The synthesis and thermotropic liquid crystalline behaviour of novel main chain poly(aryl ether ketone)s containing a lateral phenyl group

Novel main chain poly(aryl ether ketone)s containing a lateral phenyl group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and phenylhydroquinone with either 4,4'-difluorobenzophenone or 1,4-bis(4-fluorobenzoyl)benzene and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 50 and 70mol% biphenol. Melting (T-m) and isotropization (T-i) transitions both appeared on the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline nematic state. As expected, each of the copolymers had a relatively lower melting transition than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer phenylhydroquinone.

Nonisothermal crystallization behavior of a novel poly(aryl ether ketone): PEDEKmK

Nonisothermal melt crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl was investigated by differential scanning calorimetry (DSC). A convenient and reasonable kinetic approach was used to describe the nonisothermal melt crystallization behavior, and its applicability was verified when the modified Avrami analysis by the Jeziorny and Ozawa equation were applied to the crystallization process. The crystallization activation energy was estimated to be -219 kJ/mol by Kissinger method while crystallizing from the PEDEKmK melt nonisothermally. These observed crystallization characteristics were compared to those of the other members of poly(aryl ether ketone) family. (C) 1998 John Wiley & Sons, Inc.

EAA增容LLDPE/PEO共混物及其增容机理

以乙烯-丙烯酸共聚物(EAA)为增容剂,研究了它在线性低密度聚乙烯(LLDPE)/聚环氧乙烷(PEO)共混物中的增容作用及其增容机理.采用电子显微镜(SEM)、动态力学分析(DMA)、DSC和红外光谱(IR)对共混物形态及其微观结构进行了表征结果表明,EAA对LLDPE/PEO共混物有一定的增容作用;其增容机理为:EAA和LLDPE两者的非晶区部分相容,而EAA分子中的羧基与PEO分子中的醚氧基相互作用形成了分子间氢键.

热处理对Nylon-11结构的影响

对不同温度热处理过的Nylon－11样品，采用广角X射线衍射（WAXD），根据X射线衍射强度理论，用多重峰图解分峰方法研究了Nylon－11结构的变化，并导出了计算Nylon－11结晶度的公式．所得结果与密度法、DSC法进行了比较．同时也给出了Nylon－11的有关热力学参数

间规立构聚丙烯的结晶度研究

Ｎａｔａ等用Ｚｉｅｇｌｅｒ－Ｎａｔａ催化剂首次合成了间规度为～５０％间规聚丙烯，并对其进行了表征，指出其具有（ＴＴＧＧ）２螺旋构象，正交晶系，Ｃ２２２１空间群［１，２］．近年来用茂金属催化剂合成的间规立构聚丙烯（ｓＰＰ）的间规度可达９３％以上，高间规…

Studies on biodegradable poly(hexano-6-lactone) fibers 1. Structure and properties of drawn poly(hexano-6-lactone) fibers

Using high molecular weight (M-n=80,000) Poly(hexano-6-lactone) (PCL'), tough and high tenacity PCL monofilaments with various draw ratios (undrawn to 9 times drawn) were prepared by melt-spinning. The relationship between microstructure and properties of the PCL fibers is described in this current IUPAC Technical Report. Analysis of microstructure of the drawn PCL fibers by wide-angle X-ray diffraction revealed typical c-axis orientation with an increase in crystallinity. It was also supported by sonic velocity measurements. The thermal, mechanical, and dynamic mechanical properties of the PCL fibers were affected significantly by draw ratio. DSC thermograms showed that the melting temperature and the enthalpy of fusion increased with draw ratio. The temperature dependence curves of dynamic viscoelasticity showed that the temperature at tan delta peak of alpha dispersion corresponding to the glass transition temperature shifted toward higher temperature and the peak value of tan delta decreased with draw ratio. The dynamic storage modulus and the sonic modulus increased with draw ratio. These results are due to the increase in crystallinity and molecular orientation with drawing, and are responsible for an increase in tensile tenacity as well as knot tenacity of the PCL fibers.

