Metal-Free Alternating Copolymerization of CS2 and Oxetane,Macromolecules

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Metal-Free Alternating Copolymerization of CS2 and Oxetane
Macromolecules ( IF 5.1 ) Pub Date : 2023-08-22 , DOI: 10.1021/acs.macromol.3c01300
Guofei Feng ₁ , Ximin Feng ₁ , Xiong Liu ₁ , Wenqi Guo ₁ , Chengjian Zhang ₁ , Xinghong Zhang _{1,

2}

Affiliation

The conversion of CS₂, which is discarded on a large scale as a pollutant, into valuable sulfur-containing polymers is of significance for both environmental and polymer science. However, the copolymerization of CS₂ and cyclic ether suffers from complex polymer structures and massive byproducts. Here, we use a cooperative organocatalyst system composed of alkyl borane and onium salts for CS₂ and oxetane copolymerization. Of interest, the copolymerization is highly efficient with a turnover frequency up to 1103 h^–1, avoids small-molecule byproducts, and yields previously inaccessible polythiocarbonates bearing highly regular sequences. The in-chain sulfur atoms make polythiocarbonate demonstrate desirable thermal and mechanical properties, with a melting temperature of 83 °C, an ultimate tensile strength of 20.7 ± 3.1 MPa, and an elongation at break of 480 ± 20%. For the mechanism, the Lewis acid of borane activates oxetane as well as forms the borate complex with the growing anion, as revealed by density functional theory studies.

中文翻译：

CS2 和氧杂环丁烷的无金属交替共聚

将作为污染物而被大规模丢弃的CS ₂转化为有价值的含硫聚合物对于环境和聚合物科学都具有重要意义。_{然而，CS 2}与环醚的共聚存在复杂的聚合物结构和大量的副产物。在这里，我们使用由烷基硼烷和鎓盐组成的协同有机催化剂体系进行CS ₂和氧杂环丁烷共聚。有趣的是，共聚效率很高，周转频率高达 1103 h ^–1，避免了小分子副产物，并产生了以前无法获得的具有高度规则序列的聚硫代碳酸酯。链内硫原子使聚硫代碳酸酯表现出理想的热性能和机械性能，熔化温度为83℃，极限拉伸强度为20.7±3.1MPa，断裂伸长率为480±20%。对于该机制，密度泛函理论研究揭示了硼烷的路易斯酸激活氧杂环丁烷并与生长的阴离子形成硼酸盐络合物。

更新日期：2023-08-22

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