Methylmethacrylate(MMA) was copolymerized with ethylmethacrylate(EMA), butylmethacrylate(BMA), and styrene(St.) monomers, respectively, and α-methylstyrene(AMS) was copolymerized with acrylonitrile(AN) in CSTR as well as batch reactors. The kinetic parameters of those copolymerizations and thermal d...
Methylmethacrylate(MMA) was copolymerized with ethylmethacrylate(EMA), butylmethacrylate(BMA), and styrene(St.) monomers, respectively, and α-methylstyrene(AMS) was copolymerized with acrylonitrile(AN) in CSTR as well as batch reactors. The kinetic parameters of those copolymerizations and thermal degradation were obtained from copolymerization reactions. The experimental results are as follows : 1. In the case of the batch reactor system, the conversions of MMA/EMA, MMA/BMA, MMA/St., AMS/AN are 80.79, 72.52, 79.41, and 5.52%, respectively, at the monomer composition of [M_(1)]/[M_(2)]=80/20, the initiator concentration of 10mmol/l, the reaction temperature of 80℃, and in the reaction time of 720min. In the case of the CSTR, the conversions of MMA/EMA, MMA/BMA, MMA/St., AMS/AN are 42.20, 37.80, 27.10, and 3.90%, respectively, at the monomer composition of [M_(1)]/[M_(2)]=80/20, the initiator concentration of 10mmol/l, the reaction temperature of 80℃, and in the residence time of 180min. 2. In all of the copolymerizations, the best approaching monomer composition to Steady-State Approximation Method at the initiator concentration of 10mmol/l, the reaction temperature of 80℃, the residence time of 180min, was [M_(1)]/[M_(2)]=50/50 in the CSTR system. 3. In the case of the batch reactor system(initiator concentration : 10mmol/l), the activation energies of propagation step(E_(p)) of MMA/EMA, MMA/BMA, MMA/St., AMS/AN were in the range of 3.86~5.38, 3.07~3.27, 4.09~5.14, and 2.22~11.22 kcal/mol, respectively. The maximum E_(p) value of MMA/EMA, MMA/BMA, MMA/St., AMS/AN was obtained at the composition ratios of 20/80, 80/20, 20/80, and 80/20, respectively. The similar tendency was also shown in the CSTR system. 4. It was found that all of the copolymerizations approached to Mayo-Lewis theory in the correlation between composition of monomer in feed(f_(1)) and copolymer composition of monomer(F_(1)). The rate constant of propagation, K_(p) and the rate constant of termination, K_(t) were calculated according to the composition ratio(f_(1)) and were shown at Table 3~10. 5. The characteristics of thermal degradation of MMA/EMA, MMA/BMA, MMA/St. were irregular main chain degradations, while those of AMS/AN were irregular side chain degradation. These were resulted from the steric hindrances of α-carbon atom of AMS, because the activation energy of degradation of AMS/AN was larger than that of MMA copolymers. The degradation rates of each system were increased in the order MMA/BMA, MMA/EMA, MMA/St., AMS/AN.
Methylmethacrylate(MMA) was copolymerized with ethylmethacrylate(EMA), butylmethacrylate(BMA), and styrene(St.) monomers, respectively, and α-methylstyrene(AMS) was copolymerized with acrylonitrile(AN) in CSTR as well as batch reactors. The kinetic parameters of those copolymerizations and thermal degradation were obtained from copolymerization reactions. The experimental results are as follows : 1. In the case of the batch reactor system, the conversions of MMA/EMA, MMA/BMA, MMA/St., AMS/AN are 80.79, 72.52, 79.41, and 5.52%, respectively, at the monomer composition of [M_(1)]/[M_(2)]=80/20, the initiator concentration of 10mmol/l, the reaction temperature of 80℃, and in the reaction time of 720min. In the case of the CSTR, the conversions of MMA/EMA, MMA/BMA, MMA/St., AMS/AN are 42.20, 37.80, 27.10, and 3.90%, respectively, at the monomer composition of [M_(1)]/[M_(2)]=80/20, the initiator concentration of 10mmol/l, the reaction temperature of 80℃, and in the residence time of 180min. 2. In all of the copolymerizations, the best approaching monomer composition to Steady-State Approximation Method at the initiator concentration of 10mmol/l, the reaction temperature of 80℃, the residence time of 180min, was [M_(1)]/[M_(2)]=50/50 in the CSTR system. 3. In the case of the batch reactor system(initiator concentration : 10mmol/l), the activation energies of propagation step(E_(p)) of MMA/EMA, MMA/BMA, MMA/St., AMS/AN were in the range of 3.86~5.38, 3.07~3.27, 4.09~5.14, and 2.22~11.22 kcal/mol, respectively. The maximum E_(p) value of MMA/EMA, MMA/BMA, MMA/St., AMS/AN was obtained at the composition ratios of 20/80, 80/20, 20/80, and 80/20, respectively. The similar tendency was also shown in the CSTR system. 4. It was found that all of the copolymerizations approached to Mayo-Lewis theory in the correlation between composition of monomer in feed(f_(1)) and copolymer composition of monomer(F_(1)). The rate constant of propagation, K_(p) and the rate constant of termination, K_(t) were calculated according to the composition ratio(f_(1)) and were shown at Table 3~10. 5. The characteristics of thermal degradation of MMA/EMA, MMA/BMA, MMA/St. were irregular main chain degradations, while those of AMS/AN were irregular side chain degradation. These were resulted from the steric hindrances of α-carbon atom of AMS, because the activation energy of degradation of AMS/AN was larger than that of MMA copolymers. The degradation rates of each system were increased in the order MMA/BMA, MMA/EMA, MMA/St., AMS/AN.
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