The physical aging behavior of atactic polystyrene (aPS) films achieved under different drawing conditions has been studied by optical birefringence and modulate differential scanning: calorimeter (m.d.s.c.). The resu...The physical aging behavior of atactic polystyrene (aPS) films achieved under different drawing conditions has been studied by optical birefringence and modulate differential scanning: calorimeter (m.d.s.c.). The results show that on annealing at specific temperature below glass transition temperatue (T-g), the enthalpy relaxation (Delta H) and T-g decrease with increasing of birefringence (Delta n). On the other baud, the effect of molecular draw ratio (MDR) is confusing: Delta H and T-g decrease with increasing of MDR in the early stage of aging, but the MDR's effect become unobvious with the development of aging. It may be concluded that the ordered domain generated by the drawing below or above glass transition temperature will affect the development of physical aging behavior. The viewpoint of cohesional entanglement is used to account for the above observations.展开更多
Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polyme...Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polymerization and propene atactic polymerization. Styrene could be copolymerized with propene when the propene was prepolymerized for a period, to which styrene and tri-isobutylaluminum (TIBA) were then added. The titled block copolymer together with the related homopolymers was obtained. The copolymerization porducts can be divided into the homopolymers and the copolymer by successive solvent extraction with boiling butanone, heptane and tetrahydrofuran (THF), and each fraction was characterized by ~13C NMR, DSC and WAXD. It was found that aPS and aPP were soluble in boiling butanone and heptane respectively. The block copolymer (sPS-b-aPP) composed of syndiottactic polystyrene segment was soluble in boiling THF and the residue was chiefly sPS.展开更多
Stereocomplexes formed in atactic poly(methyl methacrylatc) (α-PMMA) films cast form different solvents were studied by means of Fourier transform infrared spectroscopy (FTIR). and differential scanning calorimetry (...Stereocomplexes formed in atactic poly(methyl methacrylatc) (α-PMMA) films cast form different solvents were studied by means of Fourier transform infrared spectroscopy (FTIR). and differential scanning calorimetry (DSC). The growth of stereocomplex was a function of annealing temperature and annealing time. respectively.展开更多
The condensed structure of atactic-polystyrene (a - PS ) films cast from the solutions of differ- ent concentrations in dichloromethane under vacuum and atmospheric conditions was studied by differential scanning calo...The condensed structure of atactic-polystyrene (a - PS ) films cast from the solutions of differ- ent concentrations in dichloromethane under vacuum and atmospheric conditions was studied by differential scanning calorimetry(DSC). It was found that only under vacuum evaporating conditions did the endothermic peak in the DSC curves of a-PS films depend on the concentration of the a-PS solution. For the samples cast from the solution of concentration below 0. 010 g/mL, no endothermal peak was observed, but for those cast from the solution of concentration above 0. 020 g/mL, obvious endothermal peaks appeared. The onset of the endothermal peak is correlated with the critical overlapping concentration c' (0. 010-0. 020 g/mL), which is in agreement with the theoretically calculated one (Ccal=0.014 g/mL).展开更多
The polymer reference interaction site model （PRISM） integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene （aPS） melt, in which the monomer of aPS is repre...The polymer reference interaction site model （PRISM） integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene （aPS） melt, in which the monomer of aPS is represented with an eight-site model to characterize its microstructure. The intramolecular structure factors needed in the PRISM calculations were obtained from single chain MD simulations. The calculated results indicate that the results by the integral equation method agrees well with experiments, and can reflect the fine microscopic structure of real aPS melt. This work shows that the PRISM theory is a powerful tool for investigating the structure and properties of complex polymers.展开更多
The monomolecular particle agglomerates of polystyrenes were obtained by freeze-drying of its very dilute solutions of 1.3 x 10(-5)-2.0 x 10(-5) g/mL in benzene:cylcohexane (100:1) solvents, and they were annealed at ...The monomolecular particle agglomerates of polystyrenes were obtained by freeze-drying of its very dilute solutions of 1.3 x 10(-5)-2.0 x 10(-5) g/mL in benzene:cylcohexane (100:1) solvents, and they were annealed at room temperature for hundred days before use. According to C-13-NMR measurement the polystyrenes should be practically atactic. The number average molecular weights of the samples are 2.80 x 10(3), 2.00 x 10(4), and 1.55 x 10(6), respectively. The freeze-dried aPS with a molecular weight higher than 10(4) show two new IR absorption bands at 1098 and 1261 cm(-1), which are absent in the normal aPS and freeze-dried styrene oligomer. It was also found that the low molecular weight samples can only form powders, whereas the freeze-dried aPS with higher molecular weight form a mixture of powders and fibrils, of which the longer fibrils show a much stronger 1261 cm(-1) band than the shorter fibrils and the powder. It seems that the 1261 cm(-1) band corresponds to the stacking behavior of monomolecular particles.展开更多
基金This work was Supported by the National Basic Research Project-Macromolecular Condensed State
文摘The physical aging behavior of atactic polystyrene (aPS) films achieved under different drawing conditions has been studied by optical birefringence and modulate differential scanning: calorimeter (m.d.s.c.). The results show that on annealing at specific temperature below glass transition temperatue (T-g), the enthalpy relaxation (Delta H) and T-g decrease with increasing of birefringence (Delta n). On the other baud, the effect of molecular draw ratio (MDR) is confusing: Delta H and T-g decrease with increasing of MDR in the early stage of aging, but the MDR's effect become unobvious with the development of aging. It may be concluded that the ordered domain generated by the drawing below or above glass transition temperature will affect the development of physical aging behavior. The viewpoint of cohesional entanglement is used to account for the above observations.
