Structure and properties of N-octadecylated poly(p-phenylene terephthalamide)

N-octadecylated PPTA's with various molecular weights were synthesized from PPTA and n-octadecyl bromide via the metalation reaction. The polymer exhibited side-chain crystallization at 314 K due to the long alkyl side chains and both crystallinity and the perfection of the crystal increase with increasing in the molecular weight. The results of IR spectra and the wide angle X-ray indicate that the polymer crystallizes in hexagonal form. The mechanical and the dynamic mechanical properties of N-octadecylated PPTA's were measured. Two tan δ peaks were observed in a temperature range of 310–350 K and at 260 K, respectively, which can be designated α_c and α_a relaxation, respectively. The concentrated solutions of N-octadecylated PPTA's in tetrahydrofuran, dichloroethane, tetrachloroethane, and bromoform showed liquid crystalline behavior of lyotropic type.     

正己烷溶剂对聚对苯二甲酰对苯二胺聚合反应的影响

以对苯二胺和对苯二甲酰氯为反应单体,以氯化钙的N-甲基吡咯烷酮(NMP)溶液为溶剂,同时加入不与NMP互溶的正己烷,采用低温溶液缩聚反应制得聚对苯二甲酰对苯二胺(PPTA),研究了正己烷的加入对PPTA的聚合反应及产物结构与性能的影响。结果表明:正己烷的引入可以推迟PPTA聚合反应过程中产生凝胶的时间,有利于聚合反应的进行;当正己烷与NMP的体积比为1∶2时,可以制得较高相对分子质量的PPTA;正己烷的加入可使PPTA树脂颗粒的比表面积更大,但对其结构和性能影响不大。     

Tensile and compressive behavior of poly(p-phenylene benzobisthiazole) fibers

Heat treated poly(p-phenylene benzobisthiazole) (PBZT) fibers tested in tension result in two types of failure modes. In failure mode I, the fiber exhibits a relatively sharp break; mode II is characterized by significant axial fiber splitting. Approximately 20% of the fibers failed in mode II when tested at 2.54, 7.62, and 12.7 cm gage lengths. At 1.25 cm gage length all the fibers failed in mode I. Tensile strength decreased from the 1.25 to 7.62 cm gage length, but tensile strength of the fibers tested at 7.62 and 12.7 cm gage lengths were similar. The two failure mode observation is supported by the Weibull statistical distribution. Fiber tensile properties were also measured at 150°C. Axial compressive strength of the PBZT fibers as determined from the recoil test is also reported and is found to be independent of fiber tensile modulus and fiber diameter. As-received heat-treated fibers were post heat treated between 700 and 775°C. Structural changes in the fiber were studied using infrared spectroscopy, small and wide angle x-ray scattering, and swelling studies. © 1995 John Wiley & Sons, Inc.     

含氯聚对苯二甲酰对苯二胺纤维的结构与性能

以邻氯对苯二胺(Cl-PPD)与对苯二甲酰氯(TPC)为单体,在N-甲基吡咯烷酮(NMP)/氯化钙(Ca Cl2)或氯化锂(Li Cl)体系中进行低温溶液聚合,合成了含氯聚对苯二甲酰对苯二胺(Cl-PPTA)溶液,直接进行湿法纺丝,制备了Cl-PPTA纤维。采用旋转流变仪测试了Cl-PPTA溶液的流变性能,利用傅里叶变换红外光谱、扫描电子显微镜、热失重分析、纤维强伸度仪、声速取向测量仪、氧指数测定仪对Cl-PPTA纤维的结构及性能进行了表征。结果表明:相比于NMP/Ca Cl2体系,NMP/Li Cl体系的Cl-PPTA溶液黏度更低,所制得的纤维其表面更光滑、结构更致密,纤维力学性能也较好;热处理后两种纤维力学性能均得到进一步改善;两种Cl-PPTA纤维具有较好的热稳定性,其阻燃性能均远高于PPTA纤维。     

Polymer composite of rigid and flexible molecules: Blend systems of poly(p-phenylene terephthalamide) and ABS resin

Homogeneous coagulant of poly(p-phenylene terephthalamide) (PPTA) and ABS resin was obtained by pouring the dimethylsulfoxide solution of N-sodium PPTA and ABS into acidic water. Transmission electron microscopic observation proved that PPTA was dispersed in the matrix in a form of microfibril with a diameter of 10–30 nm. The T_g of the resin component in ABS shifted to higher temperatures with increasing fraction of PPTA. Stress-strain behavior of the polymer composite showed increased tensile modulus and strength with addition of PPTA. The transition temperature from brittle to ductile fracture, however, shifted to higher temperature resulting in lower extensibility. Incorporation of the block copolymer of PPTA and polybutadiene into ABS improved the ultimate extensibility, i.e., increased toughness was provided compared with the simple composite systems of ABS and PPTA microfibrils. Scanning electron microscopic observation showed that the polymer composite made with the block copolymer generated many crazes upon deformation, while the composite with PPTA homopolymer fractured without remarkable craze formation. Thus, a new type of thermoplastic with improved mechanical properties was obtained by use of PPTA block copolymer as compatibilizer.     

