Effect of Added Poly (vinyl pyrrolidone) during Condensation on Properties of Poly(p-phenylene terephthalamide)Pulp

Poly(p-phenylene terephthalamide)(PPTA)pulp was prepared by polycondensation of the p-phenylene diamine(PPDA)with terephthaloyl chloride(TPC)in the completely anhydrous solvent system of N-methyl pyrrolidone(NMP)having calcium chloride,in the presence of poly(vinyl pyrrolidone)(PVP)having a viscosity average molecular weight lower than 40 000.It was confirmed that the polycondensation could be accelerated,the inherent viscosity of the polymer could be increased,and the polymers could be fibrillated more easily by the addition of the PVP.FTIR and X-ray spectra proved that PVP had not combined into molecular chains of the resultant PPTA pulps.The morphology of the resultant pulps,the effect of viscosity average molecular weight,amount and adding mode of PVP on inherent viscosity,specific surface area,and mean length of the resultant pulps were discussed in detail.And the friction and wear properties of the compound reinforced by the resultant pulps were simply investigated.

Mechanical Property and Crystal Structure of Poly(p-phenylene terephthalamide)(PPTA) Fibers during Heat Treatment under Tension

The relationship between property and structure of poly( p-phenylene terephthalamide)( PPTA) was investigated for the purpose of obtaining products with better performance. PPTA fiber subjected to heat treatment under different conditions was intensively studied. Simultaneous wide-angle X-ray diffraction( WAXD) technique was introduced to study the changes of crystal structure. It was found that the tensile modulus was strongly sensitive to the levels of temperature and tension. The structure parameters including crystal size and crystal orientation after heat treatment evolve similarly to the tensile modulus,indicating a direct structure-property relationship. The lattic c-dimension increases after heat treatment and is greatly affected by the tension. An optimal temperature can be found around 400 ℃,where big change can happen in the crystal structure due to α-relaxation in the crystal region as supported in dynamic mechanical analysis( DMA).

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅰ.POLY(P-PHENYLENE TEREPHTHALATE)

The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅱ. POLY(p-PHENYLENE 2,6-NAPHTHALATE)

Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that "curled up" off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius^2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm^3, space group P12_1/al.

ELECTRICALLY CONDUCTIVE COMPOSITE PREPARED BY ELECTROCHEMICAL POLYMERIZATION OF PYRROLE IN POLY-(p- PHENYLENE TEREPHTHALAMIDE) MATRIX

The preparation of PPy/PPTA conductive composite films by electrochemical method is presented.The first step is to cast a thin layer of poly (p-phenylene-terephthalamide) (PPTA) on a slice of Pt working electrode. The second step is to electrochemically polymerize pyrrole on the PPTA/Pt working electrode. Both of the electrical conductivity and the mechanical properties of the PPy/PPTA composite film are better than those of the pure PPy film, and the film has excellent flexibility at low temperature, even in liquid nitrogen.The SEM picture of the cross-section of PPy,/PPTA composite film showed that the two components were well mixed.Cyclic voltammograms of PPy,/PPTA film in aqueous solution showed that the conductive films could be reduced and reoxidized.

A STUDY OF PACKING STRUCTURE OF POLY(P-PHENYLENE BENZOBISTHIAZOLE)BY MOLECULAR SIMULATION

Molecular simulation technique was used in an examination of the possibilities of chain packing in the crystalline state for poly(ρ-phenylene benzobisthiazole).It has been found that one reason of hardly forming very ordered crystal of the polymer is the existence of so many stable positions of interchain interaction along chain axis.

The Synthesis and Electronic Characteristics of Poly(p-Phenylene Vinylene) Derivatives

A series of soluble poly(p-phenylene vinylene) (PPV) derivatives were synthesized through dehydrochlorination with the p-metaoxy phenol as starting materials. The electronic characteristics of PPV derivatives were studied.

