The polymerization of methyl methacrylate (MMA) was initiated with 1,1,2,2‐tetraphenyl‐1,2‐diphenoxyethane (TPPA), 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsiloxy)ethane (TPSA), and 1,1,2,2‐tetraphenyl‐1,2‐dicyanoethane (TPCA). The polymerization with these initiators is characterised by three steps: in the first period oligomers from MMA and initiator radicals are formed by primary radical termination. These telechelics are effective initiators for the further free radical polymerization of MMA. After consumption of the initiator radicals with increasing conversion a normal polymerization occurs.
Methyl methacrylate, benzyl methacrylate, butyl methacrylate, and methacrylic acid can be polymerized by 1,1,2,2‐tetraphenyl‐1,2‐diphenoxyethane and 1,1,2,2‐tetraphenyl‐1,2‐dicyanoethane. In the first period of the polymerization with both initiators oligomers are formed which can initiate the polymerization of other vinyl monomers yielding block‐copolymers besides the resp. homopolymers.
The rate of the free radical polymerization of styrene with substituted ethanes as initiators is characterized by a competition of "normal" and primary radical termination. With decreasing initiator concentration the reaction order with respect to monomer and initiator changes in favour of a normal termination. The kinetics of this polymerization process is derived and compared with experimental results.
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