Abstract
We have examined the initiating system consisting of t-butyl hydroperoxide, acetone and organic sulphonic derivatives for the methyl methacrylate (MMA) polymerization at 313 K. The rate of reaction depends on the concentration of an initiator component (low molecular weight or polymeric sulphonic compounds) with the exponent 0.5. The temperature coefficient for the initiation over the range 292.5–323 K is only ca 50% that for spontaneous thermal decomposition of peroxides. When the sulphonic groups are attached to a polymer chain, the activity of the initiating system depends inversely on the frequency of sulphonic groups along the chain. The activity of this initiator may be very high. MMA bulk polymerization (at concentrations of 0.2 M acetone and 0.012 M t-butyl hydroperoxide, with acid groups bound to MMA-co-styrene copolymer being one for 45 chain units on average) has a rate of 41% hr −1, approximately twice that when sulphuric acid is used.
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