Non-aqueous Suspension Polycondensation in NMP-Ca Cl_2/Paraffin System―A New Approach for the Preparation of Poly(p-phenylene terephthalamide)

A non-aqueous suspension polycondensation method was proposed to proceed the reaction ofp-phenylenediamine and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide） （PPTA）. The system was operated with NMP-CaCI2 solution as the dispersed phase and inert liquid paraffin as the continuous phase. Each of NMP-CaCl2 solution microdroplet suspended in paraffin served as a microreactor where the polycondensation took place. According to the results of TGA, XRD, IR, SEM and EA, PPTA with good quality was obtained through this novel method, and a number of main factors influencing this process were investigated to determine the optimum condition for the preparation of PPTA. Besides, this two-phase polycondensation system brings many unique advantages compared to the conventional solution polycondensation method, including a sealed reaction environment keeping the reactants away from oxygen and water, easy removal of HCI to promote the reaction, well-controlled temperature and low viscosity which means less energy cost.

Kinetics Analysis on the Polycondensation Process of Poly(p-phenylene terephthalamide):Experimental Verification and Molecular Simulation

The conventional low-temperature method of solution polycondensation was developed to realize the reaction of p-phenylenediamin and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide）（PPTA）. Some main factors influencing this process were investigated to determine the optimum condition for high molecular weight. Experiment showed significant slowing of the reaction and gradual deviation of second-order reaction kinetics due to diffusion control. These phenomena were studied theoretically via dynamic Monte Carlo simulation. A concise expression,n～c0^-0.88·t^0.37, was proposed to describe the diffusioncontrolled polycondensation process as a function of the monomer concentration and reaction time. The theoretical results provided a good description of diffusion-effected kinetics for the polycondensation process of PPTA, and demonstrated good agreement with the experimental data. Some differences of scaling relations between model and experiment results were also discussed.

聚对苯二甲酰对苯二胺气凝胶纤维的制备与性能

气凝胶纤维具有良好的柔韧性,其织物在可穿戴保温隔热领域受到了人们高度的关注。聚对苯二甲酰对苯二胺(PPTA)具有优异的耐热性、耐化学品腐蚀等性能,是制备气凝胶纤维的理想材料。然而,目前利用PPTA纤维(对位芳纶)的纳米纤维分散液制备气凝胶纤维的过程复杂、耗时且成本高,因此本工作通过合成具有良好可加工性的PPTA溶液,利用湿法纺丝和冷冻干燥工艺制备PPTA气凝胶纤维,极大地简化了工艺流程。实验分析表明,通过改变PPTA溶液的浓度可以有效地控制气凝胶纤维的孔结构及机械强度。当PPTA溶液的质量分数为2%时,制得的气凝胶纤维的孔隙率高达94.5%,断裂强度可达7.8 MPa;除此之外,该气凝胶纤维还具有高的比表面积(291 m2/g)和低的热导率,其织物的热导率为29.65 mW/(m·K)。当PPTA溶液的质量分数为5%时,气凝胶纤维的断裂强度高达20.5 MPa。本工作中所制备的气凝胶纤维具有极高的孔隙率、超低的密度和热导率以及良好的力学性能,为新一代保温隔热纺织品的设计和制造开辟了新的途径。

对位芳纶的结构与缺陷对其力学性能的影响

聚对苯二甲酰对苯二胺(PPTA)纤维具有优异的力学性能、耐化学腐蚀性能以及阻燃性能,在航空航天、国防、民用等领域得到了广泛应用,是一种新型战略性材料。对4种不同规格的对位芳纶的力学性能、相对分子质量、聚集态结构以及纤维表面及内部缺陷进行研究,建立纤维结构、缺陷与性能之间的关系。结果表明:在具有相同化学分子结构的前提下,聚合物相对分子质量是影响纤维力学性能的重要因素之一,随着相对分子质量的增加,纤维的强度和模量增加。对位芳纶的拉伸强度主要与其结晶度、取向度、表面缺陷以及内部微孔缺陷有关,其中结晶度和微孔缺陷最为重要。纤维的模量主要与纤维的取向度有关,结晶度及纤维内外部缺陷对纤维模量的影响较小。

Laser-induced Janus graphene/poly(p-phenylene benzobisoxazole)fabrics with intrinsic flame retardancy as flexible sensors and breathable electrodes for fire-fighting field

