有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚

王莹; 张成建; 王征文; 张兴宏

doi:10.11777/j.issn1000-3304.2020.20263

您当前的位置：

首页 >

文章列表页 >

有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚

研究论文 | 更新时间：2021-05-07

- 有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚
- Alternating Copolymerization of Carbonyl Sulfide and Epichlorohydrin Catalyzed by Organic Lewis Pairs
- 高分子学报 2021年52卷第5期页码：499-504
- 作者机构：
  
  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
- 作者简介：
  
  E-mail: xhzhang@zju.edu.cn Xing-hong Zhang, E-mail: xhzhang@zju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21774108，51973190)资助项目()
- DOI：10.11777/j.issn1000-3304.2020.20263
  中图分类号：
- 纸质出版日期：2021-5-3，
  
  网络出版日期：2021-1-26，
  
  收稿日期：2020-11-30，
  
  修回日期：2020-12-27，
扫描看全文
王莹, 张成建, 王征文, 张兴宏. 有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚[J]. 高分子学报, 2021,52(5):499-504.

Ying Wang, Cheng-jian Zhang, Zheng-wen Wang, Xing-hong Zhang. Alternating Copolymerization of Carbonyl Sulfide and Epichlorohydrin Catalyzed by Organic Lewis Pairs[J]. Acta Polymerica Sinica, 2021,52(5):499-504.
王莹, 张成建, 王征文, 张兴宏. 有机Lewis酸碱对催化氧硫化碳和环氧氯丙烷交替共聚[J]. 高分子学报, 2021,52(5):499-504. DOI： 10.11777/j.issn1000-3304.2020.20263.

Ying Wang, Cheng-jian Zhang, Zheng-wen Wang, Xing-hong Zhang. Alternating Copolymerization of Carbonyl Sulfide and Epichlorohydrin Catalyzed by Organic Lewis Pairs[J]. Acta Polymerica Sinica, 2021,52(5):499-504. DOI： 10.11777/j.issn1000-3304.2020.20263.

摘要

氧硫化碳作为单体可与环氧化物交替共聚，是合成含硫高分子的新途径. 将廉价的环氧氯丙烷与氧硫化碳共聚可以得到含硫和氯原子的高分子，本文报道了无金属催化2种单体的全交替共聚反应. 采用三乙基硼和Lewis碱按2/1的摩尔比组成催化剂，可以获得全交替、高区域规整性的聚单硫代碳酸酯. 研究了不同实验条件包括有机Lewis酸碱对类型、反应温度、物料配比等因素对共聚反应的影响. 结果表明：无金属催化剂能获得与金属催化剂相媲美的效果，能高效催化并得到分子量低于1000 g/mol的全交替低聚物，为氧硫化碳和环氧氯丙烷的高值化利用提供了新的选项.

Abstract

The alternating copolymerization of carbonyl sulfide (COS) with epoxides is an emerging approach to the synthesis of sulfur-containing polymers. Epichlorohydrin (ECH) is a low-cost

commercially available epoxide rich in chloride. The copolymerization of COS with ECH can afford a unique poly(monothiocarbonate) (PMTC) containing chloride and sulfur atoms that could be a functional material. In this work

we report for the first time the alternating copolymerization of COS and ECH using metal-free catalysts. A binary catalytic system consisting of triethyl boron (TEB) and Lewis base (

e.g

. PPNCl

NBu

PPh

DTMeAB and DBU) afforded PMTCs with completely alternating structures (

i.e

alternating degree

99%)

the head-to-tail diad content

99%. The effect of various experimental conditions including the types of organic Lewis acid-base pairs

reaction temperatures

feeding ratios on the copolyemrization were investigated through controlled experiments. The combination of TEB/PPNCl (molar ratio of 2/1) could effectively catalyze the copolymerization of COS with ECH at 0 °C

with ECH conversion up to 92%

and produce the copolymer with number-average molecular weight (

) of 3000 g/mol that is comparable to the previous result

via

bifunctional metal catalyst. Although it is still a big challenge to obtain ECH/COS copolymer with high molecular weights

this work also discovers that organic Lewis pairs could efficiently achieve fully alternating oligomers with

less than 1000 g/mol at 30 °C

providing a new option for high value-added utilization of COS and ECH.

关键词

氧硫化碳环氧氯丙烷交替共聚无金属催化

Keywords

Carbonyl sulfideEpichlorohydrinAlternating copolymerizationMetal-free catalysis

references

Ferm R J . Chem Rev , 1957 . 57 621 - 640 .DOI:10.1021/cr50016a002http://doi.org/10.1021/cr50016a002 .

