聚苯硫醚纤维的抗张强度与工艺和结构的关系

以熔融纺丝法制备出不同结晶度的各向同性聚苯硫醚纤维作为样品,根据密度和声速测定值确定出PPS晶相和无定形相的本征横向声模量E0⊥,c(4.40 GPa)和E0⊥,am(1.99 GPa).利用密度梯度法测定出的结晶度Xc和X-衍射法测定的晶区取向因子fc,按照Samules模型计算出不同牵伸和定型工艺下制备的PPS纤维样品的非晶区取向因子(fam),在此基础上分析PPS纤维抗张强度与牵伸定型工艺参数、结构之间的关系.结果表明,PPS纤维的最佳牵伸温度及紧张热定型温度分别在90℃和190℃附近;提高PPS纤维的牵伸温度及紧张热定型温度可以增加纤维的结晶度,在一定范围内对纤维抗张强度的增加有促进作用;但较高的牵伸温度及紧张热定型温度不利于纤维非晶区取向的提高,造成PPS纤维抗张强度降低.牵伸倍数的增加可以有效提高PPS纤维的非晶区取向程度,抗张强度也随着增加.     

热处理对聚芳醚腈的结晶行为及熔融的影响

利用广角X射线衍射 (WAXD)方法和示差扫描量热法 (DSC)研究了不同热处理温度 (Th)下聚芳醚腈(PCE)的微晶尺寸、结晶度及热性能的变化 .结果表明 ,淬火样品在熔融温度以下 ,热处理对微晶尺寸、结晶度、Tg 及Tm 均有不同程度的影响 ,且都随Th 的升高 ,其Dhkl、Xc 和Tm 也升高 .实验还发现 ,结晶样品的结晶度与原粉试样相比较均下降 ,说明PCE聚合物在熔融过程中出现了交联 ,导致了结晶度的下降     

用X射线衍射分峰法研究固相热处理对聚苯硫醚结晶行为的影响

本文应用电子计算机对固相热处理的聚苯硫醚(PPS)粉末的X射线衍射图谱进行分峰处理。结果表明,固相热处理使PPS粉末的结晶度下降,同时其平均晶粒体积和垂直于分子链轴方向的晶粒基平面面积增大。与热分析的结果对比,讨论了PPS在固相热处理过程中所发生的物理与化学过程。     

用X射线衍射法快速测定聚对次苯基硫醚的结晶度Ⅱ.

本文报道用X射线衍射测定聚对次苯基硫醚(pps)结晶度的一个快速测定方法:即选择(110)峰和峰的积分面积与对应的非晶散射峰的积分面积代表它们的强度来计算聚对次苯基硫醚的结晶度,利用这个方法测定了聚对次苯基硫醚原粉和在不同温度下热处理后样品的结晶度,最后得到了比较满意的结果。     

电纺聚氧化乙烯纤维的分散形态和结晶行为研究

将聚氧化乙烯(PEO)水溶液在不同的工艺条件下进行电纺,制备了PEO纤维.用SEM研究了纤维的分散形态;用DSC和XRD研究了纤维的结晶性能.电纺纤维分散形态是由浓度、电压、固化距离等因素综合作用的结果.其中,浓度是最关键的因素.降低溶液浓度,提高静电压和增加固化距离均会使纤维变细.电纺得到的纤维与原粉相比,电纺使纤维结晶度下降,理论上分析了可能的机理.     

聚酰亚胺对高性能树脂共混体系界面的反应增强

研究了以5-降冰片烯-2,3-二羧酸单甲酯为端基的PMR型聚酰亚胺(POI)作为界面介质对部分相容的聚醚砜/聚苯硫醚(PES/PPS)、聚醚醚酮/聚醚砜(PEEK/PES)共混体系的界面性质、形态结构及结晶行为的影响.结果表明,POI可以有效地增强两相间的界面粘结,显著降低PPS/PES共混物中PPS分散区的尺寸,改善两组分间的相容性.在熔融共混过程中,POI从本体向界面扩散并同PPS,PES产生交联和/或接枝,POI同PPS的反应活性远高于PES,但POI与PES发生反应.POI是PPS结晶的有效成核剂.     

环状苯硫醚七聚体的分离与表征

聚苯硫醚(PPS)工业化生产中除了获得PPS外,还会产生较多的副产物,如氯化钠、低聚物等,其中副产的低聚物以浆料形式存在.这些副产物不能直接排放,否则会造成严重的环境污染.就PPS低聚物浆料而言,充分认识其组成是其资源化利用的关键.     

RHEOLOGICAL BEHAVIOR OF POLYPHENYLENE SULFIDE/POLYAMIDE-66 BLENDS

Blends of polyphenylene sulfide (PPS) containing trace amounts of branching and/orcross-linking in chain and Polyamide-66(PA-66) have been prepared by melt blending. Therheological behavior of PPS/PA-66 blends has been studied by means of capillary rheo-meter, and compared with PPS. The effects of shear rate, shear stress and temperature onthe flow of PPS/PA-66 blends and PPS are discussed. The non-Newtonian indexes andthe activation energies of viscous flow are obtained. The results show that the apparentviscosity of PPS/PA-66 blends is not sensitive to shear rate and stress, but decreases withthe elevation of temperature. On the contrary, the apparent viscosity of the PPS decreasesobviously with the increasing of shear rate and shear stress, but it is increased by theelevation of temperatue.     

