CN100436522C - 一种含双键的硅烷偶联剂及其制备方法 - Google Patents
一种含双键的硅烷偶联剂及其制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000007822 coupling agent Substances 0.000 title description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- -1 insaturated acyl chlorine Chemical compound 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012263 liquid product Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 30
- 150000001263 acyl chlorides Chemical class 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 claims description 9
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 6
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 5
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 5
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 5
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- IWTYTFSSTWXZFU-QPJJXVBHSA-N [(e)-3-chloroprop-1-enyl]benzene Chemical compound ClC\C=C\C1=CC=CC=C1 IWTYTFSSTWXZFU-QPJJXVBHSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 3
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 claims description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
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- 239000006229 carbon black Substances 0.000 description 18
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- IVYZYGOOZIBZHB-UHFFFAOYSA-N 2-sulfanylideneethenone Chemical compound O=C=C=S IVYZYGOOZIBZHB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 238000004513 sizing Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
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- 239000000377 silicon dioxide Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 239000001110 calcium chloride Substances 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种含双键的硅烷偶联剂及其制备方法。它是将巯烃基硅烷加入有机溶剂中,配成质量浓度5~20%的溶液,加入摩尔数为巯烃基硅烷1~1.25倍的有机催化剂,浴冷却至0~-20℃,搅拌,以0.1~0.6m3/h速度通入氮气,以0.5~1ml/min速度滴加与巯烃基硅烷等摩尔数的不饱和酰氯,滴加完毕后继续在搅拌与排气条件下反应1~10h,过滤除去固体盐类副产物,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物。本发明工艺流程简单,产率高,易于推广。基于本发明所制得的含双键的硅烷偶联剂具有较高的热稳定性与较强的偶联效果,可代替传统硅烷偶联剂,用于含白炭黑的橡胶中。
Description
技术领域
本发明涉及一种含双键的硅烷偶联剂及其制备方法。
背景技术
与炭黑相比,白炭黑在兼顾胎面胶耐磨性、湿路面牵引性和滚动阻力方面具有明显的优势,被用于新一代低滚动阻力、低油耗“绿色轮胎”的主要补强剂,且超微细粒子白炭黑补强的硫化胶具有低损耗和耐湿滑性等优点。
白炭黑粒子表面含大量硅醇基,与橡胶的相容性差,且自炭黑粒子在橡胶混炼过程中易发生团聚,因而不经表面处理的白炭黑补强效果差。含硫元素的双官能团硅烷偶联剂,如γ-巯丙基三甲氧基硅烷、γ-硫氰基丙基三乙氧基硅烷、双(3-三乙氧基硅基丙基)二硫化物(TESPD)或双(3-三乙氧基硅基丙基)四硫化物(TESPT),在橡胶混炼时可对白炭黑进行表面改性,在橡胶成型时又可部分参与橡胶硫化,使白炭黑粒子与橡胶基体之间形成牢固的网络结构。
