Copolymers, block mixed methacrylate synthesis

Group transfer polymerization allows the synthesis of block copolymers of different methacrylate or acrylate monomers, such as methyl methacrylate and allyl methacrylate [Hertler, 1996 Webster and Sogah, 1989]. The synthesis of mixed methacrylate-acrylate block copolymers requires that the less reactive monomer (methacrylate) be polymerized first. The silyl dialkylketene acetal propagating center from methacrylate polymerization is more reactive for initiation of acrylate polymerization than the silyl monoalkylketene acetal propagating center from acrylate polymerization is for initiation of methacrylate polymerization. Bifunctional initiators such as l,4-bis(methoxytri methyl si loxymethylene)cyclohexane (XXXIII) are useful for synthesizing ABA block copolymers where the middle block is methacrylate [Steinbrecht and Bandermann, 1989 Yu et al., 1988]. 

Tiing, Y.-C. and Chen, W.-C. (2009) Poly[2,7-(9,9-dihexylfluorene)]-Wocl -poly[3-(trimethoxysilyl)propyl methacrylate] (PF-1)-PTMSPMA) rod-coil block copolymers Synthesis, morphology and photophysical properties in mixed solvents. Reactive Functional Polymers, 69,507-518. 

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