Highly branched polymers with multiple alkyl chloride functionalities at the chain ends were successfully synthesized via one-pot copolymerization of vinyl monomers and crosslinkers in the presence of 1-chloro-1, 2-benziodoxol-3(1H)-one (ClBIO) and 1-chloro-2-hexyl-1,2-benziodazol-3(2H)-one (ClHBIO), which served both as initiators and efficient chain transfer agents. ClBIO and ClHBIO are heterocyclic hypervalent iodine (III) (HVI) compounds with labile I-Cl bonds, which can be cleaved homolytically upon heating to produce a Cl atom (which initiates the polymerization) and a 9-I-2 radical. Both ClBIO and ClHBIO were found to transfer Cl atoms to the propagating polymer chains very efficiently. Due to this transfer, during the copolymerization of vinyl monomers and crosslinkers, the gelation was significantly delayed compared to systems using conventional radical initiators (such as AIBN), even when high concentrations of crosslinker were employed. The transfer coefficients for the HVI compounds were determined, and the effects of crosslinker and HVI compound concentrations on the outcome of the copolymerizations were systematically studied.

Utilizing hypervalent iodine compounds in the synthesis of branched polymers

254th National Meeting (2017)

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