文摘Some highly active η~5-pentamethylcyclopentadienyltribenzyloxy titanium complexes [Cp Ti(OBz)_3] activated by modified methylaluminoxane (mMAO) were prepared and used as the catalyst for styrene syndiospecific polymerization and propene atactic polymerization. Styrene could be copolymerized with propene when the propene was prepolymerized for a period, to which styrene and tri-isobutylaluminum (TIBA) were then added. The titled block copolymer together with the related homopolymers was obtained. The copolymerization porducts can be divided into the homopolymers and the copolymer by successive solvent extraction with boiling butanone, heptane and tetrahydrofuran (THF), and each fraction was characterized by ~13C NMR, DSC and WAXD. It was found that aPS and aPP were soluble in boiling butanone and heptane respectively. The block copolymer (sPS-b-aPP) composed of syndiottactic polystyrene segment was soluble in boiling THF and the residue was chiefly sPS.
文摘Stereocomplexes formed in atactic poly(methyl methacrylatc) (α-PMMA) films cast form different solvents were studied by means of Fourier transform infrared spectroscopy (FTIR). and differential scanning calorimetry (DSC). The growth of stereocomplex was a function of annealing temperature and annealing time. respectively.
基金Supported by the National Key Fundamental Research-" Macromolecular Condensed State" the State Scienceand Technology Commissio
文摘The condensed structure of atactic-polystyrene (a - PS ) films cast from the solutions of differ- ent concentrations in dichloromethane under vacuum and atmospheric conditions was studied by differential scanning calorimetry(DSC). It was found that only under vacuum evaporating conditions did the endothermic peak in the DSC curves of a-PS films depend on the concentration of the a-PS solution. For the samples cast from the solution of concentration below 0. 010 g/mL, no endothermal peak was observed, but for those cast from the solution of concentration above 0. 020 g/mL, obvious endothermal peaks appeared. The onset of the endothermal peak is correlated with the critical overlapping concentration c' (0. 010-0. 020 g/mL), which is in agreement with the theoretically calculated one (Ccal=0.014 g/mL).
文摘The polymer reference interaction site model （PRISM） integral equation theory was used to describe the structure and thermodynamic properties of atactic polystyrene （aPS） melt, in which the monomer of aPS is represented with an eight-site model to characterize its microstructure. The intramolecular structure factors needed in the PRISM calculations were obtained from single chain MD simulations. The calculated results indicate that the results by the integral equation method agrees well with experiments, and can reflect the fine microscopic structure of real aPS melt. This work shows that the PRISM theory is a powerful tool for investigating the structure and properties of complex polymers.
文摘The monomolecular particle agglomerates of polystyrenes were obtained by freeze-drying of its very dilute solutions of 1.3 x 10(-5)-2.0 x 10(-5) g/mL in benzene:cylcohexane (100:1) solvents, and they were annealed at room temperature for hundred days before use. According to C-13-NMR measurement the polystyrenes should be practically atactic. The number average molecular weights of the samples are 2.80 x 10(3), 2.00 x 10(4), and 1.55 x 10(6), respectively. The freeze-dried aPS with a molecular weight higher than 10(4) show two new IR absorption bands at 1098 and 1261 cm(-1), which are absent in the normal aPS and freeze-dried styrene oligomer. It was also found that the low molecular weight samples can only form powders, whereas the freeze-dried aPS with higher molecular weight form a mixture of powders and fibrils, of which the longer fibrils show a much stronger 1261 cm(-1) band than the shorter fibrils and the powder. It seems that the 1261 cm(-1) band corresponds to the stacking behavior of monomolecular particles.
