Glass transition temperature enhancement of PMMA through copolymerization with PMAAM and PTCM mediated by hydrogen bonding

A series of poly(methyl methacrylate-co-methacrylamide-co-tricyclodecyl methacrylate) (PMMA-co-PMAAM-co-PTCM) copolymers possessing high glass transition temperatures and high transparency are prepared. By incorporating the aliphatic tricyclodecyl methacrylate moiety into the PMMA-co-PMAA main chain results in high glass transition temperature and high transparency of PMMA-based polymeric material. The TCM content affects the fraction of hydrogen bonding in these terpolymers, small content of TCM does not sacrifice the fraction of hydrogen-bonded association in and does not cause Tg decrease. The extent of free amide group plays the major role in dictating moisture absorption of terpolymers. The incorporation of TCM significantly reduces the moisture absorption of terpolymers due to its hydrophobic and bulky tricyclodecyl group. In addition, the TCM plays the role of inert diluent to convert portion of the strong self-associated hydrogen bonded amide groups into inter-associated hydrogen bonding between carbonyl groups of ester units and MAAM.