CN1156149A - 双(甲硅烷基烷基)二硫烷的生产方法 - Google Patents
双(甲硅烷基烷基)二硫烷的生产方法 Download PDFInfo
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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 System
- 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
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0898—Compounds with a Si-S linkage
Abstract
本发明涉及一种用亲核试剂使相应的多硫化物进行脱硫处理而选择性地合成甲硅烷基烷基二硫化物的方法。
Description
本发明涉及一种用亲核试剂使相应的多硫化物进行脱硫反应而选择性地合成甲硅烷基烷基二硫化物的方法。
三烷氧基丙基多硫化物是一种优秀的相介体,可用于向橡胶基质中引入氧化物原料。特别是在轮胎工业中,三乙氧基甲硅烷基丙基四硫烷([(CH3CH2O)3SiCH2CH2CH2]2S4)广泛用于硅胶增强轮胎中。在该应用领域中,硅烷一方面连接于硅胶的自由羟基上,另一方面同时又与橡胶进行固化交联。在特定的应用领域中,适于提供不具有四硫烷官能团的硅烷,而代之以具有较低活性的二硫烷官能团的硅烷。在各种专利及公开出版物中均描述了甲硅烷基烷基二硫烷及相应的多硫化物的合成方法。
DE-PS 2 405758和DE-PS 2 542534涉及由巯基烷基硅烷和硫为原料的生产方法,其中反应过程会释放出硫化氢。
各种生产方法以就地形成的二硫化物开始,用这种二硫化物对卤代烷基硅烷进行亲核取代。这些方法的区别之处仅在于二硫化物亲核试剂的合成。按照DE-PS 3 311340,由硫化氢、钠和硫在乙醇中反应产生二硫化物。
按照US专利5,405,985,制备过程使用硫化钠水溶液与硫进行。本领域的技术人员公知,在硫化物与硫的反应中产生各种多硫化物的混合物,从而,当进行亲核取代时,仅可能产生出各种链长的多硫烷的混合物。硫醇或其盐与硫的反应也如此。进而,相应的二硫烷从这些产物的混合物中分离出来也很困难。
DE-PS 2 360470的确描述了一种用于生产纯双(甲硅烷基烷基)二硫烷的方法,该方法是用硫酰氯来氧化相应的硫醇,该方法导致形成高腐蚀性副产物(SO2,HCl)。进而在甲硅烷基上发生的副反应将导致目的产物的收率减少(例如:63.3%)。另一种氧化方法见于EP-A1 217178。在该方法中,相应的硫醇盐用碘氧化以得到二硫化物。在加工生产甲硅烷基烷基硫醇后,该方法还需要两个反应步骤。
本发明提供了一种通式(I)的双(甲硅烷基烷基)二硫烷的生产方法,
(R1R2R3SiR4)2S2(I)其中,R1,R2,R3可相同或不同,且为具有1-8个碳原子的支链或无支链的烷基和/或烷氧基,氢或一价芳基,特别是苯基,甲苯基,苯甲基R4为具有1-8个碳原子、优选2-4个碳原子的二价亚烷基,或其特征在于,使通式(II)的甲硅烷基烷基多硫化物或甲硅烷基烷基多硫化物的混合物与通式(III)或通式(IV)或通式(V)的亲核化合物反应,
所说的通式(II)为:(R1R2R3SiR4)2Sn
其中R1、R2、R3和R4与式(I)中定义相同,n为3-20的整数,优选n为3-10;
所说的通式(III)为:M+CN-
所说的通式(IV)为:M+ 2SO3 2-
其中M+为碱金属阳离子,取代或未取代的铵离子,或半个碱土金属离子或锌离子;
所说的通式(V)为:R5R6R7P
其中,R5、R6、R7与式(I)中R1、R2、R3定义相同,
其中,通式(III)-(V)的化合物的用量为与欲从式(II)化合物除去的硫原子等摩尔量;
过滤除去形成的固体,将得到的二硫烷提纯。
该方法可以在无溶剂的体系中或加入溶剂的体系中进行。优选的溶剂为所用的亲核试剂至少能部分溶解的溶剂。
可以使用脂肪族溶剂,如戊烷、己烷或各种支链或无支链的烷烃或芳烃溶剂的混合物,如苯、甲苯或二甲苯,或醚如乙醚、二苄醚、甲基叔丁基醚。
优选使用的有机溶剂为具有1-8个碳原子的直链或支链醇,如甲醇、乙醇、丙醇、丁醇或戊醇。具有5-8个碳原子的环烷醇、苯酚或苄基醇也适用。
为了避免发生酯基转移,例如,适于采用相应于基团R1、R2、R3(烷氧基)的醇。同样有利的是,也可非必须地使用这些醇的混合物,特别是R1、R2、R3在一个化合物中具有不同的定义时。