Conventional firefighting clothing and fire masks can protect firemen’s safety to a certain extent,whereas cannot perceive environmental hazards and monitor their physical status in real time.Herein,we fabricated two kinds of Janus graphene/poly(pphenylene benzobisoxazole)(PBO)fabrics by laser direct writing approach and evaluated their performance as intelligent firefighting clothes and fire masks.The results showed that the Janus graphene/PBO fabrics were virtually non-combustible and achieved the highest thermal protection time of 18.91 s ever reported in flame,which is due to the intrinsic flame-retardant nature of PBO fibers.The graphene/PBO woven fabrics-based sensor showed good repeatability and stability in human motion monitoring and NO_(2)gas detection.Furthermore,the piezoelectric fire mask was assembled with graphene/PBO nonwoven fabric as electrode layer and polyvinylidene fluoride(PVDF)electrostatic direct writing film as piezoelectric layer.The filtration efficiency of the fire mask reaches 95%for PM_(2.5)and 100%for PM_(3.0),indicating its effective filtration capability for smoke particles in fires.The respiratory resistance of the piezoelectric fire mask(46.8 Pa)was lower than that of commercial masks(49 Pa),showing that it has good wearing comfort.Besides,the piezoelectric fire mask can be sensitive to the speed and intensity of human breathing,which is essential for indirectly reflecting the health of the human body.Consequently,this work provides a facile approach to fabricate next-generation intrinsic flame-retardant smart textiles for smart firefighting.

苯乙烯共聚物增容玻纤增强PA10T/PPE复合材料

以熔融己内酰胺为溶剂,通过自由基共聚制得一系列苯乙烯-甲基丙烯酸缩水甘油酯(GMA)共聚物(PSG),然后通过熔融共混法制备了PSG增容玻璃纤维(GF)增强聚对苯二甲酰癸二胺(PA10T)/聚苯醚(PPE)复合材料。考察了PSG增容剂的物化特性以及PSG增容剂中GMA的含量对GF/PA10T/PPE复合材料热学性能、力学性能、微观结构和形貌的影响。结果表明,制备的PSG增容剂5%热失重温度不低于374℃,满足GF/PA10T/PPE复合材料增容剂的使用要求。加入PSG显著改善了PA10T相与PPE相的相容性,有效细化了PPE分散相,增强了GF与树脂间的界面结合。当PSG中的GMA物质的量分数为4%时,复合材料展现出最佳的力学性能,拉伸强度为130.4 MPa,弯曲强度为164.4 MPa,缺口冲击强度为7.5 kJ/m^(2),同时该复合材料的饱和吸水率降低至1.32%。该复合材料表现出良好的综合性能,有望在汽车、电器和通信等领域得到应用。

Effect of Curing Poly(<i>p</i>-Phenylene Sulfide) on Thermal Properties and Crystalline Morphologies

Commercial poly(p-phenylene sulfide) (PPS) was thermally cured, which resulted in an increase of molecular weight due to cross-linking. Non-isothermal crystallization studies of samples cured for up to 7 days at 250?C showed a monotonous increase of crystallization temperature compared to pure PPS. However, a further increase of curing time decreased the crystallization temperature. The change in the half-crystallization time (t1/2) was similar to the crystallization temperature. Thus, the cross-linking of PPS affected crystallization behaviors significantly. To a certain extent, crosslinks acted as nucleation agents, but excessive cross-linking hindered the crystallization. Morphologies observed by polarized optical microscopy suggested that thermal curing for as little as 1 day contributed to the spherulitic structure having a smaller size, that was not observed with pure PPS.

STUDIES ON THE POLYPYRROLE/POLYELECTROLYTE MOLECULAR COMPOSITES

The potyelectrolyte of propane sulfonate(PS) grafted PPTA copolymers——PPTA-PS, PPTA[O]-PS, PPTA[C]-PS were prepared and used as electrolyte in the process of electrochemical polymerization of pyrrole to form the molecular composite polypyrrole (PPY)/Polyelectrolyte.The preparation and liquid crystalline property of three kinds of polyelectrolyte, the electrical conductivity, mechanical properties, SEM and thermoproperties of PPY/polyelectrolyte are presented in detail.

KINETICS OF MESOPHASE FORMATION OF A LYOTROPIC AROMATIC POLYAMIDE

The kinetics of mesophase formation of a lyotropic aromatic polyamide from isotropic state has been studied by means of depolarized light intensity. Avrami type analysis of the data gives an exponent close to 1, which suggests the nucleation followed by one-dimensional growth. No influence of blending flexible chain from nylon 6 to the aromatic polyamide on the kinetics of mesophase formation was observed.

