Ji Ho Youk

Effects of competition between phase separation and ester interchange reactions on the phase behavior in a phase-separated immiscible polyester blend: Monte carlo simulation

The effects of rate ratio of phase separation to ester interchange reactions and the repulsive pair interaction energy on the phase behavior in a phase-separated immiscible polyester blend are investigated using a Monte Carlo simulation method. The time evolution of structure factor and the degree of randomness are monitored as a function of homogenization time. When the phase separation is dominant over ester interchange reactions, the domain size slowly increases with homogenization time. However, when the pair interaction becomes less repulsive, the domain size does not significantly change with homogenization time. On the other hand, when ester interchange reactions are dominant over the phase separation, the homogenization proceeds without a change in the domain size. The higher the extent of phase separation, the lower the increasing rate of the DR. However, when the phase separation is sufficiently dominant, the effect of the extent of phase separation on the increasing rate of the degree of randomness become less significant.

Interchange reaction kinetics and sequence distribution of liquid crystalline poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)

Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) [copoly(ET/CPT)] was prepared using poly(ethylene terephthalate) (PET) as a flexible spacer, terephthalic acid (TPA), and chlorohydroquinone diacetate (CHQDA). All reactions involved in the copolymerization were investigated using some model compounds: TPA was used for acidolysis, diphenylethyl terephthalate (DPET) for interchange reaction between PET chains, and di-o-chlorophenyl terephthalate (DOCT) and di-m-chlorophenyl terephthalate (DMCT) for interchange reaction between PET and rigid rodlike segments. Activation energies obtained for the acidolysis of PET with TPA and for interchange reaction of PET with DPET, DOCT, and DMCT were 19.8 kcal/mole, 26.5 kcal/mole, 60.2 kcal/mole, and 45.9 kcal/mole, respectively. This result supports that the copolymerization proceeds through the acidolysis of PET with TPA first and subsequent polycondensation between carboxyl end group and CHQDA or acetyl end group, which is formed from the reaction of CHQDA and TPA. Also, it was found that ester-interchange reaction can be influenced by the steric hindrance. Copoly(ET/CPT)s obtained had ethylene acetate end groups formed from acetic acid and hydroxy ethylene end groups and showed almost the random sequence distribution for all compositions.

Thermal degradation and cyclodepolymerization of poly(ethylene terephthalate-co-isophthalate)s

The thermal degradation of poly(ethylene terephthalate-co-isophthalate)s (PETIs) is investigated by using isothermal thermogravimetric analysis at the temperature range of 280–310°C. The degradation rate of PETIs is increased as the mole ratio of ethylene isophthaloyl (EI) units in PETIs increases. The activation energies for the thermal degradation of poly(ethylene terephthalate), PETI(5/5), and poly(ethylene isophthalate) are 33.4, 16.6, and 8.9 kcal/mole, respectively. The degradation rate of PETIs is influenced by their volatile cyclic oligomer components formed during the polymerization and the thermal degradation. It is simulated by the rotational isomeric state model that the content of cyclic dimer in PETIs, which is the most volatile cyclic oligomer component, increases with the EI units in PETIs.