Various types of soluble crosslinked polymers obtained from the copolymerization of methylmethacrylate (MMA) and p‐divinylbenzene (p‐DVB) in the presence of a transfer agent (CBr4) have been discussed in relation to the variation of the structure during the reaction time. When [p‐DVB]/[MMA] = 1.49 × 10−3 and [CBr4]/[MMA] = 1.28 × 10−4, only linear polymers (primary polymer; Mn = 1.0 × 105) with pendant vinyl groups are formed intially. Considerable branched structure is attained in rather large polymers (Mn = 2.5 × 105), but the number of pendant double bonds is not enough to reach the gelation. As the concentration of the transfer agent becomes high, the intermolecular crosslinking is depressed, and the formed polymers contain loops and short chains. At [p – DVB]/[MMA] = 7.43 × 10−3 and [CBr4]/[MMA] = 1.28 × 10−3, the shape of polymer with the same Mn became compact gradually with increasing reaction time. These results are considered to be useful for the preparation of soluble crosslinked polymer with controlled structure.
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Chen et al. (1984) studied this question.