RAMAN SPECTROSCOPIC STUDY ON THE CHAIN CONFORMATION OF ELECTROSYNTHESIZED POLY(ρ-PHENYLENE)FILMS

Poly（p-phenylene） （PPP） films have been electrochemically deposited on mirrorlike stainless steel （SS） electrode surfaces by direct oxidation of benzene in boron trifluoride diethyl etherate （BFEE） solutions at a constant applied potential of 1.7 V （versus Ag/AgCl）. The chain conformations of as-grown PPP films have been studied by Raman spectroscopy. The results demonstrated that high synthesis temperature favors the formation of planar PPP, and the conformation of planar PPP can be changed into torsional PPP by cooling treatment.

CONFORMATION AND CHAIN PACKING STRUCTURES OF POLY (ρ-PHENYLEN BENZOBISTHIAZOLE) BY MOLECULAR SIMULATION

The conformation, the chain packing stabilization and the unit cell modeling of poly(p-phenylene benzobisthiazole) have been investigated by using molecular simulation techniquein the present work. A coupling behaviour of σ-bond rotations at either side of the pheny-lene ring or the heterocyclic ring was found surely to exceed a length of the repeat unit ofthe polymer chain. For a single chain model, the stable torsion angle of the repeat resultedat 14°. In the crystalline cell minimization, the dihedral angle along the polymer chaincould even be stabilized in various values. It therefore indicates that the intermolecularinteraction does play a considerable role for this polymer forming the conformation. Ac-cording to cohesive energies calculated for these unit cell models, the torsion angle in themost stable crystalline cell is 0°. When the chains packing together, there exist so manyenergy stable wells along the chain axis 0.35--0.36nm apart from neighbouring chains.Most of the unit cells have quite closed cohesive energies. These factors thus cause thedifficulty of forming an unique perfect crystalline structure of the polymer. The presentstudy suggested a number of reasonable unit cells, and the most stable crystalline structurefor this polymer that is monoclinic, non-primitive unit cell.

酰胺化反应制备聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)共聚物

文中以十二碳二元胺(DDMD)和聚对苯二甲酸乙二醇酯(PET)为原料,环丁砜为溶剂,制备了聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)(Poly(12T-co-ET))共聚物。考察了反应温度、投料比和溶剂用量对产物相对黏度和转化率的影响,确定其最佳工艺条件为,反应温度为210°C、DDMD与PET的投料摩尔比为1.1:1、PET与溶剂的质量比为1:10,得到产物的相对黏度为1.37、转化率为82.1%。通过傅里叶变换红外光谱和核磁共振氢谱确认了产物的结构。差示扫描量热分析和热失重分析结果表明,产物的熔点为234°C、结晶温度为201°C,初始热分解温度为357°C。拉伸强度为37.0 MPa、断裂伸长率为9.32%、弯曲强度为49.2 MPa、缺口冲击强度为1.5 kJ/m^(2)。动态力学热分析结果显示其玻璃化转变温度(T_(g))为91°C。尽管共聚物的综合性能较差,但仍可以作为基体树脂进行共混改性使用,同时,该聚合方法对PET的回收和环境保护具有一定的实用价值。

热拉伸处理温度对PPTA纤维结晶和力学性能的影响

为提高国产聚对苯二甲酰对苯二胺(PPTA)纤维的拉伸模量,采用热拉伸法在不同温度下对PPTA纤维进行处理,利用纤维强伸度仪、乌氏黏度计、X射线散射仪对纤维进行测试,研究热拉伸处理温度对纤维结晶性能和力学性能的影响。结果表明:随着热处理温度的升高,PPTA纤维的拉伸强度降低,模量先增大后减小,在440~480℃时综合力学性能较好;PPTA纤维的结晶度与模量变化趋势相似,在拉伸温度为500℃时结晶度最大为74.0%;与未处理PPTA纤维相比,热拉伸处理后纤维的晶粒尺寸增大,取向度提高;比浓对数黏度与拉伸强度的变化趋势一致,随着热处理温度的升高而降低。