract
The application provides a kind of method for preparing methyl three (trimethylsiloxane group) silane, which comprises mixes hexamethyldisiloxane and alcohol, then instills oxygen-containing linear phosphonitrilic chloride, stirs；Instill methyl trialkoxysilane, stirring；Water is instilled, and is reacted；It neutralizes, filtering, stratification is divided into organic layer and water layer；Organic layer is distilled, methyl three (trimethylsiloxane group) silane is obtained.Methyl three (trimethylsiloxane group) silane high income that the application prepares, and waste liquid discharging amount is considerably less.
Description
Technical field
This application involves but be not limited to technical field of material chemistry, be particularly, but not limited to methyl three (trimethylsiloxane group)
The preparation method of silane.
Background technique
Traditional dry cleaning agent is all that toxic tetrachloro-ethylene is widely used because at low cost cheap.Petroleum of new generation
Detergent, liquid carbon dioxide detergent are because at high cost, equipment replacement problem, and application is very limited.In electronics industry
In middle wiring board, equipment cleaning, CF-113 causes serious pollution to the environment, and has injury to human body.Methyl three (trimethylsiloxane group) silicon
Alkane (hereinafter referred to as M3T), moderate cost, it is non-toxic and tasteless, using safe, be the substitute of current environmental protection, safety.
In cosmetics, skin care, treatment industry, decamethylcyclopentaandoxane (D5) it is one of essential carrier,
Its nontoxic, tasteless, high volatility has a kind of lubrication comfort after painting.As antiperspirant in use, D5Using effect be lower than
M3T, because of M3T ratio D5It is more volatile, -74 DEG C of freezing point, compare D5Low, noresidue is highly suitable for doing antiperspirant.M simultaneously3T
Siloxanes can be used for skin care item of taking care of hair, and can replace D in sheath industry5As slipping agent, chemistry and thermal stability, electricity are absolutely
Edge can replace CF-113 for electronics industry pcb board and various coating equipment cleaning agents, for dry-cleaning the dry cleaning agent of industry.
M3T freezing point is low, flash-point is high, and use, transport, preservation are safe, does not pollute more environmentally protective.M3T is branch siloxanes one
Kind.This branch siloxanes is bigger than linear silicone oil because molecule interchain is wound, and has shear shinning effect, is conducive to it in high shear body
Disperse in system and flow, branched structure reduces silicone oil vitrifying temperature there are the crystallization tendency of inhibition silicone oil at low temperature is conducive to
Degree, 30-35 DEG C higher than common silicone oil glass transition temperature, branch siloxanes adhesiveness ratio is high similar to viscosity linear siloxanes, with
Feeling when preparing cosmetics, when use can be more preferable, more there is fluffy sense smooth feeling when for fabric finishing agent.It is general to compare at present
The most commonly used is produced with trim,ethylchlorosilane with methyl trichlorosilane cohydrolysis；Methyl trimethoxy oxygroup or triethoxysilane,
It is produced in the oxonium ion exchanger resin of strong acid large aperture with hexamethyldisiloxane；Hexamethyldisiloxane and methyl trimethoxy oxygroup
Or triethoxysilane cohydrolysis under acidic organic solvent is produced, but it is relatively low all to there is yield, chlorosilane method exists
The more problems of sour water discharge amount.
Summary of the invention
It is the general introduction to the theme being described in detail herein below.This general introduction is not the protection model in order to limit claim
It encloses.
Originally it please provide and a kind of prepare M3The method of T siloxanes mixes hexamethyldisiloxane and alcohol, instills oxygen-containing linear
Phosphonitrilic chloride catalyst is added methyl trimethoxy oxygroup or triethoxysilane and water, is reacted, not only high income, and
Waste liquid discharging amount is considerably less.
M3T is the siloxanes being made of a function chain link M and tri functional chain T, structure composition Mn+2Tn, (n is less than
5), can be used as M chain link is primarily referred to as hexamethyldisiloxane, divinyl tetramethyl disiloxane, tetramethyl hydrogen silicon oxygen
Alkane, divinyl dimethyl diphenyl disiloxane, trim,ethylchlorosilane etc..It can be used as the mainly methyl trimethoxy of T chain link
Oxysilane, vinyltrimethoxysilane, phenyltrimethoxysila,e, r- aminopropyl trimethoxysilane, r- mercapto propyl three
The tri-alkoxies such as methoxyl group one type of silane and methyl trichlorosilane etc..