Svoronos P D N, Bruno T J . Ind Eng Chem Res , 2002 . 41 5321 - 5336 . DOI:10.1021/ie020365nhttp://doi.org/10.1021/ie020365n .

Chen Xuesi(陈学思), Chen Guoqiang(陈国强), Tao Youhua(陶友华), Wang Yuzhong(王玉忠), Lu Xiaobing(吕小兵), Zhang Liqun(张立群), Zhu Jin(朱锦), Zhang Jun(张军), Wang Xianhong(王献红) . Acta Polymerica Sinica(高分子学报) , 2019 . 50 ( 10 ): 1068 - 1082 . DOI:10.11777/j.issn1000-3304.2019.19124http://doi.org/10.11777/j.issn1000-3304.2019.19124 .

An Zesheng(安泽胜), Chen Changle(陈昶乐), He Junpo(何军坡), Hong Chunyan(洪春雁), Li Zhibo(李志波),Li Zichen(李子臣), Liu Chao(刘超), Lu Xiaobing(吕小兵), Qin Anjun(秦安军), Qu Chengke(曲程科), Tang Benzhong(唐本忠), Tao Youhua(陶友华), Wan Xinhua(宛新华), Wang Guowei(王国伟), Wang Jia(王佳), Zheng Ke(郑轲),Zou Wenkai(邹文凯) . Acta Polymerica Sinica(高分子学报) , 2019 . 50 ( 10 ): 1083 - 1132 . DOI:10.11777/j.issn1000-3304.2019.19136http://doi.org/10.11777/j.issn1000-3304.2019.19136 .

Luo M, Zhang X H, Du B Y, Wang Q, Fan Z Q . Macromolecules , 2013 . 46 5899 - 5904 . DOI:10.1021/ma401114mhttp://doi.org/10.1021/ma401114m .

Luo M, Zhang X H, Darensbourg D J . Acc Chem Res , 2016 . 49 2209 - 2219 . DOI:10.1021/acs.accounts.6b00345http://doi.org/10.1021/acs.accounts.6b00345 .

Li Y, Zhang Y Y, Liu B, Zhang X H . Chinese J Polym Sci , 2018 . 36 ( 2 ): 139 - 148 . DOI:10.1007/s10118-018-2047-5http://doi.org/10.1007/s10118-018-2047-5 .

Li Y, Zhang Y Y, Hu L F, Zhang X H, Du B Y, Xu J T .Prog Polym Sci , 2018 . 82 120 - 157 . DOI:10.1016/j.progpolymsci.2018.02.001http://doi.org/10.1016/j.progpolymsci.2018.02.001 .

Zhang C J, Zhang X H . Chinese J Polym Sci , 2019 . 37 ( 10 ): 951 - 958 . DOI:10.1007/s10118-019-2288-yhttp://doi.org/10.1007/s10118-019-2288-y .

Luo M, Zhang X H, Darensbourg D J . Macromolecules , 2015 . 48 6057 - 6062 . DOI:10.1021/acs.macromol.5b01427http://doi.org/10.1021/acs.macromol.5b01427 .

Wu H L, Yang J L, Luo M, Wang R Y, Xu J T, Du B Y, Zhang X H, Darensbourg D J . Macromolecules , 2016 . 49 8863 - 8868 . DOI:10.1021/acs.macromol.6b02285http://doi.org/10.1021/acs.macromol.6b02285 .

Li Y, Duan H Y, Luo M, Zhang Y Y, Zhang X H, Darensbourg D J . Macromolecules , 2017 . 50 8426 - 8437 . DOI:10.1021/acs.macromol.7b01867http://doi.org/10.1021/acs.macromol.7b01867 .

Zhang C J, Yang J L, Hu L F, Zhang X H . Chin J Chem , 2018 . 36 625 - 629 . DOI:10.1002/cjoc.201700810http://doi.org/10.1002/cjoc.201700810 .

Ren W M, Liu Y, Xin A X, Fu S, Lu X B . Macromolecules , 2015 . 48 8445 - 8450 . DOI:10.1021/acs.macromol.5b02108http://doi.org/10.1021/acs.macromol.5b02108 .

Yue T J, Ren W M, Chen L, Gu G G, Liu Y, Lu X B . Angew Chem Int Ed , 2018 . 130 12852 - 12856 . DOI:10.1002/ange.201805200http://doi.org/10.1002/ange.201805200 .

Gu G G, Yue T J, Wan Z Q, Zhang R, Lu X B, Ren W M . Polymers , 2017 . 9 515 DOI:10.3390/polym9100515http://doi.org/10.3390/polym9100515 .