在本发明的具体实施方案中,如果溶剂如水与所用的硫烷不混溶,反应则在两相体系中进行。
此时,以常规量使用已知的相转移催化剂,如Aliquat 336 (C8H17)3N+CH3Cl-(见E.V.Dehmlow,S.S.Dehmlow,Phase Transfer Catalysis,2nd edition,Weinheim1983)。
反应可以在室温及较高的温度下进行。为了使反应时间尽可能短,反应适于在升高的温度下进行,优选在所用溶剂的沸点下进行。
反应过程加压与否对反应的成功并不重要。
通过下述实施例对本发明的实施过程给予说明。
在本发明的优选实施方案中,二硫化物以简便方式生产。
分别生产欲脱硫的多硫烷是不必要的。按照本发明,可以在“单一容器”过程中就地合成这些多硫烷,并将它们直接转化成所要的二硫化物。
为此,制备一种溶液,也可以是一种悬浮液,其包括:a)通式为M+ 2Sn的多硫化物或多硫化物的混合物,其中M+和n如前定义;b)通式为M+CN-,M+ 2SO3 2-,R5R6R7P中的一种亲核试剂或不同亲核试剂的混合物,其中M+,R5,R6,R7如前定义;c)通式为(VI)的有机硅化合物:Cl-R4-Si(R1R2R3)3(VI),其中R1,R2,R3和R4如前定义;
特别是(a)、(b)、(c)的摩尔比为0.4-0.7∶1-1.1∶1。
(a)∶(b)的比值是由欲从式(II)中除去的硫原子数计算的。所用的溶剂,特别是相应于式(VI)的溶剂优选式(I)中R1、R2、R3为烷氧基的醇。
优选在20℃-35℃的温度下向溶剂中搅拌加入各成分,加入的次序并不重要。
反应在高于上述的温度下进行,特别是在40℃至混合物中所用的溶剂的回流温度下进行。
通常,以反应混合物的总重量计,使用10-90%(重量)的有机硅化合物的溶液。
反应后,将混合物冷却,真空除去溶剂,剩余的固体用适宜的所要的二硫化物能溶解在其中的有机溶剂如石油醚提纯。
一经除去溶剂后,即得到纯的二硫烷。
以下的实施例用于解释本发明的方法。实施例1在乙醇中用NaCN对双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理
将于60ml乙醇中的67.37g(0.125mol)的双(三乙氧基甲硅烷基丙基)四硫烷加至250ml的三颈烧瓶中,该烧瓶安装有磁性搅拌器和回流冷凝器。向混合物中加入12.25g(O.250mol)的粉状氰化钠。将混合物回流4小时。冷却至室温后,在旋转蒸发器中除去溶剂。在室温下将固体/液体混合物静置2小时,直至固体完全结晶,将混合物过滤。滤饼用50ml的石油醚洗涤三次。汽提除去石油醚后,得到纯的双(三乙氧基甲硅烷基丙基)二硫烷(经1H-NMR证实)。收率:97%。实施例2在乙醇中用KCN对双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理
将60升乙醇中的67.34kg(125mol)的双(三乙氧基甲硅烷基丙基)四硫烷加至200升的玻璃蒸馏釜中,该设备安装有高速搅拌器。向混合物中搅拌加入16.28kg(250mol)的固体氰化钠。将混合物在氮气氛下回流4小时。在80℃及真空下汽提除去溶剂,使混合物冷却,并滤出沉淀。滤饼用10升石油醚洗涤三次。70℃及真空下除去石油醚,得到58.8kg(124mol)纯的双(三乙氧基甲硅烷基丙基)二硫烷(经1H-NMR证实)。收率:99%。实施例3在两相体系中用NaCN对双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理将160ml水中的19.6g(0.4mol)的NaCN加至500ml三颈烧瓶中,该烧瓶安装有磁性搅拌器,回流冷凝器和滴液漏斗,将其加热至90℃。达到该温度后,于45分钟内,向其中滴加107.2g(0.2mol)的双(三乙氧基甲硅烷基丙基)四硫烷、120ml的甲苯及5g的相转移催化剂Aliquat 336。加完后,将混合物在该温度下再搅拌2小时。冷却后,滤出12.4g的不溶性物质。将滤液的有机相与水相分离,有机相进行真空蒸发。得到90.4g(0.19mol)纯的双(三乙氧基甲硅烷基丙基)二硫烷(经1H-NMR证实)。收率:95%。实施例4在乙醇中用三苯基磷烷(triphenylphosphane)对双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理
