CN1555381A - 带有氰硫基的有机烷氧基硅烷的制备方法 - Google Patents
带有氰硫基的有机烷氧基硅烷的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 12
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 title abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 claims description 15
- -1 γ-thiocyano propyl Chemical group 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 5
- JTFPQNYFZVXAQW-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl thiocyanate Chemical compound CO[Si](C)(OC)CCCSC#N JTFPQNYFZVXAQW-UHFFFAOYSA-N 0.000 claims description 4
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 4
- XODFSNXVWMJCOU-UHFFFAOYSA-N 3-trimethoxysilylpropyl thiocyanate Chemical compound CO[Si](OC)(OC)CCCSC#N XODFSNXVWMJCOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- AULAGNUSLUIEBP-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl thiocyanate Chemical compound CCO[Si](C)(OCC)CCCSC#N AULAGNUSLUIEBP-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical group 0.000 abstract 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GPMABNSBUJBWMW-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl thiocyanate Chemical compound CCO[Si](C)(C)CCCSC#N GPMABNSBUJBWMW-UHFFFAOYSA-N 0.000 description 1
- JMFBXUMHVSZUKY-UHFFFAOYSA-N 3-bromopropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCBr JMFBXUMHVSZUKY-UHFFFAOYSA-N 0.000 description 1
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 description 1
- XVNYMEVFHNKMIA-UHFFFAOYSA-N 3-bromopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCBr XVNYMEVFHNKMIA-UHFFFAOYSA-N 0.000 description 1
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 description 1
- IIFBEYQLKOBDQH-UHFFFAOYSA-N 3-chloropropyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CCCCl IIFBEYQLKOBDQH-UHFFFAOYSA-N 0.000 description 1
- WABUSVWLAWAORI-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]butyl thiocyanate Chemical compound CO[Si](C)(OC)CCCCSC#N WABUSVWLAWAORI-UHFFFAOYSA-N 0.000 description 1
- VJPGPCCOXUQRLT-UHFFFAOYSA-N 4-chlorobutyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCl VJPGPCCOXUQRLT-UHFFFAOYSA-N 0.000 description 1
