浏览全部资源
扫码关注微信
1.北京分子科学国家研究中心 高分子化学与物理教育部重点实验室 北京大学化学与分子工程学院 北京 100871
2.中国科学院长春应用化学研究所 长春 130022
E-mail: xhwan@pku.edu.cn Xin-Hua Wan, E-mail: xhwan@pku.edu.cn
E-mail: xhwang@ciac.ac.cn E-mail: xhwang@ciac.ac.cn
纸质出版日期:2018-7,
收稿日期:2018-6-9,
扫 描 看 全 文
宛新华, 王献红. 有机催化实现含硫高分子的精确合成[J]. 高分子学报, 2018,0(7):773-775.
Xin-hua Wan, Xian-hong Wang. Metal-free Access to Precise Synthesis of Sulfur-containing Polymers[J]. Acta Polymerica Sinica, 2018,0(7):773-775.
宛新华, 王献红. 有机催化实现含硫高分子的精确合成[J]. 高分子学报, 2018,0(7):773-775. DOI: 10.11777/j.issn1000-3304.2018.18139.
Xin-hua Wan, Xian-hong Wang. Metal-free Access to Precise Synthesis of Sulfur-containing Polymers[J]. Acta Polymerica Sinica, 2018,0(7):773-775. DOI: 10.11777/j.issn1000-3304.2018.18139.
脂肪族含硫高分子是一类重要的功能聚合物材料. 催化含硫一碳化合物(氧硫化碳(COS)、二硫化碳(CS
2
))与环氧化物共聚制备含硫高分子是近年迅速发展起来的合成路线. 最近,张兴宏等使用由有机Lewis碱和硫脲构成的无金属催化体系,实现了COS与环氧化合物室温“活性”阴离子共聚,得到了100%交替、头尾结构含量
>
99%、数均分子量近1 × 10
5
和窄分布(1.13 ~ 1.23)的聚单硫代碳酸酯,催化剂活性达112 h
−1
,揭示了硫脲和Lewis碱分别选择性活化环氧和COS并协同催化共聚的反应机制.
Sulfur-containing polymers are important functional materials and can be used as optical
anti-corrosion and antifouling materials. Using C1 monomers (
i
.
e
. carbonyl sulfide (COS)
carbon disulfide (CS
2
)) to copolymerize with epoxides have been rapidly developed in very recent years. Recently
Xing-Hong Zhang
et al
. reported a metal-free living copolymerization of COS with epoxides
via
the cooperative catalysis of organic Lewis pairs including organic bases and thioureas as hydrogen-bond donors
afforded poly(monothiocarbonate)s with 100% alternating degree
>
99% tail-to-head content
high molecular weight (up to 9.84 × 10
5
) and narrow molecular weight distributions (1.13 – 1.23). The turnover frequencies (TOFs) of the catalyst are as high as 112 h
−1
at 25 °C. Kinetic and mechanistic results suggest that the supramolecular specific recognition of thiourea to epoxide and base to COS promoted the copolymerization cooperatively. The synthesis of sulfur-containing polymer developed by Xing-Hong Zhang and co-workers is very promising to the utilization of C1 monomers derived from the use of oil and coal.
含硫高分子有机催化氧硫化碳环氧化合物
Sulfur-containing polymersCarbonyl sulfideEpoxideOrganocatalysts
Zhang X H, Liu F, Sun X K, Chen S, Du B Y, Qi G R . Macromolecules , . 2008 . 41 1587 - 1590 . DOI:10.1021/ma702290ghttp://doi.org/10.1021/ma702290g .
Yang J L, Wu H L, Li Y, Zhang X H, Darensbourg D J . Angew Chem Int Ed , . 2017 . 56 5774 - 5779 . DOI:10.1002/anie.201701780http://doi.org/10.1002/anie.201701780 .
Zhang C J, Wu H L, Li Y, Yang J L, Zhang X H . Nat Commun , . 2018 . 9 2137 - 2146 . DOI:10.1038/s41467-018-04554-5http://doi.org/10.1038/s41467-018-04554-5 .
0
浏览量
29
下载量
4
CSCD
关联资源
相关文章
相关作者
相关机构