Nonisothermal crystallization kinetics of ethylene terephthalate-ethylene oxide segmented copolymers with two crystallizing segments

The nonisothermal crystallization behavior of ethylene terephthalate-ethylene oxide segmented copolymers has been studied by means of differential scanning calorimetry (DSC). The kinetics of ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed by the Ozawa equation. During the crystallization of the high-T-m segments (PET), the low-T-m segments (PEO) act as a noncrystalline diluent, the crystallization behavior of PET obeys the Ozawa theory. When the PEO segments begin to crystallize, the PET phase is always partially solidified and the presence of the spherulitic microstructure of PET profoundly influences the crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. (C) 2000 Elsevier Science Ltd. All rights reserved.

Synthesis and characterization of alternating copolymers containing triphenylamine as hole-transporting units

A series of light-emitting poly(p-phenylene vinylene)s with triphenylamine units as hole-transporting moieties in the main chain were synthesized via Wittig condensation in good yields. The newly formed vinylene double bonds possessed a trans configuration, which was confirmed by Fourier transform infrared and NMR spectroscopy. The high glass-transition temperature (83-155 degreesC) and high decomposition temperature (> 300 degreesC) suggested that the resulting copolymers possessed high thermal stability. These copolymers, especially TAAPV1, possessed a high weight-average molecular weight (47,144) and a low polydispersity index (1.55). All the copolymers could be dissolved in common organic solvents, such as tetrahydrofuran (THF), CHCl3, CH2Cl2, and toluene, and exhibited intense photoluminesence in THF (the emission maxima were located from 478 to 535 nm) and in film (from 478 to 578 nm). The low onsets of the oxidation potential (0.6-0.75 V) suggested that the alternating copolymers possessed a good hole-transporting property due to the incorporation of triphenylamine moieties. (C) 2001 John Wiley & Sons, Inc.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Synthesis and properties of alternating copolymers containing PPV and hole-transporting units for light-emitting devices

A series of alternating copolymers containing triphenylamine (TPA) moieties and oligomeric PPV segments in the main chain have been synthesized by Wittig condensation. The resulting polymers exhibit good thermal stability with decomposition temperatures (Tds) above 305 degreesC under nitrogen at 10 degreesC/min, and high glass transition temperatures (Tgs). They show intense photoluminescence in solution and film. The single-layer electroluminescent device using TAA-PV1 as emissive layer emits green light at 522nm with a turn-on voltage of 6V and maximum brightness of about 200cd/m(2) at 20V.

Synthesis and characterization of side chain liquid crystal M5MPP/MMEANB copolymers containing NLO active group

A new series of side chain liquid crystal polymers based on the backbone of polymethacrylate containing 4-nitroazobenzene and 4-methoxybiphenyl group as side chain mesogen were prepared and characterized, FTIR, H-1 NMR, POM and WAXD were used to study the structure, phase behavior and mesophase texture of this series of SCLC copolymers. The researches show that polymer PM5MPP and copolymer M5MPP/MMEANB are enantiotropic liquid crystalline polymers, but polymer PMMEANB has no liquid crystalline properties. DSC results showed that the thermal stability of the mesophase of this series of copolymers was enhanced by the existence of intermolecular electron donor-acceptor interaction. It was found that the temperature range of the mesophase of the copolymers was broadened with increasing 4-nitroazobenzene units. The focal-conic texture observed by POM indicated that this series of the copolymers possessed the characteristics of smectic liquid crystal.

Synthesis and properties of novel random and block copolymers composed of phthalimidine- and perfluoroisopropylidene-polyarylether-sulfones

A series of novel polyarylethersulfone (AB)(n) block copolymers with different segment lengths have been synthesized by nucleophilic solution polycondensation of phenoxide-terminated and fluorine-terminated oligomers; random copolymers have been prepared over the whole composition ranges. The structures of the resultant copolymers have been confirmed by FTIR, C-13 NMR spectra and differential scanning calorimetry (DSC). Compared with two homopolymers and random copolymers, the block copolymers of this study possess excellent thermal stability (5% thermal decomposition under nitrogen atmosphere above 500 C) and high glass transition temperatures, and have a wide melt-processing temperature range. They may become a new class of mouldable high performance thermoplastics. (C) 2001 Society of Chemical Industry.

Controlled synthesis of L-lactide-b-epsilon-caprolactone block copolymers using a rare earth complex as catalyst

Well-defined block copolymers of L-lactide-b-epsilon-caprolactone were synthesized by sequential polymerization using a rare earth complex, Y(CF3COO)(3)/Al(iso-Bu)(3), as catalyst system. The compositions of the block copolymers could be adjusted by manipulating the feeding ratio of comonomers. The characterizations by GPC, H-1 NMR, C-13 NMR, and DSC displayed that the block copolymer, poly(epsilon-caprolactone-b-L-lactide) [P(CL-b-LLA)], had a narrow molecular weight distribution and well-controlled sequences without random placement.

Synthesis and enhancement of quantum efficiency of a series of novel PPV derivative copolymers

A series of novel PPV derivative copolymers with good solubility in common organic solvents were synthesized. The emitting color of these copolymers could range from red to blue by adjusting the structures and the compositions of monomers. Investigation on their optical properties showed that the PL quantum efficiency could be increased by energy transfer and conjugation reduction. The PL quantum efficiency of most green/blue copolymer films on slide glass was higher than 80%.