- CKEZAUDJDIPPIB-UHFFFAOYSA-N 4-chlorobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCl CKEZAUDJDIPPIB-UHFFFAOYSA-N 0.000 description 1
- QIILEPOYRQQPRP-UHFFFAOYSA-N 4-chlorobutyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCCl QIILEPOYRQQPRP-UHFFFAOYSA-N 0.000 description 1
- IMOICJKRTYLPFW-UHFFFAOYSA-N 4-triethoxysilylbutyl thiocyanate Chemical compound CCO[Si](OCC)(OCC)CCCCSC#N IMOICJKRTYLPFW-UHFFFAOYSA-N 0.000 description 1
- ZZQFIAIGPGTMNQ-UHFFFAOYSA-N 4-trimethoxysilylbutyl thiocyanate Chemical compound CO[Si](OC)(OC)CCCCSC#N ZZQFIAIGPGTMNQ-UHFFFAOYSA-N 0.000 description 1
- PURBTKGAOXIIQP-UHFFFAOYSA-N C(C)=C=C(C=CCCC)C=CCC Chemical group C(C)=C=C(C=CCCC)C=CCC PURBTKGAOXIIQP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MJRPMUINYAOXRW-UHFFFAOYSA-N tributylphosphane;hydrochloride Chemical compound [Cl-].CCCC[PH+](CCCC)CCCC MJRPMUINYAOXRW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
通式(3)NCS-R1-Si(OR2)nR3 3-n(其中R1是具有1-6个碳原子的二价烃基,R2和R3是单价烃基,下标n是0-3)表示的带有氰硫基的有机烷氧基硅烷(D)的制备方法,其中使通式(1)MSCN(其中M代表碱金属)表示的硫氰酸盐(A)和通式(2)XR1Si(OR2)nR3 3-n(其中X是卤素原子,和R1、R2、R3和下标n的定义同上)表示的卤代烷基烷氧基硅烷(B)在相转移催化剂(C)的存在下反应。
Description
本发明涉及带有氰硫基的有机烷氧基硅烷的制备方法。
在现有技术中,已存在制备带有氰硫基的烷氧基硅烷的方法,所述烷氧基硅烷以化合物如氰硫基烷基烷氧基硅烷为代表。例如,日本公开的未审专利申请No.Hei 12-229989(对应于US 6005129)提出了一种制备氰硫基丙基三乙氧基硅烷的方法,该方法是通过使γ-氯丙基三乙氧基硅烷与硫氰酸钠在乙醇中在加压下反应。但是,该方法的工艺上的缺点在于乙醇必须在反应终止时通过蒸馏或其它方法去除。另外,由于反应是加压反应,所以要求特殊的压力反应装置,这在经济上是不利的,等等。
针对消除上述问题的研究结果,本发明者完成了本发明。本发明的目的是提供一种以高收率生产带有氰硫基的烷氧基硅烷的方法,获得了高生产率。
本发明涉及通式(3)NCS-R1-Si(OR2)nR3 3-n(其中R1是具有1-6个碳原子的二价烃基,R2和R3是单价烃基,和下标n是0-3)表示的带有氰硫基的有机烷氧基硅烷(D)的制备方法,其中使由通式(1)MSCN(其中M代表碱金属)表示的硫氰酸盐(A)和由通式(2)XR1Si(OR2)nR3 3-n(其中X是卤原子,和R1、R2、R3和下标n的定义同上)表示的卤代烷基烷氧基硅烷(B)在相转移催化剂(C)的存在下反应。
更具体而言,通式(1)MSCN(其中M代表碱金属)表示的硫氰酸盐(A)是用于该反应的原材料之一,和上式中的碱金属M可例举的有锂、钠、钾和铷。其中,钠和钾是优选的。这种硫氰酸盐可例举的有硫氰酸钠和硫氰酸钾。如果组分(B)的水解能力强,则组分(A)导致产率降低,为此,最好彻底干燥后再使用。在减压下加热的公知常规方法或通过添加有机溶剂进行共沸脱水的方法等均可用于该干燥操作中。如果组分(B)的水解能力弱,则组分(A)不必被脱水,可以水溶液的形式使用。该组分的量优选在0.1-2.0mol的范围内,更优选在0.5-1.5mol的范围内。
