Synthesis and Properties of Dual-curable Polymers Containing Oxetanyl, Methacryloyl and Carboxyl Grous

Abstract

The polyaddition reactions of 3, 3-bis (4-carboxylphenyloxymethyl) oxetane (OX) to bisepoxides [bisphenol A diglycidylether (BPGE), 4, 4′-bisglycidyloxybiphenyl (GBiPhe), and 1, 4-bisglycidyloxybenzene (GPhe)] were carried out in the presence of tetrabutylammonium bromide (TBAB) at 90°C for 24 h to give the polymers (P₁-OX, P₂-OX, and P₃-OX) with M_n′s = 14000, 13800 and 13300 in 91, 89, and 88% yields, respectively. The reactions of P₁-OX, P₂, -OX, and P₃-OX with methacrylic anhydride were performed to give the corresponding dual-curable polymers (P₁-OX-MA, P₂-OX-MA, and P₃-OX-MA) with both methacryloyl and oxetanyl groups in the side chains. Furthermore, the reactions of P₁-OX, P₂-OX, and P₃-OX with tetrahydrophthalic anhydride were performed to give the corresponding dualcurable polymers (P₁-OX-CA, P₂-OX-CA and P₃-OX-CA) with both carboxyl and oxetanyl groups in the side chains. The photo-polymerization reactions of P₁-OX-MA, P₂-OX-MA, and P₃-OX-MA were performed in a film state using a photo-radical initiator or a photo-acid generator. The thermally curing reactions of P₁-OX-CA, P₂-OX-CA and P₃-OX-CA were performed in a film state using TPPI. Thus combining both the photo and thermal reactions, dually-curing reactions were successfully performed in a film state using the photo-radical initiator and the photo-acid generator to give the corresponding cured films. The thermal properties of resulting cured films were examined.