Deformation band studies of axially compressed poly(p-phenylene terephthalamide) fiber

Deformation mechanism of poly(p-phenylene terephthalamide) (PPTA) fiber during axial compression was studied. PPTA fibers were embedded in resin and axialy compressed in a tensile machine. PPTA fibers were then taken out from resin at various stages of compression. Kink band formation was examined by means of polarizing microscopy, X-ray diffraction (WAXD), electron diffraction (ED), and electron microscopy. WAXD pattern of seriously compressed PPTA fiber shows that (200) reflection spots and arcs appear on the equator and meridian respectively. On the other hand, (110) reflection spots are confined to the equator. PPTA fiber could be splitted tangentially and radially into two kinds of thin fibrillar fragments (I and II) which reveal two distinct types of kink band and ED pattern. In fragment I obtained by tangential splitting, kink bands are formed at about 55° with respect to fibril axis, whereas in fragment II obtained by radial splitting kink bands are formed perpendicular to the fibril axis. These results were confirmed by ED studies. It was assumed that slip of (200) planes containing hydrogen bonded sheets as well as intermicrofibril slip plays an important role in the deformation of PPTA fiber during axial compression.     

Morphology effect on water sorption behavior in a thermoplastic modified epoxy resin system

Water sorption behavior in polyetherimide (PEI) modified diglycidyl ether bisphenol-A/4,4′-diaminodiphenyl sulfone (DGEBA/DDS) systems was investigated by gravimetric analysis, positron annihilation lifetime spectroscopy and scanning electron microscopy. The equilibrium water uptake showed strong composition-dependent, which suggested that hydrophilic groups rather than free volume were more significant in determining ultimate water sorption. While besides the number of hydrophilic groups and fractional free volume, morphology induced by phase separation was another key factor that decided the value of diffusion coefficient, which was chiefly responsible for the anomalous diffusion behavior observed at the beginning of co-continuous phase. In addition, morphology not only had the function of decreasing fractional free volume, but also changed the number of hydrophilic groups in epoxy rich regions, which obviously distinguished water sorption behavior in the blends from that in single component systems.     

Mesomorphic polyblends of poly(p-phenylene terephthalamide) and poly(4,4′-terephthanilide adipamide)

A simultaneous dissolution of two lyotropic polyamides, poly(p-phenylene terephthalamide) (PPTA) and poly(4,4′-terephthanilidc adipamide) (PTAd), in a concentrated H₂SO₄ (1 to 1.5% wt) produced an isotropic single phase solution. The crystallinity of PPTA/PTAd blends confirmed formation of a mesomorphic polyblend to the molecular level. With increasing concentration, solutions of these PPTA/PTAd blends in 100% H₂SO₄ showed a sequential phase change typical of a single lyotropic polymer. Further, the ternary solution exhibited a wider biphase range than both binary solutions of PPTA/100% H₂SO₄ and PTAd/100% H₂SO₄. Dry-jet wet spinning of anisetropic solution of this ternary composition with a PTAd weight fraction less than 0.5 enabled us to obtain PPTA/PTAd blend fibers. Including a PTAd weight fraction of 0.1-0.15 reduced both the orientation angle and fibrillation. The particular blend fiber with a PTAd weight fraction of 0.15 exhibited a synergistic effect on the mechanical properties.     

聚对苯二甲酰对苯二胺降解性研究

通过测量不同条件下聚对苯二甲酰对苯二胺(PPTA)溶液的比浓对数黏度,分析在PPTA纺丝前可能引起聚合物降解的因素,这些因素包括纺丝液浓度、残余的CaCl2、N-甲基-2-吡咯烷酮、水分和氢氧化钙等,最终得到水分和氢氧化钙对PPTA的降解影响很大,其余影响较小的结论。同时,分析了降解前后聚合物的结构和性能,发现降解结果是部分端胺基被氧化成硝基。     

Characterization of the adhesion of single-walled carbon nanotubes in poly(p-phenylene terephthalamide) composite fibres

Poly(p-phenylene terephthalamide)/single-walled carbon (PPTA/SWNT) composite fibres with different draw ratios have been spun using a dry-jet wet spinning process and their structure and deformation behaviour analysed using Raman spectroscopy. The dispersion of nanotube has been examined by Raman scattering intensity mapping along the fibre. The nanotubes improved the polymer orientation in composite fibre with a draw ratio of 2 but degraded the orientation at higher draw ratios. The mechanical reinforcing effect by nanotubes is related to the change of polymer orientation, suggesting a dominant role of polymer orientation in mechanical performance of the composite fibre. High efficiency of stress transfer within the strain range of 0-0.35% and breakdown of the interface at higher strains has been found in the composite fibres through an in situ Raman spectroscopic study during fibre deformation. Cyclic loading applied on the fibre has indicated reversible deformation behaviour at low strain and gradual damage of the interface at high strains.     