Specifically, this application provides a kind of method for preparing methyl three (trimethylsiloxane group) silane, the methods
Include:
(1) hexamethyldisiloxane and alcohol are mixed, then instills oxygen-containing linear phosphonitrilic chloride, stirred；
(2) methyl trialkoxysilane, stirring are instilled；
(3) water is instilled, and is reacted；
(4) it neutralizes, filtering, stratification is divided into organic layer and water layer；
(5) organic layer is distilled, obtains methyl three (trimethylsiloxane group) silane.
In this application, according to the weight of methyl trialkoxysilane, the amount of hexamethyldisiloxane is 5%-25%.
In this application, in step (1), the alcohol can be selected from any in methanol, ethyl alcohol, normal propyl alcohol, n-butanol
Kind or more, preferably isopropanol.
In this application, the molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2.
In this application, in step (1), the oxygen-containing linear phosphonitrilic chloride can be Commercial reagents, such as purchased from Ji
Nan Yada new material Science and Technology Ltd..
In this application, based on the weight of methyl trialkoxysilane, the amount of the catalyst can be 0.001%-
0.01%.
In this application, in step (3), the molar ratio of water and methyl trialkoxysilane can be 2-5.
In this application, the methyl trialkoxysilane can be methyltrimethoxysilane or methyltriethoxy silane
Alkane.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%；It is cooled to 5-10 DEG C after blending, then
Oxygen-containing linear phosphonitrilic chloride is instilled within 15-20 minutes, stirring continues 30-50 minutes.
In this application, in step (2), the methyl trialkoxysilane was instilled through 30-40 minutes, and stir 1-
1.5 hour.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%；It is cooled to 5-10 DEG C after blending, then
Oxygen-containing linear phosphonitrilic chloride is instilled within 15-20 minutes, stirring continues 30-50 minutes；In step (2), three alcoxyl of methyl
Base silane can be methyltrimethoxysilane or methyltriethoxysilane；Three alcoxyl of methyl was instilled through 30-40 minutes
Base silane, and stir 1-1.5 hours.
In this application, it in step (3), at 5-10 DEG C, through 1-1.2 hours instillation water, and reacts at 20-25 DEG C
Lower progress 3-4 hours.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%；It is cooled to 5-10 DEG C after blending, then
Oxygen-containing linear phosphonitrilic chloride is instilled within 15-20 minutes, stirring continues 30-50 minutes；In step (2), three alcoxyl of methyl
Base silane can be methyltrimethoxysilane or methyltriethoxysilane；Three alcoxyl of methyl was instilled through 30-40 minutes
Base silane, and stir 1-1.5 hours；In step (3), the molar ratio of water and methyl trialkoxysilane is 2-5；At 5-10 DEG C
Under, through 1-1.2 hours instillation water；And it reacts and is carried out 3-4 hours at 20-25 DEG C.
In this application, in step (4), ammonium hydrogen carbonate or tetrabutylammonium hydroxide phosphorus can be used, in 80-100 DEG C
With 2-3 hours.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%；It is cooled to 5-10 DEG C after blending, then
Oxygen-containing linear phosphonitrilic chloride is instilled within 15-20 minutes, stirring continues 30-50 minutes；In step (2), three alcoxyl of methyl
Base silane can be methyltrimethoxysilane or methyltriethoxysilane；Three alcoxyl of methyl was instilled through 30-40 minutes
Base silane, and stir 1-1.5 hours；In step (3), the molar ratio of water and methyl trialkoxysilane is 2-5；At 5-10 DEG C
Under, through 1-1.2 hours instillation water；And it reacts and is carried out 3-4 hours at 20-25 DEG C；In step (4), carbonic acid can be used
Hydrogen ammonium or tetrabutylammonium hydroxide phosphorus, in 80-100 DEG C and 2-3 hours.
In this application, in step (5), 120-125 DEG C of fraction is collected.
In some embodiments of the application, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount is 5%-25%；In step (1), the alcohol can be selected from any one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol or more
It is a variety of, preferably isopropanol；The molar ratio of the alcohol and the methyl trialkoxysilane can be 1-2；Based on three alkane of methyl
The weight of oxysilane, the amount of the catalyst can be 0.001%-0.01%；It is cooled to 5-10 DEG C after blending, then
Oxygen-containing linear phosphonitrilic chloride is instilled within 15-20 minutes, stirring continues 30-50 minutes；In step (2), three alcoxyl of methyl
Base silane can be methyltrimethoxysilane or methyltriethoxysilane；Three alcoxyl of methyl was instilled through 30-40 minutes
Base silane, and stir 1-1.5 hours；In step (3), the molar ratio of water and methyl trialkoxysilane is 2-5；At 5-10 DEG C
Under, through 1-1.2 hours instillation water；And it reacts and is carried out 3-4 hours at 20-25 DEG C；In step (4), carbonic acid can be used
Hydrogen ammonium or tetrabutylammonium hydroxide phosphorus, in 80-100 DEG C and 2-3 hours；In step (5), 120-125 DEG C of fraction is collected.
