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Hydrogenation of Polybutadiene at High Pressure
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2021-12-29 , DOI: 10.1021/acs.iecr.1c03873 Matías Menossi 1 , Andrés Ciolino 2, 3 , Lidia M. Quinzani 2 , Marcelo S. Zabaloy 2, 3 , Juan M. Milanesio 1
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2021-12-29 , DOI: 10.1021/acs.iecr.1c03873 Matías Menossi 1 , Andrés Ciolino 2, 3 , Lidia M. Quinzani 2 , Marcelo S. Zabaloy 2, 3 , Juan M. Milanesio 1
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The problem of low reaction rate due to poor mass transfer in the two-fluid-phase conventional hydrogenation of unsaturated polymers can be overcome by using dimethyl ether/n-pentane as a light solvent mixture as the medium to carry out the reaction. In this work, a series of polybutadiene (PB) batch hydrogenation reactions were performed at high-pressure using Wilkinson/triphenylphosphine as a homogeneous catalyst/cocatalyst. Hydrogenated PBs with 86%–100% of saturation degree were obtained by changing processing variables: overall density, temperature, stirring frequency, initial hydrogen (H2)/double bonds ratio, global concentration of catalyst/cocatalyst, and reaction time. The variables that most affect the process are temperature, H2 excess, stirring frequency, and reaction time. By increasing these variables, the larger the saturation degree will be. The use of Wilkinson’s catalyst gives place to totally hydrogenated PB four times faster than conventional hydrogenation based on homogeneous catalysis (e.g., RhCl(PPh3)3, RhCl(P(C6H4-m-SO3Na))3, RhCl(PPh2(C6H4-m-SO3Na))) but giving place to some scission and cross-linking reactions.
中文翻译：
聚丁二烯高压加氢
采用二甲醚/正戊烷作为轻溶剂混合物作为介质进行反应，可以克服不饱和聚合物两相常规加氢过程中传质差导致反应速率低的问题。在这项工作中，使用 Wilkinson/三苯膦作为均相催化剂/助催化剂，在高压下进行了一系列聚丁二烯 (PB) 间歇式加氢反应。通过改变工艺变量获得饱和度为 86%–100% 的氢化 PB：总密度、温度、搅拌频率、初始氢 (H 2 )/双键比、催化剂/助催化剂的整体浓度和反应时间。对过程影响最大的变量是温度 H 2过量、搅拌频率和反应时间。通过增加这些变量，饱和度将越大。Wilkinson 催化剂的使用使 PB 的完全氢化速度比基于均相催化的常规氢化（例如 RhCl(PPh 3 ) 3、RhCl(P(C 6 H 4 -m-SO 3 Na)) 3、RhCl (PPh2(C6H4-m-SO3Na)))，但会发生一些断裂和交联反应。
更新日期：2022-01-12
中文翻译：
聚丁二烯高压加氢
采用二甲醚/正戊烷作为轻溶剂混合物作为介质进行反应，可以克服不饱和聚合物两相常规加氢过程中传质差导致反应速率低的问题。在这项工作中，使用 Wilkinson/三苯膦作为均相催化剂/助催化剂，在高压下进行了一系列聚丁二烯 (PB) 间歇式加氢反应。通过改变工艺变量获得饱和度为 86%–100% 的氢化 PB：总密度、温度、搅拌频率、初始氢 (H 2 )/双键比、催化剂/助催化剂的整体浓度和反应时间。对过程影响最大的变量是温度 H 2过量、搅拌频率和反应时间。通过增加这些变量，饱和度将越大。Wilkinson 催化剂的使用使 PB 的完全氢化速度比基于均相催化的常规氢化（例如 RhCl(PPh 3 ) 3、RhCl(P(C 6 H 4 -m-SO 3 Na)) 3、RhCl (PPh2(C6H4-m-SO3Na)))，但会发生一些断裂和交联反应。
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