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高分子合成与功能构造教育部重点实验室 浙江大学高分子科学与工程学系 杭州 310027
[ "张兴宏,男,1977年生,浙江大学高分子科学与工程学系教授. 2006年于浙江大学获得博士学位并留校为讲师,2006年6月 ~ 2008年8月在浙大高分子系从事博士后研究,2009年底晋升为副教授,2016年底晋升为教授. 2012年7月至2013年8月在美国伊利诺伊大学厄巴纳-香槟分校(UIUC) Jeffrey Moore课题组访学一年. 研究方向是高分子合成化学,近年主要从事催化一碳化合物(CO2,COS,CS2)的聚合研究. 迄今主持国家自然科学基金项目6项,浙江省杰出青年基金项目1项,入选浙江省151人才工程二层次,担任《功能高分子学报》青年编委" ]
纸质出版日期:2020-9-1,
网络出版日期:2020-7-24,
收稿日期:2020-4-9,
修回日期:2020-5-3,
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王莹, 杨嘉良, 张成建, 张兴宏. 有机催化含硫一碳单体与环氧化物共聚[J]. 高分子学报, 2020,51(10):1092-1103.
Ying Wang, Jia-liang Yang, Cheng-jian Zhang, Xing-hong Zhang. Organocatalytic Polymerization of Sulfur-containing One-carbon Monomer and Epoxides[J]. Acta Polymerica Sinica, 2020,51(10):1092-1103.
王莹, 杨嘉良, 张成建, 张兴宏. 有机催化含硫一碳单体与环氧化物共聚[J]. 高分子学报, 2020,51(10):1092-1103. DOI: 10.11777/j.issn1000-3304.2020.20096.
Ying Wang, Jia-liang Yang, Cheng-jian Zhang, Xing-hong Zhang. Organocatalytic Polymerization of Sulfur-containing One-carbon Monomer and Epoxides[J]. Acta Polymerica Sinica, 2020,51(10):1092-1103. DOI: 10.11777/j.issn1000-3304.2020.20096.
近几年,采用含硫一碳单体(氧硫化碳和二硫化碳)与环氧化物共聚合成含硫高分子的路线快速发展起来. 有机催化剂由于底物耐受性好、对空气和水不敏感以及低毒等优势,成功用于催化含硫一碳单体与环氧化物的聚合,得到了无色无味无金属残留的含硫聚合物. 结合本课题组在含硫一碳单体聚合领域的研究结果,本文讨论了有机催化氧硫化碳与环氧化物共聚的体系,阐述了两类有机路易斯(Lewis)酸碱对即三烷基硼/有机碱和硫脲/有机碱体系的种类和结构与共聚选择性及活性之间的关系,介绍了由含硫一碳单体出发合成脂肪族聚硫醚的新路线. 在此基础上,总结了有机Lewis酸碱协同催化机制,归纳提出了“超分子阴离子”链末端控制聚合的策略,并介绍了体现这一策略的若干含氧单体的可控聚合反应. 希望这些认识能为设计高活性高选择性的有机协同催化体系提供新的思路.
The harmlessness and high-value utilization of one-carbon (C1) building blocks are the frontier issues in synthetic polymer chemistry. The copolymerization of carbonyl sulfide (COS) or carbon disulfide (CS
2
) with epoxides is a promising method of synthesizing sulfur-containing polymers. In recent years
organocatalysts have been successfully developed to catalyze the polymerization process of COS(CS
2
) owing to their low toxicity
insensitivity to air and water
and good substrate resistance
resulting in colorless
odorless
and metal-free sulfur-containing polymers. This work comprehensively summarizes the fundamental research activities on the organocatalytic polymerization of COS(CS
2
) with epoxides
affording a variety of poly(thiocarbonate)s and poly(thioether)s with well-defined structures. The catalysis of several organic Lewis pairs
i.e
. the trialkyl borane/ organic base and (thio)urea/organic base systems
for the polymerizations of COS(CS
2
) with epoxides is discussed in detail. Of significance
the conceptualization of O/S ER
a unique phenomenon in the copolymerization process of COS(CS
2
) with epoxides
guided us to have success in synthesizing a variety of poly(thioether)s. By inhibiting O/S ER
poly(monothiocarbonate)s have been developed by the catalysis of many organocatalysts. In addition
this study proposes the “supramolecular anion” strategy for the controlled copolymerization of COS with epoxides. This strategy can be expanded to the controlled polymerization of many types of monomers with heteroatoms (
e.g
.
O
S
N) under the catalysis of organic Lewis pairs. The properties of the COS(CS
2
)-derived polymers including optical
electronic
crystalline properties are presented. Future efforts can be directed to the development of robust
versatile
highly active and stereoselective organocatalysts for the copolymerization of COS(CS
2
) with epoxides
as well as the synthesis of sequence-controlled sulfur-containing polymers.
有机催化含硫一碳单体环氧化物开环共聚合含硫聚合物
OrganocatalystSulfur-containing one-carbon monomersEpoxidesRing-opening copolymerizationSulfur-containing polymers
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