将60ml乙醇中的67.37g(0.125mol)的双(三乙氧基甲硅烷基丙基)四硫烷加至250ml的三颈烧瓶中,该烧瓶安装有磁性搅拌器和回流冷凝器。向混合物中加入65.57g(0.250mol)的固体三苯基磷烷。将混合物回流4小时。冷却至室温后,在旋转蒸发器中除去溶剂。在室温下将固体/液体混合物静置2小时,直至固体完全结晶,将混合物过滤。滤饼用50ml的石油醚洗涤三次。汽提除去石油醚后,得到纯的双(三乙氧基甲硅烷基丙基)二硫烷(经1H-NMR证实)。收率:98%。实施例5用亚硫酸钠水合物对双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理
在安装有KPG搅拌器、回流冷凝器和滴液漏斗的1000ml的三颈烧瓶中,将160ml水和105.9g(0.85mol)的亚硫酸钠水合物的混合物加热至90℃。在该温度下,于30分钟内,向其中滴加226.4g(0.42mol)的的双(三乙氧基甲硅烷基丙基)四硫烷、20ml的乙醇及5g的相转移催化剂Aliquat336。加完后,再向混合物中加入100ml的乙醇,在80℃下将混合物搅拌3.5小时。将混合物冷却至室温后,将水相分离,有机相在旋转蒸发器中进行真空蒸发。得到198.9g(0.41mol)纯的双(三乙氧基甲硅烷基丙基)二硫烷(经1H-NMR证实)。收率:99%。实施例6用NaCN对就地形成的双(三乙氧基甲硅烷基丙基)四硫烷进行脱硫处理
在安装有磁性搅拌器和回流冷凝器的500ml三颈烧瓶中加入43.5g(0.25mol)的平均组成为Na2S4的多硫化物、24.5g(0.5mol)的NaCN和120.4g(0.5mol)氯代丙基三乙氧基硅烷于120ml乙醇中的混合物。将混合物回流2小时。将产物混合物冷却至室温后,真空除去溶剂。将剩余物再溶解于150ml石油醚中,并过滤。滤饼用50ml石油醚洗涤三次。真空下除去合并后的滤饼中的溶剂。得到108.7g(0.21mol)纯的二硫烷(经1H-NMR证实)。收率:94%。
Claims (6)
1、一种通式(I)的双(甲硅烷基烷基)二硫烷的生产方法,
(R1R2R3SiR4)2S2 (I)
其中,
R1,R2,R3可相同或不同,且为具有1-8个碳原子的支链或无支链的烷基和/或烷氧基,氢或一价芳基,特别是苯基、甲苯基、苯甲基,
其特征在于,使通式(II)的甲硅烷基烷基多硫化物或甲硅烷基烷基多硫化物的混合物与通式(III)或通式(IV)或通式(V)的亲核化合物反应,
所说的通式(II)为:(R1R2R3SiR4)2Sn
其中R1、R2、R3和R4与式(I)中定义相同,n为3-20的整数,优选n为3-10;
所说的通式(III)为:M+CN-
所说的通式(IV)为:M+ 2SO3 2-
其中M+为碱金属阳离子,取代或未取代的铵离子,或半个碱土金属离子或锌离子;
所说的通式(V)为:R5R6R7P
其中,R5、R6、R7与式(I)中R1、R2、R3定义相同,
其中,通式(III)-(V)的化合物的用量为与欲从式(II)化合物除去的硫原子等摩尔量;
过滤除去形成的固体,将得到的二硫烷提纯。
2、根据权利要求1的方法,其特征在于式(III)-(V)的化合物以混合物使用。
3、根据权利要求1和2的方法,其特征在于反应在可溶解亲核化合物的溶剂存在下进行。
4、根据权利要求1和3的方法,其特征在于反应是在20℃至所用溶剂的沸点间的温度下进行。
5、根据权利要求1-4的方法,其特征在于反应是在有相转移催化剂存在下的两相体系中进行的。
6、根据权利要求1的方法,其特征在于欲反应的通式(II)的甲硅烷基烷基多硫烷是通过就地形成一种溶液而合成的,该溶液包含:
a)由通式M+ 2Sn代表的多硫化物或多硫化物的混合物,其中M+和n如前定义;
b)亲核试剂M+CN-,M+ 2SO3 2-,R5R6R7P中的一种或其混合物,其中M+,R5,R6,R7如前定义;
c)通式(VI)代表的有机硅化合物:Cl-R4-Si(R1R2R3)3(VI),其中R1,R2,R3和R4如前定义;
(a)、(b)、(c)的摩尔比为0.4-0.7∶1-1.1∶1,该混合物一起反应,通过常规的提纯方法分离出所要的二硫化物。
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DE19541404A DE19541404A1 (de) | 1995-11-07 | 1995-11-07 | Verfahren zur selektiven Synthese von Silylalkyldisulfiden |
DE19541404.7 | 1995-11-07 |