In the preferred embodiment of the application, which comprises
By hexamethyldisiloxane, isopropanol is cooled at 10 DEG C in mixing hereinafter, being instilled within 15 minutes oxygen-containing linear
The dichloromethane solution of phosphonitrilic chloride 5% drips off subsequent stirring 30 minutes, then again through 30 minutes instillation methyl trimethoxy oxygroup silicon
Alkane, and continue stirring 1 hour, then at 5-10 DEG C, through 1 hour instillation water, at 20-25 DEG C, the reaction was continued 3 hours after dripping off.
Then ammonium hydrogen carbonate is added, at 80-100 DEG C in and 2 hours, cooling filtering, static layering taken several layers of distillations, in 12kpa
The lower fraction for collecting 120-125 DEG C.
In another preferred embodiment of the application, which comprises
By hexamethyldisiloxane, isopropanol is cooled at 10 DEG C in mixing hereinafter, being instilled within 30 minutes oxygen-containing linear
The dichloromethane solution of phosphonitrilic chloride 5% drips off subsequent stirring 60 minutes, then again through 30 minutes instillation methyl trimethoxy oxygroup silicon
Alkane, and continue stirring 2 hours, then at 5-25 DEG C, through 1 hour instillation water, it is 4.5 small that at 15-20 DEG C, the reaction was continued after dripping off
When.Then ammonium hydrogen carbonate is added, at 80-100 DEG C in and 2 hours, cooling filtering, static layering taken several layers of distillations,
120-125 DEG C of fraction is collected under 12kpa.
In the other preferred embodiment of the application, which comprises
By hexamethyldisiloxane, isopropanol is cooled at 10 DEG C in mixing hereinafter, being instilled within 40 minutes oxygen-containing linear
The dichloromethane solution of phosphonitrilic chloride 5% drips off subsequent stirring 60 minutes, then again through 60 minutes instillation methyl trimethoxy oxygroup silicon
Alkane, and continue stirring 4 hours, then at 5-25 DEG C, through 2 hours instillation water, at 15-20 DEG C, the reaction was continued 5 hours after dripping off.
Then ammonium hydrogen carbonate is added, at 80-100 DEG C in and 3 hours, cooling filtering, static layering taken several layers of distillations, in 12kpa
The lower fraction for collecting 120-125 DEG C.
In this application, the M that the application prepares3The viscosity that T siloxanes has is in 0.65s/mm2-2.0s/mm2Range
Interior, molecular weight is in the range of 310g/mol-1162g/mol.Compared with existing preparation method, the application takes high yield
M3T siloxanes, sour usage amount is considerably less, activity it is very high, reaction solution can be used ammonium hydrogen carbonate or tetrabutylammonium hydroxide phosphorus into
Row neutralizes, and ammonium hydrogen carbonate is decomposed at 130 DEG C or more, does not generate contaminated wastewater.
Other features and advantage will illustrate in the following description, also, partly become from specification
It obtains it is clear that being understood and implementing the application.The purpose of the application and other advantages can by specification and
Specifically noted structure is achieved and obtained in claims.
Specific embodiment
It, hereinafter will be to embodiments herein for the purposes, technical schemes and advantages of the application are more clearly understood
It is described in detail.It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can
With mutual any combination.
Embodiment 1
486 grams of hexamethyldisiloxane, 64 grams of isopropanols are cooled at 10 DEG C in mixing hereinafter, instilling through 15 minutes
The dichloromethane solution of 0.4 gram of oxygen-containing linear phosphonitrilic chloride 5% drips off subsequent stirring 30 minutes, then instilled again through 30 minutes
136.2 grams of methyltrimethoxysilane simultaneously continue stirring 1 hour, then at 5-10 DEG C, through the 105 grams of water of instillation in 1 hour, drip off
At 20-25 DEG C, the reaction was continued afterwards 3 hours.Then be added 0.68 gram of ammonium hydrogen carbonate, at 80-100 DEG C in and 2 hours, cooled down
Filter, static layering have taken several layers of distillations, collect 120-125 DEG C (fraction at 12kpa).Obtain three (trimethicone of methyl
Base) it is 293 grams of clear, colorless of silane product, tasteless, nontoxic.Properties of product are as follows: purity 99.6%, yield 94.5%, boiling point: 190
DEG C, -74 DEG C of freezing point, viscosity 1.57s/mm2, 0.856 gram/cm of density3, flash-point；64℃.
