Hybrid Dual-Cure Polymer Networks Via Sequential Thiol-ene Photopolymerization and Thermal Ring-Opening Polymerization of Benzoxazines

Document Type

Article

Publication Date

11-1-2012

School

Polymer Science and Engineering

Abstract

Dual-cure hybrid polymer networks were prepared by sequential thiol–ene photopolymerization followed by thermal ring-opening polymerization of benzoxazines with the aim of increasing the glass transition temperature range of thiol–ene based materials and improving the processibility of polybenzoxazines. The hybrid networks are derived from a multifunctional, dually-polymerizable monomer possessing both bis-“ene” and bis-benzoxazine moieties enabling the formation of two networks through a common constituent monomer when combined with a multifunctional thiol. The photopolymerization kinetics of the thiol–ene reaction were investigated by real-time infrared spectroscopy. Sequential thermal ring-opening polymerization of the benzoxazine moieties incorporated into the thiol–ene network was characterized by FTIR and differential scanning calorimetry. The glass transition of the hybrid material was observed at 150 °C; however, competing thiol–ene (radical-mediated) and thiol–benzoxazine (nucleophilic ring-opening) reactions during the UV cure yield a heterogeneous network structure.

Publication Title

Reactive and Functional Polymers

Volume

72

Issue

11

First Page

799

Last Page

806

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