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1995
- 1995-11-07 DE DE19541404A patent/DE19541404A1/de not_active Withdrawn
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1996
- 1996-09-23 PT PT96115226T patent/PT773224E/pt unknown
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- 1996-09-23 DE DE59608364T patent/DE59608364D1/de not_active Expired - Fee Related
- 1996-09-23 EP EP96115226A patent/EP0773224B1/de not_active Expired - Lifetime
- 1996-09-23 ES ES96115226T patent/ES2168424T3/es not_active Expired - Lifetime
- 1996-10-30 PL PL96316746A patent/PL183494B1/pl unknown
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- 1996-10-30 TW TW085113256A patent/TW382018B/zh not_active IP Right Cessation
- 1996-11-04 CN CN96120660A patent/CN1070862C/zh not_active Expired - Fee Related
- 1996-11-05 US US08/743,842 patent/US5663395A/en not_active Expired - Fee Related
- 1996-11-05 CA CA002189601A patent/CA2189601A1/en not_active Abandoned
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DE19541404A1 (de) | 1997-05-15 |
SK143596A3 (en) | 1997-05-07 |
CZ318096A3 (en) | 1997-05-14 |
PL316746A1 (en) | 1997-05-12 |
AU713295B2 (en) | 1999-11-25 |
KR970027094A (ko) | 1997-06-24 |
EP0773224B1 (de) | 2001-12-05 |
CN1070862C (zh) | 2001-09-12 |
US5663395A (en) | 1997-09-02 |
TW382018B (en) | 2000-02-11 |
ES2168424T3 (es) | 2002-06-16 |
EP0773224A3 (de) | 1998-03-18 |
HRP960516A2 (en) | 1998-02-28 |
HUP9603081A3 (en) | 1998-09-28 |
HUP9603081A2 (en) | 1997-10-28 |
SI0773224T1 (en) | 2002-06-30 |
BR9605476A (pt) | 1998-08-11 |
EP0773224A2 (de) | 1997-05-14 |
HRP960516B1 (en) | 2002-04-30 |
HU217297B (hu) | 1999-12-28 |
AU7062496A (en) | 1997-05-15 |
CA2189601A1 (en) | 1997-05-08 |
DE59608364D1 (de) | 2002-01-17 |
HU9603081D0 (en) | 1996-12-30 |
JPH09169774A (ja) | 1997-06-30 |
PT773224E (pt) | 2002-05-31 |
PL183494B1 (pl) | 2002-06-28 |
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