Metal-free photo-induced electron transfer reversible addition fragmentation chain transfer polymerization (PET-RAFT), as one of the most promising controlled/living polymerization technologies, has aroused worldwide interest recently. In this study, a microporous polyimide (PI) network was synthesized and used as the photocatalyst for PET-RAFT polymerization of methyl methacrylate (MMA) with oxygen tolerance.<br/>The microporous polyimide (PI) network was synthesized from perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and 1,3,5-triazine-2,4,6-triamine (melamine) using a Lewis acid catalyst zinc acetate/imidazole complex. Because of the π-π conjugated structure, the PI network exhibited favorable fluorescent properties which were highly influenced by the solvent effect. PET-RAFT polymerization of MMA monomers was carried out, by using the PI network photocatalyst, in different solvents, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), methylbenzene, and Petroleum ether. PMMA products with controlled molecular weights, narrow dispersity, and high conversion were obtained. Besides, the effects of RAFT agents (i.e., trithiocarbonates), catalyst concentrations, and residue oxygen in this system were investigated. The mechanism of deoxygenation and the PET-RAFT polymerization was discussed.

Porous polyimide network as a new photoactive organocatalyst for PET-RAFT polymerization with oxygen tolerance

256th National Meeting (2018)

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