Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free-radical crosslinking monomethacrylate/dimethacrylate copolymerizations

d-Bornyl methacrylate (BoMA) was chosen as a typical example of bulky monomethacrylate monomers, the polymerization of which led to the formation of a rigid polymer chain. To discuss the effect of primary polymer chain rigidity on intramolecular cyclization, we compared the solution copolymerization results of BoMA with 1 mol % ethylene dimethacrylate (EDMA; n = 1) and poly(ethylene glycol dimethacrylate) [CH2=C(CH3)CO(OCH2CH2),,OCOC(CH3)=CH2, n = 9 (PEGDMA-9)] with those of methyl methacrylate (MMA) with 1 mol % EDMA and PEGDMA-9; the dependence of the weight-average degree of polymerization on conversion for the former BoMA copolymerization systems was completely opposed to that for the latter MMA systems, and this was a reflection of a reduced occurrence of intramolecular cyclization caused by the rigidity of the primary polymer chain. The effect of primary polymer chain rigidity on intramolecular crosslinking was discussed through a comparison of both BoMA/EDMA and MMA/EDMA copolymerizations. The correlations of the intrinsic viscosity, root-mean-square (rms) radius of gyration, and second virial coefficient with the molecular weight were examined for both BoMA/EDMA (90/10) and MMA/ EDMA (90/10) copolymerizations in a dilute solution because microgelation was observed in solution MMA/EDMA (90/10) copolymerization as a reflection of a locally extensive occurrence of intramolecular crosslinking. The logarithmic plots of both the intrinsic viscosity and rms radius of gyration versus the molecular weight for MMA/EDMA copolymerization were compared with those for the corresponding BoMA/EDMA copolymerizations. The second virial coefficients were greater than 10(-5) mol cm(3) g(-2) for BoMA/EDMA copolymers, even when the conversion was very close to the gel point, whereas they were quite low, that is, less than 10(-5) mol cm(3) g(-2), for an MMA/EDMA copolymer obtained at more than 15% conversion. These were ascribed to a suppressed occurrence of intramolecular crosslinking, a reflection of the lessened flexibility of the polymer main chain and a steric effect due to the bulky d-bornyl groups. @ 2004 Wiley Periodicals, Inc.