Synthesis and Characterization of Side-Chain Liquid Crystalline (M6MPP/M6NPAP) Copolymers with NLO Properties

A series of novel thermotropic side-chain liquid crystalline polymer based on polymethacrylate backbone containing electron-accepting 4-(4'-nitrophenylazo)phenoxy as nonlinear optical active group and electron-donating 4(4'-methoxyphenyl) phenoxy group as mesogen attached covalently to the backbone through the flexible spacer was prepared and characterized, respectively. The results from differential scanning calorimetry showed that these series of copolymers were enantiotropic liquid crystal with single mesophase. The melting points and the relative enthalpy change of the copolymers depressed with increasing the molar percent of 4'-nitroazobenzene monomer units over 0 similar to 50mol%, but the enthalpies change of the transition from mesophase to isotropic state increased for the copolymers containing 0 similar to 50mol% 4'-nitroambenzene units. The texture observed under polarized optical microscope identified that the copolymers containing 24molar% or more than 24mol% 4-nitroambenzene monomer units could form smectic mesophase with the focal-conic texture. The results detected by WAXD were in good agreement with the results observed by POM.

Blue-light emitting diodes and flat display based on poly(p-phenylenevinylene) copolymers

Copolymers containing alternating flexible aliphatic blocks and rigid poly(p-phenylenevinylene) (PPV) blocks were synthesized and characterized. It was found that the fluorescent intensity increases with increasing length of the flexible blocks. Bright blue-light emitting diodes were fabricated using PPV copolymers as electroluminescent layers. The devices show 190 cd/m(2) light-emitting brightness at 460 nm and 15 V rum-on voltage. The effects of oxadiazole derivative PBD and tris(8-hydroxyquinoline) aluminum Alq(3) electron-transporting layers on the luminance and stability of the devices are discussed.

Synthesis and characterization of (phenolphthalein/4,4 '-thiodiphenol) PES copolymers

Copolymers based on monomers phenolphthalein (PP)/4,4'-thiodiphenol (Bis-T)/4,4'-dichlorodiphenylsulfone (DCDPS) were prepared by a route involving the toluene, N-methyl-2-pyrrolidone and anhydrous potassium carbonate synthesis. The range of optimum reaction temperature was between 185 and 195 degrees C. The copolymers were characterized by C-13 NMR, differential scanning calorimetry (DSC) and torsion braid analysis. It was found that all of the copolymers were random and homogeneous and their glass transition temperatures (T-g) decreased linearly with an increase of Bis-T contents in the copolymers. The thermal stability determined by thermogravimetry analysis in air atmosphere indicated that the copolymer had better resistance to thermo-oxidative degradation. Dynamic mechanical measurement showed that (PP/Bis-T) PES copolymers containing 0-50 mol% of Bis-T components had two secondary relaxations. (C) 1998 Elsevier Science Ltd. All rights reserved.

Morphology and properties of [PPO-PDMS-PHS](n) segmented ternary copolymers

The morphology and properties of [ PPO-PDMS-PHS](n) segmented ternary copolymers were investigated by DMA, TEM and SAXS techniques. It is shown that the continuous phase of [PPO-PDMS-PHS](n) is the compatible phase composed of PDMS, PPO and PHS segments, and that there exist two dispersed phases, i, e. the PDMS phase and a mixed phase of half hard ( PHS) and hard ( PPO) segments. The tan delta vs. T curve of the segmented ternary copolymer with 66.7% (W/W) PDMS shows a rather high plateau in the temperature range from -120 degrees C to 200 degrees C, which indicates that the copolymer has the characteristics of microphase separation as well as compatibility of block copolymers, respectively. Meanwhile, it has good tensile properties, which means that [PPO-PDMS-PHS](n) has overcome the weakness of low strength of block or segmented copolymers containing PDMS.

Barrier property and structure of acrylonitrile/acrylic copolymers

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerisation. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor also measured at 100% relative humidity and at 30 degrees C. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

Studies on poly(ether ether ketone ketone) poly(ether biphenyl ether ketone ketone) copolymers and blends

We synthesized a series of polymers: poly(ether ether ketone ketone)(PEEKK), poly(ether biphenyl ether ketone ketone) (PEBEKK) and their copolymer by polycondensation, We also prepared a series of PEEKK-PEBEKK blends, By using DSC method, we found that T-g of the copolymers and the blends rose with the increasing of biphenyl contents in the polymers, T-c of the copolymers and the blends is higher than the corresponding homopolymer. From the results, we think that PEEKK-PEBEKK copolymer and blends are miscible and the copolymer is random.

Studies on water-swellable elastomers .2. Thermal properties and crystalline behavior of amphiphilic graft copolymers with poly(ethylene glycol) side chains

The thermal properties and crystalline structure of the amphiphilic graft copolymers CR-g-PEG600, CR-g-PEG2000, and CR-g-PEG6000 using chloroprene rubber (CR) as the hydrophobic backbone and poly(ethylene glycol) (PEG) with different molecular weights as the hydrophilic side chains were studied by DSC and WAXD. The results showed that a distinct phase-separated structure existed in CR-g-PEGs because of the incompatibility between the backbone segments and the side-chain segments. For all the polymers studied, T-m2, which is the melting point of PEG crystalline domains in CR-g-PEG, decreased compared to that of the corresponding pure PEG and varied little with PEG content. For CR-g-PEG600 and CR-g-PEG2000, T-m1, which is the melting point of the CR crystalline domains, increased with increasing PEG content when the PEG content was not high enough, and at constant PEG content, the longer were the PEG side chains the higher was the T-m1. The crystallite size L-011 of CR in CR-g-PEGs increased compared to that of the pure CR and decreased with increasing PEG content. (C) 1997 John Wiley & Sons, Inc.