在轮胎胎面胶中,以白炭黑尤其是高分散性沉淀法白炭黑与偶联剂并用,可同时提高轮胎寿命(提高耐磨性)和安全性(提高抗湿滑性)、降低燃油消耗(降低滚动阻力)。轮胎工业目前使用的几乎全是含硫硅烷偶联剂,其中多硫硅烷偶联剂TESPD与TESPT用量最大。在橡胶混炼过程中,多硫硅烷偶联剂需较长时间和较高温度才能与白炭黑充分反应。当混炼温度高于160℃时,多硫硅烷偶联剂的多硫键断裂,引起胶料焦烧、门尼粘度增大,不利于白炭黑粒子在橡胶中的分散。用多硫硅烷偶联剂改性白炭黑还存在混炼时间长、混炼段数(3~6段)多、胶料气孔率高、因焦烧而产生次品等缺点。
针对多硫硅烷偶联剂的这些问题,Crompoton Osi公司开发了硅烷偶联剂3-辛酰基硫代-1-丙基三甲氧基硅烷(NXT)
NXT用于白炭黑填充的胎面胶可降低胶料粘度,减少混炼段数,改善胶料加工性能,促进白炭黑分散,延长胶料焦烧时间与储存期,减少成品中挥发物含量,提高胎面胶耐老化性能等一系列优点(Joshi P G.,Pickwell R J.,Weller K J.,Hofstetter M H.,Pohl E R.,Stout M E.,Osterholtz F D.,Next-generation silianecoupling agent for silica/siliane reinforcement tire tread compounds.Tire Tech.Int.,2002,80-84;Yan H.,Sun K.,Zhang Y.,Zhang Y.,Fan Y.,Effects of silane couplingagents on the vulcanization characteristics of natural rubber.J.Appl.Polym.Sci.,2004,94:1511-1518)。
发明内容
本发明的目的是提供一种含双键的硅烷偶联剂及其制备方法。
含双键的硅烷偶联剂的分子结构式为:
m=1~3的线性饱和烃基,R1为含双键的烃基,R2为甲基或乙基。
含双键的硅烷偶联剂的制备方法是将巯烃基硅烷加入有机溶剂中,配成质量浓度5~20%的溶液,加入摩尔数为巯烃基硅烷1~1.25倍的有机催化剂,冷却至0~-20℃,搅拌,以0.1~0.6m3/h速度通入氮气,以0.5~1ml/min速度滴加与巯烃基硅烷等摩尔数的不饱和酰氯,滴加完毕后继续在搅拌与排气条件下反应1~10h,过滤除去固体盐类副产物,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物。
在本发明的制备方法中:
巯烃基硅烷是巯甲基三甲氧基硅烷、β-巯乙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、巯甲基三乙氧基硅烷、β-巯乙基三乙氧基硅烷或γ-巯丙基三乙氧基硅烷;有机溶剂是氯仿、四氯化碳、乙醚、丁醚、苯、甲苯、己烷或环己烷;有机催化剂是吡啶、三乙胺、三正丙胺、三正丁胺、N,N-二甲基丁胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、N,N-二甲基环己胺、N,N-二乙基环己胺、N,N-二乙基苯胺或十二烷基二甲基胺;不饱和酰氯是丙烯酰氯、甲基丙烯酰氯、2-丁烯酰氯、4-戊烯酰氯、10-十一碳烯酰氯、肉桂酰氯或油酰氯。
本发明的优点是:
1)利用不巯烃基硅烷与饱和酰氯在低温与氮气保护下反应制备含双键的硅烷偶联剂,生产工艺简单;
2)硅烷偶联剂分子1个羰基碳-硫键、1个双键与3个烷氧基,偶联效果明显,分子中的羰基碳-硫键稳定,在橡胶混炼加工温度下基本不发生分解,不易引起橡胶焦烧,有利于白炭黑粒子在橡胶中的分散;
3)含双键的硅烷偶联剂用于硫黄或过氧化物硫化的橡胶中时,其羰基碳-硫键在橡胶热压成型过程中发生分解,所产生的自由基参与橡胶硫化,大大减小硫化胶中挥发分含量,并提高交联密度,改善硫化胶的力学性能。
具体实施方式
本发明开发一种结合NXT与TESPT优点的硅烷偶联剂,其分子含有1个羰基碳-硫键、1个双键与3个烷氧基。在橡胶混炼时,该硅烷偶联剂的烷氧基能够对白炭黑起表面改性作用,但羰基碳-硫键基本不发生分解,不易引起胶料焦烧,有利于白炭黑在橡胶中的分散。在橡胶硫化过程中,羰基碳-硫键发生断裂,产生含双键的自由基。该自由基可参与橡胶硫化,使白炭黑粒子与橡胶基体之间形成牢固的网络结构。
本发明使用的巯烃基硅烷是巯甲基三甲氧基硅烷、β-巯乙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、巯甲基三乙氧基硅烷、β-巯乙基三乙氧基硅烷或γ-巯丙基三乙氧基硅烷。巯基硅烷偶联剂的制备技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“顾文秀,杨倩,廖学巍,邓建平,张海兵,史保川,巯烃基硅烷偶联剂的合成.有机硅材料,2002,16(5):9-11”。一些巯烃基硅烷可以从商业硅烷偶联剂产品中选择,如可以从美国联合碳化物公司、武汉天目科技发展有限公司或杭州大地化工有限公司等购买γ-巯丙基三甲氧基硅烷或γ-巯丙基三乙氧基硅烷。
使用的不饱和酰氯是丙烯酰氯、甲基丙烯酰氯、2-丁烯酰氯、4-戊烯酰氯、10-十一碳烯酰氯、肉桂酰氯或油酰氯。
