新型CBS凝胶催化剂的合成及催化性能

doi:10.16085/j.issn.1000-6613.2018-0368

摘要/Abstract

摘要：

1,1-二苯基-1-[(2S,4R)-4-(4-乙烯基-苄氧基)-2-吡咯烷基]-甲醇（功能单体4）、苯乙烯与聚醚Pluronic F-127在过氧化月桂酰引发下进行溶液聚合，得到独特的梳状接枝共聚物。接枝共聚物进一步反应，形成交联的CBS催化剂前体（G-CBSP）。前体与甲基硼酸在甲苯-四氢呋喃中进行缩合反应，得到新型CBS凝胶催化剂（G-CBS），用于催化苯乙酮的不对称还原反应。通过FTIR对催化剂结构进行表征，利用SEM观察反应介质中聚醚Pluronic F-127组分对催化剂凝胶形态的影响，考察G-CBS的催化效果及循环使用情况，比较了其与聚苯乙烯负载的CBS催化剂的催化性能。结果表明：聚醚Pluronic F-127片段的引入对G-CBS具有增溶效应，强化了催化剂与反应体系的相容性，有效解决了高交联度负载型催化剂选择性下降的问题。使用该催化剂还原产物苯乙醇ee值达94%，接近CBS均相催化反应的性能，优于目前报道的异相负载体系。催化剂循环使用5次，苯乙醇ee值仍可达到90%以上，苯乙酮转化率接近100%。

关键词: 凝胶, CBS催化剂, 还原, 聚合, 选择性

Abstract:

1,1-Diphenyl-1-[(2S,4R)-4-(4-vinyl-benzyloxy)-pyrrolidin-2-yl]-methanol (monomer4), styrene and polyether Pluronic F-127 were initiated by lauroyl peroxide for solution polymerization, to obtain a unique comb graft-copolymer, which was further reacted to form the gel crosslinked CBS catalyst precursor (G-CBSP). The novel CBS gel catalyst (G-CBS) was then prepared by condensation reaction of the G-CBSP with methylboronic acid in toluene-tetrahydrofuran and subsequently used for the asymmetric reduction of acetophenone. The structure of the catalyst was characterized by FTIR. The influence of the polyether Pluronic F-127 component on the gel morphology of the catalyst was observed by SEM. Besides, the catalytic performance and the recyclability of catalyst were investigated. The G-CBS catalyst was compared with the polystyrene supported CBS catalyst. The results showed that the introduction of polyether Pluronic F-127 component had a solubilizing effect on G-CBS which enhanced the compatibility between the catalyst and the reaction system, which effectively solved the problem of the selective reduction of the highly crosslinked supported catalyst. With the catalyst, the ee value of the reduced product phenylethanol was 94%, which was close to the performance of homogeneous system and better than the currently reported catalysts in heterogeneous system. After the catalyst was recycled for 5 times, the ee value of phenylethanol can still reach 90%, and the conversion of acetophenone approached 100%.

Key words: gel, CBS catalyst, reduction, polymerization, selectivity

中图分类号:

黄迪, 李国华, 宋晓玲, 戴双雄, 胡凌峰. 新型CBS凝胶催化剂的合成及催化性能[J]. 化工进展, 2019, 38(02): 905-912.

Di HUANG, Guohua LI, Xiaoling SONG, Shuangxiong DAI, Lingfeng HU. Preparation of novel CBS gel catalyst and its catalytic properties[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 905-912.

图/表 8

图1 G-CBS的合成路线及苯乙酮的不对称催化还原反应

图2 功能单体（4）的核磁氢谱图

图3 Pluronic F-127、G-CBSP和G-CBS的红外光谱图（a）和其局部放大图（b）

图4 Pluronic F-127与功能单体（4）、St的聚合机理

图5 G-CBS在干凝胶状态下（a～c）、THF反应介质中（d）、THF中溶胀后（e～h）及水中（i）的SEM图

表1 新型凝胶型与传统聚苯乙烯型催化剂在THF中的

负载类型	溶胀比（R _v）	吸液倍率（Q）
新型凝胶型	4.1×10⁵	2.77
聚苯乙烯型	1.1	0.53

图6 G-CBS的结构及对酮不对称还原反应机理图

图7 G-CBS循环利用的转化率和ee值

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