Crystallization kinetics and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends

The crystallization behavior and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends have been studied with DSC, POM, SAXS and WAXD methods. The results indicate that the overall crystallization rate and spherulite growth rate are slower in the blends than that in the pure PHB. The addition of PVAc has no effect on the crystal structure of PHB, but affects its crystalline morphology. During crystallization of PHB, PVAc chains were being rejected into the region between the lamellae of crystalline PHB. (C) 1997 Elsevier Science Ltd.

Effects of molecular weight and interaction parameter on the glass transition temperature of polystyrene mixtures and its blends with polystyrene/poly(2,6-dimethyl-p-phenylene oxide)

The glass transition temperature (T-g) of mixtures of polystyrene (PS) with different molecular weight and of blends of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and polystyrene with different molecular weight (DMWPS) was studied by a DSC method. For the whole range of composition, the curves of T-g vs composition obtained by experiment were compared with predictions from the Fox, Gordon-Taylor, Couchman and Lu-Weiss, equations. It was found that the experimental results were not in agreement with those from the Fox, Gordon-TayIor and Couchman equations for the binary mixtures of DMWPS, where the interaction parameter chi was approximately zero. However, for the blends PPO/DMWPS (chi < 0), with an increase of molecular weight of PS, it was shown that the experimental results fitted well with those obtained from the Couchman, Gordon-Taylor and Fox equations, respectively. Furthermore, the Gordon-Taylor equation was nearly identical to the Lu-Weiss equation when \chi\ was not very large. Further, the dependence of the change of heat capacity associated with the glass transition (Delta C-p) on the molecular weight of PS was investigated and an empirical equation was presented. (C) 1997 Elsevier Science Ltd.

Thermal analysis of ethylene propylene copolymer-grafted-acrylic acid

The thermal properties of ethylene propylene copolymer-grafted-acrylic acid (EP-g-AA) were investigated by using differential scanning calorimetry (DSC). Compared with the ethylene propylene copolymer (EP), the peak values of the melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, the crystallization temperature (T-c) increased about 8-12 degrees C, and the melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of the ungrafted sample was 1.6-1.8, and that of grafted samples were all above 2, which indicated that the grafted monomer could become the crystal nuclei for the crystallization of propylene sequence. With increasing grafted monomer content, the crystallization rate of propylene sequence in grafted EP increased; it might be the result of rapid nucleation rate and crystal growth rate.

Polymerization of ethylene by zirconocene-B(C6F5)(3) catalysts with aluminum compounds

Ethylene polymerization by zirconocene-B(C6F5)(3) catalysts with various aluminum compounds has been investigated. It is found that the catalytic activity depended on zirconocenes used, and especially on the type of aluminum compounds. For Et(H(4)Ind)(2)ZrCl2 (H(4)Ind : tetrahydroindenyl), the activity decreases in the following order: Me3Al > i-Bu3Al > Et3Al much greater than Et2AlCl. While for Cp2ZrCl2(Cp : cyclopentadienyl), it varies as follows: i-Bu3Al > Me3Al much greater than Et3Al. Furthermore, the activity is significantly affected by the addition mode of the catalytic components, which may imply that the formation of active centers is associated with an existing concentration of catalytic components. Results of thermal behavior of polyethylene (PE) studied by differential scanning calorimetry(DSC) show that crystallinity of the polymer prepared with Et3Al is higher than that with Me3Al or i-Bu3Al. It is also found that the number-average molecular weight ((M) over bar) of the polymers prepared with Me3Al or i-Bu3Al is much higher than that with Et3Al. H-1-NMR studies substantiate that i-Bu3Al is a more efficient alkylation agent of Cp2ZrCl2 in comparison with Me3Al. (C) 1997 John Wiley & Sons, Inc.

