Synthesis of Polyethylenes with In-Chain Isolated Carbonyls from CO_(2)and Ethylene via a Tandem Photoreduction/Polymerization Protocol  

作　　者：Fulin Zhou Haojie Dai Shan Tang Yongfeng Zhou 

机构地区：[1]Frontiers Science Center for Transformative Molecules,Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2024年第6期1591-1599,共9页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.21890730,21890733,and 22231007);the Program for Basic Research of Shanghai Science and Technology Commission(grant no.19JC1410400);the Fundamental Research Funds for the Central Universities(grant no.23X010301599);the Shanghai Pujiang Program(grant no.21PJ1406500);the China Postdoctoral Science Foundation(grant no.2022M722073).

摘　　要：Aiming at accessing polyethylene-bearing in-chain degradable functionality,copolymerization of carbon dioxide(CO_(2))with ethylene has long been recognized as a significant but highly challenging transformation.Nevertheless,most trials have resulted in ethylene homopolymerization because of the endothermic property and high energy barriers of CO_(2)insertion during polymer chain propagation.Here we report an unprecedented tandem reaction protocol for the synthesis of polyethylenes with in-chain carbonyls from CO_(2)and ethylene by the combination of photocatalytic CO_(2)reduction and palladium-catalyzed coordination/insertion polymerization.This protocol provides an easy way to adjust the carbonyl content(from 0.13 to 12 mol%)and insertion selectivity(up to 99%isolated carbonyls)of the polyethylene copolymers,which enables the polymers tomaintain the main properties of highdensity polyethylene and simultaneously endows them with good photodegradability.In addition,besides apolar polyethylene copolymers,polar-functionalized polyethylenes with in-chain isolated carbonyls can also be synthesized from CO_(2),ethylene and a polar monomer using the same protocol.We believe our present work sheds new light on the synthesis of degradable polyethylenes by employing CO_(2)as a green carbonyl source.

关 键 词：carbon dioxide coordination polymerization polyethylene PHOTOREDUCTION PHOTODEGRADATION 

分 类 号：O62[理学—有机化学]