Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates

Bing Yu; Jin-lei Huo; Rong-rong Hu; Ben Zhong Tang

doi:10.11777/j.issn1000-3304.2023.23117

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Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates

Research Article | 更新时间：2023-09-25

- Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates
  增强出版
- ACTA POLYMERICA SINICA Vol. 54, Issue 10, Pages: 1509-1520(2023)
- 作者机构：
  
  1.华南理工大学发光材料与器件国家重点实验室广东省分子聚集发光重点实验室广州 510640
  2.香港中文大学（深圳）理工学院深圳 518172
  3.聚集诱导发光高等研究院广州 510530
- 作者简介：
  
  Rong-rong Hu, E-mail: msrrhu@scut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23117
  CLC：
- Published：20 October 2023，
  
  Published Online：01 September 2023，
  
  Received：27 May 2023，
  
  Accepted：08 July 2023
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于冰,霍金磊,胡蓉蓉等.单质硫、异腈和硫醇的多组分串联聚合合成聚二硫代氨基甲酸酯[J].高分子学报,2023,54(10):1509-1520.

Yu Bing,Huo Jin-lei,Hu Rong-rong,et al.Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates[J].ACTA POLYMERICA SINICA,2023,54(10):1509-1520.
于冰,霍金磊,胡蓉蓉等.单质硫、异腈和硫醇的多组分串联聚合合成聚二硫代氨基甲酸酯[J].高分子学报,2023,54(10):1509-1520. DOI： 10.11777/j.issn1000-3304.2023.23117.

Yu Bing,Huo Jin-lei,Hu Rong-rong,et al.Multicomponent Tandem Polymerizations of Sulfur, Diisocyanides and Dithiols toward Polydithiocarbamates[J].ACTA POLYMERICA SINICA,2023,54(10):1509-1520. DOI： 10.11777/j.issn1000-3304.2023.23117.

摘要

聚二硫代氨基甲酸酯具有优异的力学性质和动态可逆性，是一类富有前景的功能高分子材料，然而其合成方法较为有限，限制了其结构和功能的拓展.在本文中，我们针对单质硫、异腈和硫醇的反应中存在副反应、效率低等问题，通过设计分步投料的方式、有机碱的种类和反应温度，提高了反应效率和选择性，并成功发展为有机碱催化的单质硫、异腈和硫醇的多组分串联聚合，以

-二异丙基乙胺为碱，在二甲亚砜溶剂中分步反应，得到数均分子量可达1.77×10

g/mol的聚二硫代氨基甲酸酯.该聚合条件温和、操作便捷，可适用于苄基异腈和芳香异腈单体，用于合成结构多样的聚二硫代氨基甲酸酯.这类聚合物具有较好的热稳定性，并可在硫醇存在下高效降解为低聚物.该多组分串联聚合为聚二硫代氨基甲酸酯材料提供了温和便捷的合成方法，有望促进这类新型可降解高分子材料的发展.

Abstract

Polydithiocarbamates are a group of promising functional polymer materials with unique mechanical property and dynamic reversible property

however

the exploration of structures and functionalities of these polymers are limited by the synthetic approaches. In this work

considering the problems regarding the side reactions and low efficiency in the reaction of elemental sulfur

isocyanide

and thiol

one-pot two-step tandem strategy

organic bases

and reaction temperature were carefully designed to improve the efficiency and selectivity of the reaction. The organic base-catalyzed multicomponent tandem polymerizations of elemental sulfur

diisocyanides and dithiols were developed

with

-diisopropylethylamine as the base in DMSO

affording polydithiocarbamates with

s of up to 1.77×10

g/mol. The polymerization was mild and convenient

which could be applied to both aliphatic and aromatic isocyanides

to synthesize polydithiocarbamates with different structures. These polymers possessed good thermal stability

and could be degraded to oligomers in the presence of thiol. The multicomponent tandem polymerizations could provide a mild and convenient synthetic approach for polydithiocarbamates

which may accelerate the development of these sulfur-containing degradable polymer materials.

关键词

单质硫多组分串联聚合聚二硫代氨基甲酸酯可降解高分子

Keywords

Elemental sulfurMulticomponent tandem polymerizationPolydithiocarbamatesDegradable polymers

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