聚对次苯基硫醚(PPS)非晶态结构的径向分布函数研究

本文根据PPS的晶体结构模型,建立了近似的P(r)曲线。把它与实验结果比较,发现第5,6,7峰随结晶度下降而降低,这是和晶态结构中分子链间的三个S—S间距(5.16,5.61,6.76)遭到破坏相一致的;相应增加的S—C间距数与非晶态样品中第4,7峰的增高相一致。这个现象则认为是分子链沿纤维轴方向发生位移引起的。同时还发现第6峰的峰顶位置由5.7移到6.0,说明分子链间发生侧向膨胀。结合宽散峰的峰顶位置、高度变化趋势及存在范围,非晶态PPS在r=10-15的近程范围以内,仍属侧向有序,分子链处在类似于晶态结构的配位堆积状态,有序周期为～5.2。     

PA6/PPS共混物介观形貌的DPD模拟

应用耗散粒子动力学(DPD)模拟方法研究了PA6/PPS共混物的介观形貌及动力学演变过程.详细分析了不同比例下PA6/PPS共混物的介观形貌、密度、扩散系数以及界面张力等变化情况,同时还考察了不同剪切速率对体系介观形貌的影响.结果表明,PA6/PPS共混物中随PA6含量的增加,PA6的介观形貌依次出现球状、柱状、层状以及连续相等结构,PA6的扩散系数大于PPS,说明PA6的加入可以改善共混物的加工流动性,这与文献报道的实验结果相一致.同时剪切速率的大小对PA6/PPS体系形貌有着重要影响.     

聚苯硫醚/低熔点玻璃复合体系的熔融制备与力学性能

选取低熔点玻璃(LMTG)为无机组分,聚苯硫醚(PPS)为聚合物基体,在适宜的温度下熔融制备了复合体系(PPS/LMTG).探讨了加工工艺对体系中LMTG无机相形态的影响,研究了加工温度低于LMTG软化温度制备的普通填充体系(PPS/LMTG300)和高于软化温度制备的熔融液-液复合体系(PPS/LMTG400)的力学性能.结果表明,对于所选择的体系,可以在325~450℃内实现有机无机相液-液复合;温度场、剪切场均影响LMTG分散相的形貌,液-液复合过程中LMTG分散相液滴在剪切场中呈现类似变形、破裂、凝聚和松弛回复等特征;与普通填充体系PPS/LMTG300相比,由液-液复合得到的PPS/LMTG400体系中无机相在复合过程中原位生成平均粒径更小的形态,其粒子基体相互作用减弱;且经过液-液复合,粒子分散性得到了较大的改善,PPS/LMTG400体系中即使含量高达66 wt%,无机粒子仍然具有优良的增强效果.     

INVESTIGATIONS ON THE CRYSTALLINE MORPHOLOGIES OF POLYPHENYLENE SULFIDE AND THE CARBON FIBRE SURFACE EFFECTS

By the use of polarized light microscopy, chemical etching and scanning electron micro-scopy, the erystalline morphologies of polyphenylene sulfide (PPS) have been studied. Thecrystalline morphologies of PPS are greatly affected by the curing conditions. Either gra-phite fibres and carbon fibres, or glass fibres, possess the ability of inducing the transcry-stallization of PPS at different degrees. The corrosive resistance of PPS resin is not onlyrelated with its chemical structure, but also with its aggregation structure, and furthermorewith the "interface effects" of carbon fibres in the composites.     

苯基硅氧烷改性TiO2在聚苯硫醚抗紫外中的性能研究

首先以苯基三乙氧基硅烷（PTES）为改性剂,采用凝胶-溶胶法对金红石型TiO₂进行表面化学修饰,制备了抗紫外TiO₂/PTES纳米粒子.然后通过对TiO₂/PTES纳米粒子的系统表征,发现PTES的载入显著地抑制了TiO₂的光催化性能.最后将抗紫外性能优异的TiO₂/PTES-2纳米粒子以不同比例加入PPS中,制备了PPS复合薄膜,探讨了纳米粒子的添加对PPS抗紫外老化性能的影响.结果表明,当TiO₂/PTES-2纳米粒子的添加量为2.0 wt%时,PPS抗紫外性能达到最佳,即TiO₂/PTES-2/PPS复合薄膜紫外辐射192 h后的断裂强度保留率和断裂伸长保留率分别为93.75%和94.00%.     

STUDIES ON THE EXCIMER FLUORESCENCE AND THE STERIC TACTICITY OF POLYPHENYLSILSESQUIOXANES

The steric tacticity of polyphenylsilsesquioxanes (PPS) was studied by exeimer fluorescence spectroscopy. It was found that the fluorescence of PPS come mainly from its intramolecular excimers, The experimental results indicated that the steric-structure of PPS is most probably cisisotactic rather than the cis-syndiotactic as suggested in the literature. With the increase in defect content monomer fluorescence intensity increases because of the enhanced mobility of phenyl groups. Molecular weights and molecular weight distributions do not affect the fluorescence spectra of PPS.     

