We prepared the geometric isomers of decahydro-2-naphthols as the source materials for the synthesis of poly(decahydro-2-naphthyl methacrylate)s [poly-(DNMA)-I, -II, -III, and -IV] including alicyclic ester groups with different geometric structures. The geometry and conformational dynamics of the decahydro-2-naphthyl moieties were investigated by NMR spectroscopy and DFT calculations. We synthesized each isomer of the methacrylic monomers, polymerized them, and investigated the optical, thermal, and mechanical properties of poly(DNMA)s with different isomer compositions. The T g values of the poly-(DNMA)s were in the following order: 139.3 °C for poly(DNMA)-II < 142.7 °C for poly(DNMA)-I < 146.2 °C for poly(DNMA)-III < 152.9 °C for poly(DNMA)-III/IV. On the basis of the dynamic motion of the alicyclic substituents determined by dynamic mechanical analysis, the tan δ peaks due to the β-relaxation for the a conformation change of the side group were observed for poly(DNMA)-I, while no peak was observed for poly(DNMA)-III. The activation energies for the β-relaxation were 65 kJ/mol for poly(DNMA)-I and 56−63 kJ/mol for the poly(DNMA)s including the four isomeric ester groups with various compositions. An increase in the DNMA-II content in the repeating units accelerated a dynamic conformation change, resulting in a decrease in the tan δ peak temperature and the activation energy value, as well as the glass transition temperature of the polymers. The optical property of the resulting polymers as the transparent polymer materials was also investigated. The density, refractive index value, and Abbe number of poly(DNMA)s were 1.04−1.10 cm 3 /g, 1.489, and 42−44, respectively.

A detailed investigation of addition-fragmentation chain transfer (AFCT) in the free-radical polymerization of methyl methacrylate (MMA) in the presence of methyl ␣-(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k add ) over 60 -120°C resulted in E add ϭ 21.7 kJ mol Ϫ1 and A add ϭ 2.18 ϫ 10 6 M Ϫ1 s Ϫ1 and a very weak temperature dependence of the chain-transfer constant (E add Ϸ E p ). The rate coefficient for fragmentation of adduct radicals at 60°C was estimated as k f Ϸ 39 s Ϫ1 on the basis of experimental data of the MMA conversion and the concentration of 2-carbomethoxy-2propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions.