Bifunctional initiators with two labile groups (e.g. peroxides or azo groups) are frequently used in the polymer industry for the synthesis of vinyl polymers and resin curing. In general

there are two types of bifunctional initiators: one is symmetrical bifunctional initiators containing two labile groups of equal structure

the other is unsymmetrical bifunctional initiators containing two labile groups of unequal structure. One of the potential advantages of using bifunctional initiators is that high polymer molecular mass and high polymerization rate can be obtained simultaneously by controlling the initiator decomposition rate through optimal reaction temperature programming. For free radical polymerization of methyl methacrylate (MMA) with monofunctional initiators

the kinetics is reasonably well understood in both low and high monomer conversion regimes. However

the presence of an additional labile group in bifunctional initiators makes the polymerization kinetics very complicated. This is because labile groups such as peroxides become redistributed repeatedly in the growing and inactive polymers and they are engaged in further initiation

propagation

chain transfer and termination reactions during the course of polymerization. The effects of temperature and initiator concentration on the kinetics of MMA bulk polymerization initiated by 2

5-dimethyl-2

5-bis(2-ethyl hexanoyl peroxide) hexane (TX-141) were investigated.The energy of activation of MMA bulk polymerization initiated by TX-141 was about 91 kJ8226;mol-1

and that of TX-141 decomposition was about 140 kJ8226;mol-1

which was more close to the experimental data.The reaction order of TX-141 concentration was about 0.72

because there was mono- and bi-molecule termination. The kinetic comparison initiated by TX-141 and benzoyl peroxide (BPO) with the same half life period showed that the kinetics was the same when the concentration of TX-141 was half of that of BPO.But

the number-average molecular mass ratio of that initiated by TX-141 to that by BPO was from 1.2 to 1.33 increasing with the conversion.There was an exothermal peak in the DSC curve of polymer initiated by TX-141 at low conversion

but there was no peak at high conversion and no peak was observed for the polymer initiated by BPO.It was shown that the two functional groups of bifunctional initiator decomposed at different times during the polymerization process.