Insertion of Degradable Thioester Linkages into Styrene and Methacrylate Polymers

10 January 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The thionolactone 3,3-dimethyl-2,3-dihydro-5H-benzo[e][1,4]dioxepine-5-thione (DBT) is shown to homopolymerize and, for the first time, copolymerize with styrene and methacrylates, introducing degradable thioester backbone functionality. The rapid copolymerization with styrene was exploited to produce copolymers through free-radical polymerization in a starve-fed semi-batch setup. The copolymerization of DBT with tert-butyl methacrylate under RAFT conditions was hypothesized to involve selective retardation of DBT-terminal chains that led to a more uniform distribution of degradable thioester linkages between chains. Surprisingly, the aminolysis of DBT homopolymers was accompanied by the intramolecular ether cleavage within the primary degradation product leading to the formation of 2,2-dimethylthiirane and salic-ylamides.


degradable polymers
radical ring-opening polmyerization
TARO polymerization

Supplementary materials

Supporting Information: Insertion of Degradable Thioester Linkages into Styrene and Methacrylate Polymers
Experimental section, homo- and copolymer NMR and IR da-ta, copolymerization kinetics, homo- and copolymer degrada-tion data.


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