聚对苯二甲酰对苯二胺的合成方法

分别介绍了聚对苯二甲酰对苯二胺的应用及界面缩聚法、酯交换法、气相聚合法、低温溶液缩聚法、直接缩聚法等几种合成方法的优缺点,分析了国内外聚对苯二甲酰对苯二胺的发展趋势。     

Degradation of respirable fibrils of poly(p-phenylene terephthalamide) by solar ultraviolet radiation

After ～ 160 days in the environment, the polymer in a respirable-size poly(p-phenylene terephthalamide) fibril (diameter = 0.3 μm) is expected to degrade, due to solar ultraviolet radiation, from an initial molecular weight of ～ 20,000 to less than 400. This estimate is based on ultraviolet absorption characteristics, photolytic degradation kinetics, and judgments regarding how these translate into actual time in the environment. Degradation to this molecular weight level will cause the fibril tensile strength and modulus to decrease to ～ 1% of their initial values. Mechanically, such a degraded fibril will be weak and brittle with properties similar to those of uncooked spaghetti. © 1994 John Wiley & Sons, Inc.     

Tensile deformation of poly(p-phenylene terephthalamide) fibres,an experimental and theoretical analysis

The tensile deformation of poly(p-phenylene terephthalamide) fibres has been investigated. Functional relationships observed between stress, crystallite orientation distribution, dynamic modulus and strain are derived from an analysis of the deformational behaviour of a series model consisting of a linear arrangement of crystallites. It is shown that the deformation of these fibres is largely brought about by the elastic strain and irreversible rotation of the crystallites. A formula is derived for the stress—strain relationship of a crystalline polymeric fibre with a narrow crystallite orientation distribution.     

Rheological properties of liquid-crystalline solutions of poly(p-phenylene terephthalamide) and behavior of the jet in spinning through an air space

LC solutions of PPTA behave like liquids with a power law of flow and n =0.65–0.78 for flow through the channels of standard spinnerets with small diameters and q =0.88–0.95 for longitudinal flow in jets. Spinneret expansion of a freely falling jet in channels with small diameters is equal to 1.70–1.75 and is not a function of the shear rate on the wall. Spinneret expansion is preserved in conditions of repeated drawing of the jets in the air space until very small air spaces at 1.5–2.5 mm are used. In spinning PPTA fibres through an air space with a high jet draw ratio, only a small fraction of this drawing in the spinning bath is possible. Translated from Khimicheskie Volokna, No. 2, pp. 3–7, March–April, 1997.     

聚对苯二甲酰对苯二胺共缩聚工艺研究

通过添加第三单体3,4'-二氨基二苯醚(3,4'-ODA)对聚对苯二甲酰对苯二胺(PPTA)进行改性,能够使其溶于一般的极性有机溶剂中,得到的聚合物溶液可以直接纺丝。研究了PPTA共聚合工艺,探讨了反应时间、反应温度、单体摩尔浓度、CaCl2含量以及第三单体含量和初始投料比对共聚物比浓对数黏度的影响。     

Dielectric characterization of water sorption in epoxy resin matrices

Water sorption in epoxy based materials was analyzed by dielectric spectroscopy using remote sensors. A method to determine diffusion coefficients from the changes in permittivity during water absorption is proposed and was verified experimentally by comparison with standard water gain measurements. Although the technique is limited by electrode polarization phenomena, it is sensitive to the presence of water molecules and is capable of detecting different levels of water concentration as a function of frequency. The utilization of remote sensors demonstrated the capability of dielectric analysis to be applied both in the laboratory environment, and on a larger scale, as a nondestructive technique for monitoring environmental changes in actual polymer matrix composite parts.     

Plasma surface treatment of poly(p-phenylene benzobisthiozol) fibers

Poly(p-phenylene benzobisthiozol) (PBZT) fibers were subjected to radio-frequency (RF)-induced, glow-discharge plasma treatments using argon and carbon dioxide gases in order to modify the adhesion of the fibers to bisphenol-A epoxy. The interfacial shear strength (IFSS) was used as a measure of the adhesion and was determined using the microbond technique. Scanning electron photomicrographs revealed no visible surface etching at magnifications of up to 10 000 x . Slight, but statistically significant, improvements in IFSS were noted with the CO₂ plasma-treated fibers as compared with control fibers, but Ar plasma-treated fibers showed no improvement.     

Preparation and properties of graft and block copolymers of poly(p-phenylene terephthalamide) with polybutadiene

Graft copolymers of polybutadiene (PBD) onto poly(p-phenylene terephthalamide) (PPTA) were prepared by the nucleophilic substitution of N-metalated PPTA with telechelic PBD having bromide end groups. Block copolymers were synthesized by the condensation reaction of telechelic PBD having acid chloride end groups with amino-group-terminated PPTA. The structure of these copolymers was identified by IR spectra. Graft and block copolymers contained PBD segments up to 85 wt % and 45 wt %, respectively. Thermomechanical analyses (TMA) proved the existence of distinctive primary absorption peak corresponding with T_g of PBD for both graft and block copolymers. The T_g's of both types of the copolymers were further ascertained by the DSC curves. TMA curves suggested that the microphase separation occurred between PPTA and PBD. The incorporation of PPTA segments into PBD increased the decomposition temperature compared with the blend polymer composed of PPTA and PBD with the same composition.