Crystal and phase morphologies and structures determined by self-organization of crystalline-amorphous diblockcopolymers, crystallization of the crystallizable blocks, and vitrification of the amorphous blocks are rev...Crystal and phase morphologies and structures determined by self-organization of crystalline-amorphous diblockcopolymers, crystallization of the crystallizable blocks, and vitrification of the amorphous blocks are reviewed through asystematic study on a series of poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers. On the base ofcompetitions among these three processes, molecular and supramolecular ordering in confined environments can beinvestigated. In a concentration-fluctuation-induced disordered (D_(CF)) diblock copolymer, the competition between crystalli-zation of the PEO blocks and vitrification of the PS blocks is momtored by time-resolved simultaneous small angle X-rayscattering (SAXS) and wide angle X-ray diffraction (WAXD) techniques. In the case of T_c<T_g^(PS-rich), the crystallization of thePEO blocks is observed to be confined within the bicontinuous D_(CF) phase due to the rapid vitrification of the PS-rich phase.Overall crystallization rate, crystal melting behavior, and crystallinity results further confirm the competition betweencrystallization and vitrification at different temperatures. In an ordered lamellar PEO-b-PS diblock copolymer, the crystalli-zation of the PEO blocks is completely confined within the ordered lamellae due to rapid vitrification of the PS layers asobserved by time-resolved SAXS and WAXD experiments. From the combined two-dimensional SAXS and WAXDmeasurements, the crystal orientation within the confined lamellar geometry is found parallel to the lamellar surface normalwhen it is isothermally crystallized at 35℃. In an ordered cylindrical PEO-b-PS sample, the crystallization of the PEO blocksis also observed to be confined within the ordered cylinders because of rapid vitrification of the PS matrix. The crystalorientation within the confined cylinders is found perpendicular to the cylinder axis as it is crystallized at 35℃.展开更多
A novel blue light-emitting coil-rod-coil triblock oligomer, PEO-PHP-PEO, which consists of para-hexaphenyl (PHP) as the rigid rod and poly(ethylene oxide) (PEO, M w = 750) as the flexible coil, has been synthesized. ...A novel blue light-emitting coil-rod-coil triblock oligomer, PEO-PHP-PEO, which consists of para-hexaphenyl (PHP) as the rigid rod and poly(ethylene oxide) (PEO, M w = 750) as the flexible coil, has been synthesized. It is the first soluble poly(para-phenylene) molecule containing no lateral substituent, which can dissolve not only in organic solvents such as chloroform and THF, but also in water. The critical micelle concentration (CMC) of PEO-PHP-PEO in water is 5.25×10-4 mol·L-1 and the surface tension at CMC, 鉉MC, is 61.29 mN·m-1. The absorption peak of the molecularly dissolved PEO-PHP-PEO in water is centered at 323 nm and the fluorescence spectrum has a maximum at 432 nm and shows the vibronic fine structure typical of molecular dissolution. The photoluminescence spectrum of the aggregate solution is similar to that of the PHP polycrystal film, indicating that the ordered packing of PHP block has taken place due to a combination of hydrophobic interaction and p-p stacking. The oligomer self-assembles into cotton-like nanofibers with diameter of about 20 nm in 5.0×10-3 mol·L-1 aqueous solution.展开更多
文摘Crystal and phase morphologies and structures determined by self-organization of crystalline-amorphous diblockcopolymers, crystallization of the crystallizable blocks, and vitrification of the amorphous blocks are reviewed through asystematic study on a series of poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers. On the base ofcompetitions among these three processes, molecular and supramolecular ordering in confined environments can beinvestigated. In a concentration-fluctuation-induced disordered (D_(CF)) diblock copolymer, the competition between crystalli-zation of the PEO blocks and vitrification of the PS blocks is momtored by time-resolved simultaneous small angle X-rayscattering (SAXS) and wide angle X-ray diffraction (WAXD) techniques. In the case of T_c<T_g^(PS-rich), the crystallization of thePEO blocks is observed to be confined within the bicontinuous D_(CF) phase due to the rapid vitrification of the PS-rich phase.Overall crystallization rate, crystal melting behavior, and crystallinity results further confirm the competition betweencrystallization and vitrification at different temperatures. In an ordered lamellar PEO-b-PS diblock copolymer, the crystalli-zation of the PEO blocks is completely confined within the ordered lamellae due to rapid vitrification of the PS layers asobserved by time-resolved SAXS and WAXD experiments. From the combined two-dimensional SAXS and WAXDmeasurements, the crystal orientation within the confined lamellar geometry is found parallel to the lamellar surface normalwhen it is isothermally crystallized at 35℃. In an ordered cylindrical PEO-b-PS sample, the crystallization of the PEO blocksis also observed to be confined within the ordered cylinders because of rapid vitrification of the PS matrix. The crystalorientation within the confined cylinders is found perpendicular to the cylinder axis as it is crystallized at 35℃.
基金supported by the National Natural Science Fundation of China(Grant Nos.29874003 and 29992590-4)the Teaching and Research Award Fund for Outstanding Young Teachers in Higher Education Institutions of the Ministry of Education of China.
文摘A novel blue light-emitting coil-rod-coil triblock oligomer, PEO-PHP-PEO, which consists of para-hexaphenyl (PHP) as the rigid rod and poly(ethylene oxide) (PEO, M w = 750) as the flexible coil, has been synthesized. It is the first soluble poly(para-phenylene) molecule containing no lateral substituent, which can dissolve not only in organic solvents such as chloroform and THF, but also in water. The critical micelle concentration (CMC) of PEO-PHP-PEO in water is 5.25×10-4 mol·L-1 and the surface tension at CMC, 鉉MC, is 61.29 mN·m-1. The absorption peak of the molecularly dissolved PEO-PHP-PEO in water is centered at 323 nm and the fluorescence spectrum has a maximum at 432 nm and shows the vibronic fine structure typical of molecular dissolution. The photoluminescence spectrum of the aggregate solution is similar to that of the PHP polycrystal film, indicating that the ordered packing of PHP block has taken place due to a combination of hydrophobic interaction and p-p stacking. The oligomer self-assembles into cotton-like nanofibers with diameter of about 20 nm in 5.0×10-3 mol·L-1 aqueous solution.