由通式(2)XR1Si(OR2)nR3 3-n(其中X是卤原子,R1是具有1-6个碳原子的二价烃基,R2和R3是单价烃基,下标n是0-3)表示的卤代烷基烷氧基硅烷(B)也是用于该反应的原材料之一,上式中代表卤原子的X可例举的有氯原子和溴原子。二价烃基R1可例举的有亚甲基、亚乙基、亚丙基、亚丁基、异亚丁基、和其它亚烷基。单价烃基R2和R3可例举的有甲基、乙基、丙基、异丙基、和其它烷基;乙烯基、烯丙基和其它链烯基;以及苯基、甲苯基和其它芳基。这种卤代烷基硅烷可例举的有γ-氯丙基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、γ-氯丙基甲基二甲氧基硅烷、γ-氯丙基甲基二乙氧基硅烷、γ-氯丙基二甲基甲氧基硅烷、γ-氯丙基二甲基乙氧基硅烷、δ-氯丁基三甲氧基硅烷、δ-氯丁基甲基二甲氧基硅烷、δ-氯丁基三乙氧基硅烷、γ-氯-β-甲基丙基三甲氧基硅烷、γ-氯-β-甲基丙基甲基二甲氧基硅烷、γ-氯-β-甲基丙基三乙氧基硅烷、γ-溴丙基三甲氧基硅烷、γ-溴丙基甲基二甲氧基硅烷和γ-溴丙基三乙氧基硅烷。
用于促进组分(A)和组分(B)之间的反应的相转移催化剂(C)可例举的有三丁基溴化铵、三辛基甲基氯化铵和其它季铵盐;三丁基氯化鏻和其它季鏻盐;三乙胺和其它叔胺;冠醚;聚乙二醇;1,8-二氮杂二环[5.4.0]十一-7-烯(DBU),1,5-二氮杂二环[4.3.0]-壬-5-烯(DBN)和其它环胺化合物。相转移催化剂的量优选为每1mol组分(B)0.0001-20mol,更优选0.001-10mol,甚至更优0.001-5mol。
在本发明的制备方法中,使组分(A)和组分(B)在组分(C)的存在下反应,反应温度此时优选为30-180℃,更优选为100-160℃。根据组分(A)、组分(B)和组分(C)的类型和量,反应时间可不同;但是,通常持续30分钟到15小时。
在本发明的制备方法中,组分(B)既作为反应底物又作为溶剂,其消除了对特殊有机溶剂的需要。但是如果必要,也可能使用对组分(A)、组分(B)和组分(C)惰性的有机溶剂。可例举的这种有机溶剂有甲苯、二甲苯、辛烷和二甲基甲酰胺。
在本发明的制备方法中,在组分(A)和组分(B)间的反应终止时,优选采用过滤、在水中水解或其它方法去除作为副产物产生并包含在反应产物中的盐。另外,如果必要,通过蒸馏的方法进行进一步的提纯。
本发明的制备方法确保通式(3)NCS-R1-Si(OR2)nR3 3-n(其中R1、R2、R3和下标n的定义同上)表示的带有氰硫基的有机烷氧基硅烷(D)将以高产率获得。这种带有氰硫基的有机烷氧基硅烷可例举的有:γ-氰硫基丙基三甲氧基硅烷、γ-氰硫基丙基三乙氧基硅烷、γ-氰硫基丙基甲基二甲氧基硅烷、γ-氰硫基丙基甲基二乙氧基硅烷、γ-氰硫基丙基二甲基甲氧基硅烷、γ-氰硫基丙基二甲基乙氧基硅烷、δ-氰硫基丁基三甲氧基硅烷、δ-氰硫基丁基甲基二甲氧基硅烷、δ-氰硫基丁基三乙氧基硅烷、γ-氰硫基-β-甲基丙基三甲氧基硅烷、γ-氰硫基-β-甲基丙基甲基二甲氧基硅烷和γ-氰硫基-β-甲基丙基三乙氧基硅烷。
根据如上描述的本发明的制备方法获得的带有氰硫基的有机烷氧基硅烷无需任何进一步处理就可用于如硅烷偶联剂的应用中;另外,它们可适合地用作其它含硫有机烷氧基硅烷或含硫有机聚硅氧烷的合成中的原料。
应用实施例
下面,通过参考应用实施例详细解释本发明。
应用实施例1
将106.9g(1.10mol)硫氰酸钾、240.8g(1.00mol)γ-氯丙基三乙氧基硅烷和作为催化剂的0.77g(0.005mol)1,8-二氮杂二环[5.4.0]十一-7-烯(DBU)置于500mL装配有回流冷凝器、搅拌器和温度计的四颈烧瓶中,并在150℃搅拌6小时。随后,通过过滤从反应产物中去除反应副产物。在减压下通过蒸馏滤液,分离了242.3g(0.92mol)的目的物γ-氰硫基丙基三乙氧基硅烷。γ-氰硫基丙基三乙氧基硅烷的产率为92%。
对比例1
以与应用实施例1相同的方式进行反应,只是没有将1,8-二氮杂二环[5.4.0]十一-7-烯(DBU)添加到500mL装配有回流冷凝器、搅拌器和温度计的四颈烧瓶中;根本没有生产出目的物氰硫基丙基三乙氧基硅烷。
应用实施例2
将106.9g(1.10mol)硫氰酸钾、198.7g(1.0mol)γ-氯丙基三甲氧基硅烷、作为催化剂的0.77g(0.005mol)1,8-二氮杂二环[5.4.0]十一-7-烯(DBU)和30g甲苯置于500mL装配有回流冷凝器、搅拌器和温度计的四颈烧瓶中,并在125℃搅拌10小时。将水加入最终反应产物中以促使相分离,且去除反应副产物。在减压下通过蒸馏甲苯层,分离出199.2g(0.90mol)的目的物γ-氰硫基丙基三甲氧基硅烷。γ-氰硫基丙基三甲氧基硅烷的产率为90%。
应用实施例3
将106.9g(1.10mol)硫氰酸钾、182.7g(1.0mol)γ-氯丙基甲基二甲氧基硅烷和作为催化剂的1.61g(0.005mol)四丁基溴化铵置于500mL装配有回流冷凝器、搅拌器和温度计的四颈烧瓶中,并在120℃搅拌12小时。随后,通过过滤从反应产物中去除反应副产物。在减压下通过蒸馏滤液,分离出180.7g(0.88mol)的目的物γ-氰硫基丙基甲基二甲氧基硅烷。γ-氰硫基丙基甲基二甲氧基硅烷的产率为88%。
在本发明的制备方法中,组分(A)和组分(B)在组分(C)的存在下反应,因此,具有高产率的带有氰硫基的有机烷氧基硅烷可以以高收率生产。
Claims (12)