Poly(vinyl methyl ether) poly(methyl methacrylate) blends using diblock copolymer of styrene and methyl methacrylate as compatibilizer

Blends of poly(vinyl methyl ether) (PVME) and poly(methyl methacrylate) (PMMA) compatibilized by poly(styrene-block-methyl methacrylate) (P(S-b-MMA)) ale studied by FT-IR, DSC, excimer fluorescence spectrometry, and scanning electron microscopy (SEM). In FT-IR measurement the ratio of absorption intensity at 1107 cm(-1) to that at 1085 cm(-1) (I-1107/I-1085) reaches a minimum at about 10wt% block copolymer content. DSC results show that the glass transition temperature of PVME in the blends has a maximum at 10 wt% copolymer content. In plots of the ratio of excimer-to-monomer fluorescence emission intensities (I-E/I-M) VS block copolymer content, I-E/I-M increases rapidly above 10%. Ail these phenomena show that PS block chains penetrate into PVME: domains on addition of block copolymer. Above 10% copolymer content, block copolymer chains tend to form micelles in bulk phase.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .2. Chemorheological modeling

Chemorheology and corresponding models for an epoxy-terminated poly(phenylene ether ketone) (E-PEK) and 4,4'-diaminodiphenyl sulfone (DDS) system were investigated using a differential scanning calorimeter (DSC) and a cone-and-plate rheometer. For this system, the reported four-parameter chemorheological model and modified WLF chemorheological model can only be used in an isothermal or nonisothermal process, respectively. In order to predict the resin viscosity variation during a stepwise temperature cure cycle actually used, a new model based on the combination of the four-parameter model and the modified WLF model was developed. The combined model can predict the resin viscosity variation during a stepwise temperature cure cycle more accurately than the above two models. In order to simplify the establishment of this model, a new five-parameter chemorheological model was then developed. The parameters in this five-parameter model can be determined through very few rheology and DSC experiments. This model is practicable to describe the resin viscosity variation for isothermal, nonisothermal, or stepwise temperature cure cycles accurately. The five-parameter chemorheological model has also successfully been used in the E-PEK systems with two other curing agents, i.e., the diamine curing agent with the addition of a boron trifluride monoethylamine (BF3-MEA) accelerator and an anhydride curing agent (hexahydrophthalic acid anhydride). (C) 1997 John Wiley & Sons, Inc.

Studies on the PTC/NTC effect of carbon black filled low density polyethylene composites

The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effect of carbon black (CB) filled low density polyethylene (LDPE) composites was studied using electrical resistivity spectra, DSC, tensile mechanical analysis (TMA) and small-angle X-ray scattering (SAXS) techniques. The three LDPEs used have a similar crystallinity and different melting index (MI). The experimental results indicate that the CB has no significant effect on the crystallinity and the long spacing of crystalline domains of LDPE. Based upon the TMA and dynamic elastic modulus spectra, it can be concluded that the PTC effect is related to the thermal expansion of the polymer matrix, and the NTC effect is caused by a decrease of the elastic modulus of the polymer at high temperatures. The NTC effect can be reduced by enhancing either the elastic modulus or the interaction between carbon black and matrix. (C) 1997 Elsevier Science Ltd.

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.

Liquid crystalline polymer as a processing agent in blends of poly(ether-ketone)/LCP70

Blends of a liquid crystalline thermotropic copolyester (LCP70) and an amorphous phenolphthalein based poly(ether-ketone)(PEK-C) with two viscosities were prepared by melt blending. The blends' morphology, rheological and mechanical properties were investigated by DSC, SEM, mechanical and rheological tests. It was observed that the optimum composition of the PEK-C/LCP70 blend was 10 wt% LCP for both mechanical and rheological properties. When the LCP content was less than 10%, the LCP phase existed as finely dispersed fibrous domains with a diameter of about 1 mu m in the matrix, and both tensile and flexural properties were improved. In contrast, when the LCP content reached 20% or more, the LCP domains coalesced to ellipsoidal particles with a diameter of about 5 mu m, and the mechanical properties decreased as a result. It is demonstrated that pure PEK-C with a high viscosity which was difficult to process by melt extrusion, could be extruded conveniently when 10% LCP70 was incorporated. It is emphasized that LCP not only can be used as a reinforcing phase but also an effective processing agent for engineering thermoplastics, especially for those with high viscosity and narrow processing window. (C) 1997 Elsevier Science Ltd.