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 DOI:10.1038/s41467-018-04554-5http://doi.org/10.1038/s41467-018-04554-5 .

Zhang C J, Zhang X, Zhang X H . Sci China Chem , 2020 . 63 1807 - 1814.

Yang J L, Wang H L, Hu L F, Hong X, Zhang X H . Polym Chem , 2019 . 10 6555 - 6560 . DOI:10.1039/C9PY01371Ghttp://doi.org/10.1039/C9PY01371G .

Zhang C J, Zhu T C, Cao X H, Hong X, Zhang X H . J Am Chem Soc , 2019 . 141 5490 - 5496 . DOI:10.1021/jacs.9b00544http://doi.org/10.1021/jacs.9b00544 .

Wan Xianhua(宛新华), Wang Xianhong(王献红) . Acta Polymerica Sinica(高分子学报) , 2018 . ( 7 ): 773 - 775 . DOI:10.11777/j.issn1000-3304.2018.18139http://doi.org/10.11777/j.issn1000-3304.2018.18139 .

Yue T J, Ren W M, Liu Y, Wan Z Q, Lu X B . Macromolecules , 2016 . 49 ( 8 ): 2971 - 2976 . DOI:10.1021/acs.macromol.6b00272http://doi.org/10.1021/acs.macromol.6b00272 .

Yue T J, Bhat G A, Zhang W J, Ren W M, Lu X B, Darensbourg D J . Angew Chem Int Ed , 2020 . 59 13633 - 13637 . DOI:10.1002/anie.202005806http://doi.org/10.1002/anie.202005806 .

Zhang D Y, Boopathi S K, Hadjichristidis N, Gnanou Y, Feng X S . J Am Chem Soc , 2016 . 138 11117 - 11120 . DOI:10.1021/jacs.6b06679http://doi.org/10.1021/jacs.6b06679 .

Boopathi S K, Hadjichristidis N, Gnanou Y, Feng X S . Nat Commun , 2019 . 10 293 DOI:10.1038/s41467-018-08251-1http://doi.org/10.1038/s41467-018-08251-1 .

Patil N G, Boopathi S K, Alagi P, Hadjichristidis N, Gnanou Y, Feng X S . Macromolecules , 2019 . 52 2431 - 2438 . DOI:10.1021/acs.macromol.9b00122http://doi.org/10.1021/acs.macromol.9b00122 .

Zhao N, Ren C L, Li H K, Li Y X, Liu S F, Li Z B . Angew Chem Int Ed , 2017 . 56 12987 - 12990 . DOI:10.1002/anie.201707122http://doi.org/10.1002/anie.201707122 .

Hong M, Chen E Y X . Angew Chem Int Ed , 2016 . 55 4188 - 4193 . DOI:10.1002/anie.201601092http://doi.org/10.1002/anie.201601092 .

Zhang C J, Zhang X H . Sci China Chem , 2019 . 62 ( 9 ): 1087 - 1089 . DOI:10.1007/s11426-019-9483-2http://doi.org/10.1007/s11426-019-9483-2 .

Li M S, Tao Y, Tang J D, Wang Y C, Zhang X Y, Tao Y H, Wang X H . J Am Chem Soc , 2019 . 141 281 - 289 . DOI:10.1021/jacs.8b09739http://doi.org/10.1021/jacs.8b09739 .

Hu S Y, Zhao J P, Zhang G Z, Schlaad H . Prog Polym Sci , 2017 . 74 34 - 77 . DOI:10.1016/j.progpolymsci.2017.07.002http://doi.org/10.1016/j.progpolymsci.2017.07.002 .

Ji H Y, Wang B, Pan L, Li Y S . Angew Chem Int Ed , 2018 . 57 16888 - 16892 . DOI:10.1002/anie.201810083http://doi.org/10.1002/anie.201810083 .

Carlotti S, Labbé A, Rejsek V, Doutaz S, Gervais M, Deffieux A . Macromolecules , 2008 . 41 7058 - 7062 . DOI:10.1021/ma801422chttp://doi.org/10.1021/ma801422c .

Wu G P, Wei S H, Ren W M, Lu X B, Xu T Q, Darensbourg D J . J Am Chem Soc , 2011 . 133 15191 - 15199 . DOI:10.1021/ja206425jhttp://doi.org/10.1021/ja206425j .

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

氮丙啶衍生物与环状酸酐共聚合成聚酯酰胺

微量酸酐诱导增强的二氧化碳/环氧氯丙烷共聚反应

基于氮杂环烯烃的Lewis酸碱对催化二氢香豆素基聚酯合成的机理研究