Embodiment 2
324 grams of hexamethyldisiloxane, 96 grams of isopropanols are cooled at 10 DEG C in mixing hereinafter, instilling through 30 minutes
The dichloromethane solution of 0.6 gram of oxygen-containing linear phosphonitrilic chloride 5% drips off subsequent stirring 60 minutes, then instilled again through 30 minutes
136.2 grams of methyltrimethoxysilane, and continue stirring 2 hours, then at 5-25 DEG C, through the 105 grams of water of instillation in 1 hour, drop
At 15--20 DEG C, the reaction was continued 4.5 hours after complete.Then be added 1 gram of ammonium hydrogencarbonate, at 80-100 DEG C in and 2 hours, cooling
Filtering, static layering have taken several layers of distillations, collect 120-125 DEG C (fraction at 12kpa).Obtain (the trimethyl silicane oxygen of methyl three
Alkyl) it is 289 grams of clear, colorless of silane product, tasteless, nontoxic.Properties of product are as follows: purity 99.5%, yield 93.2%.
Embodiment 3
648 grams of hexamethyldisiloxane, 120 grams of isopropanols are cooled at 10 DEG C in mixing hereinafter, instilling through 40 minutes
The dichloromethane solution of 0.82 gram of oxygen-containing linear phosphonitrilic chloride 5% drips off subsequent stirring 60 minutes, then instilled again through 60 minutes
272 grams of methyltrimethoxysilane, and continue stirring 4 hours, then at 5-25 DEG C, through the 210 grams of water of instillation in 2 hours, drip off
At 15--20 DEG C, the reaction was continued afterwards 5 hours.Then be added 1.5 grams of ammonium hydrogencarbonates, at 80-100 DEG C in and 3 hours, cooled down
Filter, static layering have taken several layers of distillations, collect 120-125 DEG C (fraction at 12kpa).Obtain three (trimethicone of methyl
Base) it is 601 grams of clear, colorless of silane product, tasteless, nontoxic.Purity 99.7%, yield 96.9%.
Comparative example 1
486 grams of hexamethyldisiloxane, 64 grams of isopropanols at cooling to 10 DEG C in mixing, instilled 10 grams through 20 minutes
The concentrated sulfuric acid drips off subsequent stirring 30 minutes, then instills 136 grams of methyltrimethoxysilane again, and continues stirring 1 hour, so
Afterwards at 20-25 DEG C, through the 105 grams of water of instillation in 1 hour, at 20-25 DEG C, the reaction was continued 3 hours after dripping off.Static, layering separates
Aqueous acid, organic moiety are first washed with water twice, then are neutralized with sodium bicarbonate to neutrality, distill, and 120-125 DEG C of collection/
The fraction of 12kpa.Obtain 267 grams of clear, colorless of final products, tasteless, nontoxic.Aqueous acid is by neutralizing qualified discharge.Purity
99.5%, yield about 86%.
Comparative example 2
324 grams of hexamethyldisiloxane, 96 grams of isopropanols cool down at 10 DEG C in mixing hereinafter, instilling 7.8 through 30 minutes
Gram 35% hydrochloric acid of concentration drips off subsequent stirring 60 minutes, then again through the 136 grams of hexamethyl trimethoxy silanes of instillation in 30 minutes,
And continue stirring 2 hours, then at 20-25 DEG C, through the 105 grams of water of instillation in 2 hours, it is 4 small that at 20-25 DEG C, the reaction was continued after dripping off
When.Static, layering separates aqueous acid, and organic moiety is washed with water twice, then is neutralized with sodium bicarbonate to neutrality, distills, receives
Collect the fraction of 120-125 DEG C/12kpa.Obtain 278 grams of clear, colorless of final products, tasteless, nontoxic.Aqueous acid is by neutralizing
Qualified discharge.Purity 99.3%, yield about 89.6%.
As can be seen that using sulfuric acid and salt using oxygen-containing linear phosphonitrilic chloride ratio from embodiment 1-3 and comparative example 1-2
Acid obtains higher yield.
Embodiment 4
The M that the application prepares3The performance test of T siloxanes:
The sample for taking 10 grams of embodiments -13 to prepare respectively is tested under 25 DEG C of environment, 65%RH of test, different temperatures
The volatile quantity data of three samples, and calculate the average value of these data.D4 is octamethylcy-clotetrasiloxane, and D6 is ten dimethyl
Six siloxanes of ring.
