硅氢加成反应合成硅烷偶联剂KH-560的研究
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摘要
硅氢加成反应是有机硅化学中生成C-Si键最重要的方法之一,通过硅氢加成反应可以合成许多含有不同官能团的有机硅单体和聚合物。工业上最常用的硅氢加成催化剂是Pt络合物催化剂,如Speier催化剂和Kastedt催化剂。但是这些催化剂存在很严重的缺点,如催化剂不稳定、易产生凝胶化物质、烯烃异构化严重等。因此开发合适的催化剂,选择适当的催化剂配体,提高催化剂的活性和选择性是硅氢加成反应的关键。
本文以烯丙基缩水甘油醚(AGE)和三甲氧基硅烷(TMOS)为原料,以Pt络合物为催化剂经硅氢加成反应制备了目标产物γ-烯丙基缩水甘油醚氧丙基三甲氧基硅烷(KH-560)。选择了10种配体分别制备了Pt-N(C_2H_5)_3、Pt-N(CH_2CH_2CH_3)_3、Pt-P(Ph)_3、Pt-Piperidine等一系列Pt络合物催化剂,其中Pt-N(C_2H_5)_3催化剂显示出尤为突出的催化活性和选择性,并以Pt-N(C_2H_5)_3为催化剂考察了n(N(C_2H_5)_3)与n(Pt)的配比、温度、催化剂用量、反应时间及原料配比对该硅氢加成反应的影响。经GC-MS确定产物中各组分,并对该硅氢加成反应的机理进行了初步探讨,优化了反应过程,使反应能够在较低温度(55℃～75℃)下,较短时间(20min～60min)内进行,当n(AGE):n(TMOS):n(Pt-N(C_2H_5)3)=(1:1.05～1:1.10):6.72×10~(-6)(n(AGE)=0.064mol)时,KH-560的收率可达87%,且产品为无色透明液体,产品不易产生凝胶化,改善了产品质量。
本文还探索了由对苯二甲酸二甲酯(DMT)经两步法加氢制备1,4-环己烷二甲醇(CHDM)的实验,采用wt5%的Ru/C催化剂,用于第一步加氢制各中间体1,4-环己烷二甲酸二甲酯(DMCD)取得了较好进展。实验结果表明:在温度110℃,H2压力3.0MPa,催化剂量0.5g,DMT5g,THF30mL,DMT转化率和DMCD选择性分别是99.6%和96.5%。催化剂循环使用17釜后,反应时间延长至8.5h,反应温度升至140℃,DMT的平均转化率大于99.0%,DMCD的选择性保持在95.0%。
The catalytic hydrosilylation of unsaturated compounds is one of the most elegant methods for the synthesis of organosilicon compounds.Platinum catalysts displayed very high activity in the hydrosilylation reaction.The Speier catalyst(H_2PtCl_6 dissolved in i-propanol), and the Karstedt catalyst(H_2PtCl_6 dissolved in tetramethyldivinyldisioxane[(CH_2=CHSi Me_2)_2O]),have found widespread use in the silicon industry.Unfortunately,the drawbacks of these catalysts were their very limited stability,rapid formation of platinum colloids, significant amounts(20%～40%) of the isomeric alkenes.All the drawbacks often resulted in undesired side reactions.To overcome some of these undesired side reactions,there has been a marked interest in the development of newer and different catalysts for the hydrosilylation reaction.
In this paper,Pt-complexes as catalysts for the hydrosilylation of allyl glycidyl ether (AGE) with trimethoxysilane(TMOS) to prepareγ-glycidoxypropyltrimethoxysilane(KH-560), is studied.The Pt complexes with different ligands(such as Pt-N(C_2H_5)_3,Pt-N (CH_2CH_2CH_3)_3,Pt-P(Ph)_3 and Pt-Piperidine) for the catalyzing hydrosilylation were compared.The results showed that the Pt-N(C_2H_5)_3 for the hydrosilylation reaction had higher activity.The Pt-N(C_2H_5)_3 complexes catalyzing the synthesis of KH-560 were investigated in details.The structures of the products were analyzed by GC-MS;The mechanism of the hydrosilylation reaction was in a preliminary discussion.Under the optimal conditions:n (AGE):n(TMOS):n(Pt-triethylamine)=(1:1.05～1:1.10):6.72×10~(-6),55℃～75℃,20min～60min,the yield of KH-560 mount to above 86%;And the formation of colloidal Pt species was not found during the course of the hydrosolylation reaction.
1,4-Cyclohexanedimethanol(CHDM) was produced commercially by the hydrogenation of dimethyl terephthalate(DMT) in a two-stage catalytic process.Dimethyl 1,4-cyclohexane dicarboxylate(DMCD) is product of the first stage.In this paper,we found Ru/C was a good catalyst for hydrogenation of DMT to DMCD under low pressure.Under the optimized conditions of 110℃,3.0MPa,catalyst dosage 0.5g,DMT dosage 5g,THF dosage 30mL, conversion of DMT is as high as 99.6%and selectivity of DMCD is about 96.5%.Meanwhile, the Ru/C catalyst is reused for 17 runs.During lifetime test,reaction time is gradually prolonged to 8.5h and reaction temperature is step-wisely increased to 140℃to keep about 99.0%conversion of DMT and 95.0%selectivity of DMCD.