1.通式(3)NCS-R1-Si(OR2)nR3 3-n(其中R1是具有1-6个碳原子的二价烃基,R2和R3是单价烃基,下标n是0-3)表示的带有氰硫基的有机烷氧基硅烷(D)的制备方法,其中使通式(1)MSCN(其中M代表碱金属)表示的硫氰酸盐(A)和通式(2)XR1Si(OR2)nR3 3-n(其中X是卤原子,R1、R2、R3和下标n的定义同上)表示的卤代烷基烷氧基硅烷(B)在相转移催化剂(C)的存在下反应。
2.权利要求1的制备方法,其中通式(1)中的M代表钠或钾。
3.权利要求1的制备方法,其中组分(A)是硫氰酸钾。
4.权利要求1的制备方法,其中组分(B)是γ-氯丙基三甲氧基硅烷。
5.权利要求1的制备方法,其中组分(B)是γ-氯丙基三乙氧基硅烷。
6.权利要求1的制备方法,其中组分(B)是γ-氯丙基甲基二甲氧基硅烷。
7.权利要求1的制备方法,其中组分(C)是1,8-二氮杂二环[5.4.0]十一-7-烯。
8.权利要求1的制备方法,其中组分(C)是四丁基溴化铵。
9.权利要求1的制备方法,其中带有氰硫基的烷氧基硅烷是γ-氰硫基丙基三甲氧基硅烷。
10.权利要求1的制备方法,其中带有氰硫基的烷氧基硅烷是γ-氰硫基丙基三乙氧基硅烷。
11.权利要求1的制备方法,其中带有氰硫基的烷氧基硅烷是γ-氰硫基丙基甲基二甲氧基硅烷。
12.权利要求1的制备方法,其中带有氰硫基的烷氧基硅烷是γ-氰硫基丙基甲基二乙氧基硅烷。
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CN102731560A (zh) * | 2012-06-25 | 2012-10-17 | 青岛科技大学 | 一种硫氰基丙基三乙氧基硅烷的合成方法 |
CN105061485A (zh) * | 2015-08-07 | 2015-11-18 | 荆州市江汉精细化工有限公司 | 一种硫氰基丙基三烷氧基硅烷的合成方法 |
CN106831852A (zh) * | 2017-01-25 | 2017-06-13 | 湖北新蓝天新材料股份有限公司 | 一种硫氰基丙基三乙氧基硅烷的合成方法 |
CN109734743A (zh) * | 2019-01-11 | 2019-05-10 | 广州艾科普新材料有限公司 | 一种硫氰基丙基三甲氧基硅烷的制备方法 |
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KR100856162B1 (ko) * | 2001-10-29 | 2008-09-03 | 다우 코닝 도레이 캄파니 리미티드 | 열경화성 유기 수지 조성물 |
CN103401021B (zh) * | 2013-08-23 | 2016-02-03 | 轻工业化学电源研究所 | 一种非水电解液及钛酸锂电池 |
CN114174307A (zh) * | 2019-07-30 | 2022-03-11 | 松本精密化学株式会社 | 含有异氰酸硅化合物的组合物及其制造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN102731560A (zh) * | 2012-06-25 | 2012-10-17 | 青岛科技大学 | 一种硫氰基丙基三乙氧基硅烷的合成方法 |
CN105061485A (zh) * | 2015-08-07 | 2015-11-18 | 荆州市江汉精细化工有限公司 | 一种硫氰基丙基三烷氧基硅烷的合成方法 |
CN105061485B (zh) * | 2015-08-07 | 2017-11-10 | 荆州市江汉精细化工有限公司 | 一种硫氰基丙基三烷氧基硅烷的合成方法 |
CN106831852A (zh) * | 2017-01-25 | 2017-06-13 | 湖北新蓝天新材料股份有限公司 | 一种硫氰基丙基三乙氧基硅烷的合成方法 |
CN109734743A (zh) * | 2019-01-11 | 2019-05-10 | 广州艾科普新材料有限公司 | 一种硫氰基丙基三甲氧基硅烷的制备方法 |
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US6867319B2 (en) | 2005-03-15 |
CN1249069C (zh) | 2006-04-05 |
EP1428829A1 (en) | 2004-06-16 |
KR20040035834A (ko) | 2004-04-29 |
JPWO2003027126A1 (ja) | 2005-01-06 |
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ATE423124T1 (de) | 2009-03-15 |
US20040210075A1 (en) | 2004-10-21 |
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