The M that the application prepares under 1 different temperatures of table3T siloxanes and D4, D5, D6 before testing after mass loss with
The ratio of pre-test quality
From table 1 it follows that the M that the application prepares3T volatile ratio D4, D5, D6 is fast.
The M that the embodiment of the present application is prepared3T is compared with the freezing point of D4, D5, D6, finds M3T < D4 < D5 <
D6, M3T nodeless mesh is precipitated, and D4, D5 have crystallization to be precipitated, and D6 uses perceptual difference, and use is fewer.
Although embodiment disclosed by the application is as above, the content only for ease of understanding the application and use
Embodiment is not limited to the application.Technical staff in any the application fields, is taken off not departing from the application
Under the premise of the spirit and scope of dew, any modification and variation, but the application can be carried out in the form and details of implementation
Scope of patent protection, still should be subject to the scope of the claims as defined in the appended claims.
Claims (11)
1. a kind of method for preparing methyl three (trimethylsiloxane group) silane, which comprises
(1) hexamethyldisiloxane and alcohol are mixed, then instills oxygen-containing linear phosphonitrilic chloride, stirred；
(2) methyl trialkoxysilane, stirring are instilled；
(3) water is instilled, and is reacted；
(4) it neutralizes, filtering, stratification is divided into organic layer and water layer；
(5) organic layer is distilled, obtains methyl three (trimethylsiloxane group) silane.
2. according to the method described in claim 1, wherein, according to the weight of methyl trialkoxysilane, hexamethyldisiloxane
Amount be 5%-25%.
3. according to the method described in claim 1, wherein, in step (1), the alcohol is selected from methanol, ethyl alcohol, normal propyl alcohol, just
Any one of butanol or more, preferably isopropanol；
The molar ratio of the alcohol and the hexamethyldisiloxane is 1-2.
4. according to the method described in claim 1, wherein, the weight based on methyl trialkoxysilane, the oxygen-containing linear chlorine
The amount for changing phosphonitrile is 0.001%-0.01%.
5. according to the method described in claim 1, wherein, in step (3), the molar ratio of methyl trialkoxysilane and water is
2-5。
6. according to the method described in claim 1, wherein, the methyl trialkoxysilane is methyltrimethoxysilane or first
Ethyl triethoxy silicane alkane.
7. method according to any one of claim 1 to 6, wherein in step (1), be cooled to 5- after blending
10 DEG C, oxygen-containing linear phosphonitrilic chloride is then instilled within 15-20 minutes, stirring continues 30-50 minutes.
8. according to method described in any one of claims 1 to 6, wherein in step (2), instilled the first through 30-40 minutes
Base trialkoxy silane, and stir 1-1.5 hours.
9. method according to any one of claim 1 to 6, wherein in step (3), at 5-10 DEG C, through 1-1.2
Hour instills water, and the reaction carries out 3-4 hours at 20-25 DEG C.
10. method according to any one of claim 1 to 6, wherein in step (4), use ammonium hydrogen carbonate or four fourths
Base phosphonium hydroxide, in 80-100 DEG C and 2-3 hours.
11. method according to any one of claim 1 to 6, wherein in step (5), 120-125 DEG C of collection evaporates
Point.
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Citations (3)
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|---|---|---|---|---|
| US20020133035A1 (en) * | 2001-03-14 | 2002-09-19 | Satoshi Asai | Preparation of low molecular weight branched siloxanes |
| CN1382033A (en) * | 1999-08-30 | 2002-11-27 | 钟纺株式会社 | Comestios |
| CN104945628A (en) * | 2015-06-26 | 2015-09-30 | 中国日用化学工业研究院 | Polyglycerine modified organosilicon and method for preparing the same |
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2019
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| CN1382033A (en) * | 1999-08-30 | 2002-11-27 | 钟纺株式会社 | Comestios |
| US20020133035A1 (en) * | 2001-03-14 | 2002-09-19 | Satoshi Asai | Preparation of low molecular weight branched siloxanes |
| CN104945628A (en) * | 2015-06-26 | 2015-09-30 | 中国日用化学工业研究院 | Polyglycerine modified organosilicon and method for preparing the same |
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| ISAO HASEGAWA等: "Treatment of alkyltriethoxysilanes with Amberlyst 15 cationexchange resin in the presence of hexamethyldisiloxane", 《JOURNAL OF ORGANOMETNLLIC CHEMISTRY》 * |
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Application publication date: 20190809 |