在有机催化剂的作用下,将等摩尔巯烃基硅烷与不饱和酰氯在有机溶剂中、在氮气保护条件下进行低温反应,一步合成含双键的硅烷偶联剂。不饱和酰氯是活泼的化学试剂,与空气中的水分接触而发生水解,因而滴加不饱和酰氯前需向反应介质中通氮气,将介质中的空气与水分全部排出。不饱和酰氯与巯烃基硅烷剧烈反应而生成硫醇酯,同时释放大量氯化氢。氯化氢与有机催化剂反应而剧烈放热,因而反应需控制在低温下进行,且需向巯烃基硅烷溶液中缓慢滴加不饱和酰氯。反应所释放出的氯化氢不利于硫醇酯的生成,向反应介质中通氮气的另一目的是将反应所生产的大部分氯化氢排出。可将氯化氢气体直接排到大气中,也可排到与反应容器相连接的废气接收器内,废气接收器内放置氢氧化钠、氧化钾或氧化钙。考虑到环保要求,本发明推荐使用废气接收器内来吸收氯化氢。
有机催化剂除具有催化功效外,还能氯化氢副产物。以吡啶为例,反应原理为
没有被氮气排出的氯化氢与有机催化剂结合,产生白色沉淀,需经过虑除去。
在强烈搅拌条件下缓慢滴加不饱和酰氯来控制反应速度、避免局部过热是本发明的关键之一。为防止不饱和酰氯与空气中的水分接触而发生水解,可以将不饱和酰氯置于与反应器相连的滴液装置内,滴液装置的另一端应配置装有干燥剂氯化钙、无水硫酸钠、无水硫酸铜或失水硅胶粉末的干燥管。
在低温条件下进行巯烃基硅烷与不饱和酰氯间的反应是本发明的关键之一。采用冰盐浴控制低温反应的技术是公知的,本发明推荐的反应温度为0~-20℃。冰盐浴采用的无机盐是氯化铵、硝酸铵、硝酸钠、氯化钠或氯化钙,无机盐可以采用工业粗产品以降低成本。
以下结合具体实施例进一步说明本发明。
实施例1:
以巯甲基三甲氧基硅烷、丙烯酰氯为原料制备含双键的硅烷偶联剂的方法:
称取0.2mol(16.8g)巯甲基三甲氧基硅烷与320g氯仿,置于圆底三口烧瓶中,配成5%的溶液,加入0.2mol(17g)吡啶和1枚磁子,冷却至0℃,并从三口烧瓶的一侧口以0.1m3/h的速度通入氮气,将三口烧瓶的另一侧口连接内置氢氧化钠的废气接收器,在三口烧瓶中间口上安装内盛0.2mol(18.1g)丙烯酰氯的滴液漏斗,滴液漏斗上端配置内装氯化钙的干燥管,在磁力搅拌的同时以0.5
ml/min的速度向三口烧瓶中滴加乙二酰氯,滴加完毕后继续在氮气保护下搅拌1h,过滤,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物,收率78.2%。
实施例2:
以β-巯乙基三甲氧基硅烷、甲基丙烯酰氯为原料制备含双键的硅烷偶联剂的方法:
称取2mol(364g)β-巯乙基三甲氧基硅烷与1.4Kg四氯化碳,置于不锈钢容器中,配成20%的溶液,加入2.5mol(222g)三乙胺,冷却至-20℃,搅拌使溶液混合均匀,以0.6m3/h的速度通入氮气,采用滴液漏斗以1ml/min速度滴加2mol(209g)甲基丙烯酰氯,滴加完毕后继续在氮气保护下搅拌10h,过滤反应产物,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物,收率85.2%。
实施例3:
以γ-巯丙基三甲氧基硅烷、2-丁烯酰氯为原料制备含双键的硅烷偶联剂的方法:
称取0.2mol(39.2g)γ-巯丙基三甲氧基硅烷与353g乙醚,置于圆底三口烧瓶中,配成10%的溶液,加入0.25mol(35.8g)三正丙胺与1枚磁子,冷却至-10℃,并从三口烧瓶的一侧口以0.4m3/h的速率通入氮气,将三口烧瓶的另一侧口连接内置氢氧化钾的废气接收器,在三口烧瓶中间口装上滴液漏斗,在磁力搅拌的同时以0.8ml/min速度滴加0.1mol(20.9g)2-丁烯酰氯,滴加完毕后在氮气保护下继续搅拌5h,过滤反应产物,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物,收率81.4%。
实施例4~6:
分别以巯甲基三乙氧基硅烷、β-巯乙基三乙氧基硅烷或γ-巯丙基三乙氧基硅烷代替γ-巯丙基三甲氧基硅烷,其余条件同实施例3。
实施例7~11
分别以丁醚、苯、甲苯、己烷或环己烷代替乙醚,其余条件同实施例3。
实施例12~19
分别以三正丁胺、N,N-二甲基丁胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、N,N-二甲基环己胺、N,N-二乙基环己胺、N,N-二乙基苯胺或十二烷基二甲基胺代替三正丙胺,其余条件同实施例3。
实施例20~23
分别以4-戊烯酰氯、10-十一碳烯酰氯、肉桂酰氯或油酰氯代替2-丁烯酰氯,其余条件同实施例3。
本发明提供了一种含双键的硅烷偶联剂及其制备方法。硅烷偶联剂的制备流程简单,产率高,分离工艺简单,易于推广。基于本发明制得的含双键的硅烷偶联剂具有较高的热稳定性与较强的偶联效果,可代替传统硅烷偶联剂,采用公知的混炼方法添加到含白炭黑的橡胶组合物中,提高硫化胶的综合性能。
Claims (5)
1.一种含双键的硅烷偶联剂的制备方法,其特征在于,将巯烃基硅烷加入有机溶剂中,配成质量浓度5~20%的溶液,加入摩尔数为巯烃基硅烷1~1.25倍的有机催化剂,冷却至0~-20℃,搅拌,以0.1~0.6m3/h速度通入氮气,以0.5~1ml/min速度滴加与巯烃基硅烷等摩尔数的不饱和酰氯,滴加完毕后继续在搅拌与排气条件下反应1~10h,过滤除去固体盐类副产物,将滤液进行减压蒸馏除去低沸点馏分,获得淡黄色液体产物。
2.根据权利要求1所述的含双键的硅烷偶联剂制备方法,其特征在于,所说的巯烃基硅烷为:巯甲基三甲氧基硅烷、β-巯乙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、巯甲基三乙氧基硅烷、β-巯乙基三乙氧基硅烷或γ-巯丙基三乙氧基硅烷。