本文以烯丙基缩水甘油醚(AGE)和三甲氧基硅烷(TMOS)为原料,以Pt络合物为催化剂经硅氢加成反应制备了目标产物γ-烯丙基缩水甘油醚氧丙基三甲氧基硅烷(KH-560)。选择了10种配体分别制备了Pt-N(C_2H_5)_3、Pt-N(CH_2CH_2CH_3)_3、Pt-P(Ph)_3、Pt-Piperidine等一系列Pt络合物催化剂,其中Pt-N(C_2H_5)_3催化剂显示出尤为突出的催化活性和选择性,并以Pt-N(C_2H_5)_3为催化剂考察了n(N(C_2H_5)_3)与n(Pt)的配比、温度、催化剂用量、反应时间及原料配比对该硅氢加成反应的影响。经GC-MS确定产物中各组分,并对该硅氢加成反应的机理进行了初步探讨,优化了反应过程,使反应能够在较低温度(55℃～75℃)下,较短时间(20min～60min)内进行,当n(AGE):n(TMOS):n(Pt-N(C_2H_5)3)=(1:1.05～1:1.10):6.72×10~(-6)(n(AGE)=0.064mol)时,KH-560的收率可达87%,且产品为无色透明液体,产品不易产生凝胶化,改善了产品质量。
本文还探索了由对苯二甲酸二甲酯(DMT)经两步法加氢制备1,4-环己烷二甲醇(CHDM)的实验,采用wt5%的Ru/C催化剂,用于第一步加氢制各中间体1,4-环己烷二甲酸二甲酯(DMCD)取得了较好进展。实验结果表明:在温度110℃,H2压力3.0MPa,催化剂量0.5g,DMT5g,THF30mL,DMT转化率和DMCD选择性分别是99.6%和96.5%。催化剂循环使用17釜后,反应时间延长至8.5h,反应温度升至140℃,DMT的平均转化率大于99.0%,DMCD的选择性保持在95.0%。
The catalytic hydrosilylation of unsaturated compounds is one of the most elegant methods for the synthesis of organosilicon compounds.Platinum catalysts displayed very high activity in the hydrosilylation reaction.The Speier catalyst(H_2PtCl_6 dissolved in i-propanol), and the Karstedt catalyst(H_2PtCl_6 dissolved in tetramethyldivinyldisioxane[(CH_2=CHSi Me_2)_2O]),have found widespread use in the silicon industry.Unfortunately,the drawbacks of these catalysts were their very limited stability,rapid formation of platinum colloids, significant amounts(20%～40%) of the isomeric alkenes.All the drawbacks often resulted in undesired side reactions.To overcome some of these undesired side reactions,there has been a marked interest in the development of newer and different catalysts for the hydrosilylation reaction.
In this paper,Pt-complexes as catalysts for the hydrosilylation of allyl glycidyl ether (AGE) with trimethoxysilane(TMOS) to prepareγ-glycidoxypropyltrimethoxysilane(KH-560), is studied.The Pt complexes with different ligands(such as Pt-N(C_2H_5)_3,Pt-N (CH_2CH_2CH_3)_3,Pt-P(Ph)_3 and Pt-Piperidine) for the catalyzing hydrosilylation were compared.The results showed that the Pt-N(C_2H_5)_3 for the hydrosilylation reaction had higher activity.The Pt-N(C_2H_5)_3 complexes catalyzing the synthesis of KH-560 were investigated in details.The structures of the products were analyzed by GC-MS;The mechanism of the hydrosilylation reaction was in a preliminary discussion.Under the optimal conditions:n (AGE):n(TMOS):n(Pt-triethylamine)=(1:1.05～1:1.10):6.72×10~(-6),55℃～75℃,20min～60min,the yield of KH-560 mount to above 86%;And the formation of colloidal Pt species was not found during the course of the hydrosolylation reaction.
1,4-Cyclohexanedimethanol(CHDM) was produced commercially by the hydrogenation of dimethyl terephthalate(DMT) in a two-stage catalytic process.Dimethyl 1,4-cyclohexane dicarboxylate(DMCD) is product of the first stage.In this paper,we found Ru/C was a good catalyst for hydrogenation of DMT to DMCD under low pressure.Under the optimized conditions of 110℃,3.0MPa,catalyst dosage 0.5g,DMT dosage 5g,THF dosage 30mL, conversion of DMT is as high as 99.6%and selectivity of DMCD is about 96.5%.Meanwhile, the Ru/C catalyst is reused for 17 runs.During lifetime test,reaction time is gradually prolonged to 8.5h and reaction temperature is step-wisely increased to 140℃to keep about 99.0%conversion of DMT and 95.0%selectivity of DMCD.
引文
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