Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properti...Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.展开更多
基金partially supported by the National Natural Science Foundation of China(22325102 and 52173005)the Ministry of Science and Technology of China(2021YFA1501600)+2 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2019B030301003)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040003)the Fundamental Research Funds for the Central Universities(2022ZYGXZR107)。
文摘Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.