3.根据权利要求1所述的含双键的硅烷偶联剂的制备方法,其特征在于,所说的有机溶剂为:氯仿、四氯化碳、乙醚、丁醚、苯、甲苯、己烷或环己烷。
4.根据权利要求1所述的含双键的硅烷偶联剂的制备方法,其特征在于,所说的有机催化剂为:吡啶、三乙胺、三正丙胺、三正丁胺、N,N-二甲基丁胺、N,N-二异丙基乙胺、N,N-二甲基苯胺、N,N-二甲基环己胺、N,N-二乙基环己胺、N,N-二乙基苯胺或十二烷基二甲基胺。
5.根据权利要求1所述的含双键的硅烷偶联剂的制备方法,其特征在于,所说的不饱和酰氯为:丙烯酰氯、甲基丙烯酰氯、2-丁烯酰氯、4-戊烯酰氯、10-十一碳烯酰氯、肉桂酰氯或油酰氯。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63270751A (ja) * | 1987-04-30 | 1988-11-08 | Bridgestone Corp | タイヤトレツド用ゴム組成物 |
CN1434839A (zh) * | 2000-06-08 | 2003-08-06 | 尤尼罗亚尔化学公司 | 橡胶组合物和提高门尼烧焦值的方法 |
US6608125B2 (en) * | 1997-08-21 | 2003-08-19 | Crompton Corporation | Blocked mercaptosilane coupling agents for filled rubbers |
US6777569B1 (en) * | 2003-03-03 | 2004-08-17 | General Electric Company | Process for the manufacture of blocked mercaptosilanes |
US6852358B1 (en) * | 2003-08-28 | 2005-02-08 | Chang Chun Plastics Co., Ltd. | Process for preparing an optical waveguide component from acrylate/titanium alkoxide composite material and the prepared optical waveguide component |
CN1781979A (zh) * | 2004-09-10 | 2006-06-07 | 固特异轮胎和橡胶公司 | 具有橡胶组合物的胎面的轮胎 |
US20060128868A1 (en) * | 2004-12-10 | 2006-06-15 | Martter Teresa D | Tire with tread containing combination of specialized elastomer and coupling agent |
-
2007
- 2007-01-31 CN CNB2007100671256A patent/CN100436522C/zh not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63270751A (ja) * | 1987-04-30 | 1988-11-08 | Bridgestone Corp | タイヤトレツド用ゴム組成物 |
US6608125B2 (en) * | 1997-08-21 | 2003-08-19 | Crompton Corporation | Blocked mercaptosilane coupling agents for filled rubbers |
US20040210001A1 (en) * | 1997-08-21 | 2004-10-21 | Cruse Richard W. | Blocked mercaptosilane coupling agents for filled rubbers |
CN1434839A (zh) * | 2000-06-08 | 2003-08-06 | 尤尼罗亚尔化学公司 | 橡胶组合物和提高门尼烧焦值的方法 |
US6777569B1 (en) * | 2003-03-03 | 2004-08-17 | General Electric Company | Process for the manufacture of blocked mercaptosilanes |
US6852358B1 (en) * | 2003-08-28 | 2005-02-08 | Chang Chun Plastics Co., Ltd. | Process for preparing an optical waveguide component from acrylate/titanium alkoxide composite material and the prepared optical waveguide component |
CN1781979A (zh) * | 2004-09-10 | 2006-06-07 | 固特异轮胎和橡胶公司 | 具有橡胶组合物的胎面的轮胎 |
US20060128868A1 (en) * | 2004-12-10 | 2006-06-15 | Martter Teresa D | Tire with tread containing combination of specialized elastomer and coupling agent |
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