聚苯硫醚共混合金的研究进展

本文简述了特种工程塑料聚苯硫醚（PPS）与其它多种高聚物的共混改性，分别介绍了PPS／PA、PPS／PEEK、PPS／PSF、PPS／TLCP、PPS／PF、PPS／PBT、PPS／PES、PPS／PC、PPS／PEK－C、PPS／PS以及其它PPS共混合金在国内外的研究进展及其生产应用，其中重点论述了PPS与聚四氟乙烯（PTFE）树脂的共混改性及其该共混合金的性能与用途。并展望了PPS合金的发展。     

SOLUTION PROPERTIES OF LADDER-LIKE POLYMER POLYPHENYLSILSESQUIOXANES

Solution properties of ladder-like polymer polyphenylsilsesquioxane (PPS) were studied by measurement of intrinsic viscosity, small angle laser light scattering and gel permeation chromatography. It was found that PPS can be modeled with a wormlike continuous cylinder rather than a wormlike coil. A plot of (M~2/[η])~(1/3) vs. M~(1/2) was employed in obtaining the persistence length (2λ)~(-1) and effective hydrodynamic diameter. When MW≤5×10~5, Mark-Houwink equation is adequate in describing the relationship between MW and [η] with αabout unity. This implies that PPS chain is semi-stiff. For GPC experiments, it was shown that universal calibration can be applied in PPS. When molecular weights of PPS are sufficiently high, their molecular weight distributions are often very broad.     

A NEW POLYMERIC FLAME RETARDANT ADDITIVE FOR NYLON

The present paper deals with the use of a new polymeric flame retardant material, polyphenylene sulphide (PPS) for plastics. Incorporation of 15—20% PPS into nylon-6 has provided UL V-0 rating for the system and there is enhancement in tensile and flexural properties. The results obtained on the thermal, crystallization and flow characteristics of the nylon-PPS system upto a loading of 40% PPS are also discussed.     

Non-isothermal crystalliztion kinetics of poly(phenylene sulfide) with low crosslinking levels

Poly(phenylene sulfide) (PPS) with different crosslinking levels was successfully fabricated by means of high- temperature isothermal treatment (IT). The crosslinking degree of PPS was increased with IT time as revealed by Fourier-transform infrared spectroscopy and dynamic viscosity measurements. Its influence on the non-isothermal crystallization behaviors of PPS was studied by differential scanning calorimeter (DSC). The crystallization peak temperature of PPS with 6 h IT was 15 K higher than that of the one with 2 h IT at 30 K/min cooling rate. The non-isothermal crystallization data were also analyzed based on the Ozawa model. The Ozawa exponent m decreased from 3.5 to 2.2 at 232℃ with the increase of the IT time, suggestive of intensive thermal oxidative crosslinking reducing the crystallite dimension as PPS crystal grew. The reduced cooling crystallization function K(T) was indicative of the larger activation energy of crosslinked PPS chain diffusion into crystal lattice, resulting in a slow crystal growth rate. Additionally, the overall crystallization rate of PPS was also accelerated with the increase of crosslinking degree from the observation of polarized optical micrograph. These results indicated that the chemical crosslinked points and network structures formed during the high-temperature isothermal treatment acted as the effective nucleating sites, which greatly promoted the crystallization process of PPS and changed the type of nucleation and the geometry of crystal growth accordingly.     

STUDIES ON REGULARITY OF POLY PHENYLSILSESQUIOXANE CHAINS

IR and ~(29)Si NMR were used to determine the structures of ladderlike polymer polyphenylsilsesquioxanes (PPS). It was found that PPS with lots of defects had a wide and strong absorption band in 1000—1400 cm~(-1) with only one sharp peak at 1137 cm~(-1) while two peaks (1130 and 1045 cm~(-1) were observed for PPS with perfect ladderlike structure. Branching and crosslinking of PPS lead to the reduction of 1045 cm~(-1) peak. ~(29)Si NMR spectra, however, showed two peaks (δ=-78 ppm and -87 ppm when δ_(HMDS)=0 ppm) for defective or branched PPS. The -87 ppm peak is related to the ladderlikely constructed Si atoms and -78 ppm corresponds to defective Si atoms. PPS with defects less than 0.1% chain units was obtained by azeotropic polycondensations.     

Insight into the Excellent Tribological Performance of Highly Oriented Poly(phenylene sulfide)

Achieving low friction and wear of poly(phenylene sulfide)(PPS) without using fillers or blending is a challenging task, but one of considerable practical importance. Here we describe how neat PPS with high tribological performance is achieved by manipulating processing parameters(pressure, flow and temperature). The key to achieving high tribological performance is comparatively high molecular chain orientation, realized in neat PPS, at high shear rates and low pressure. The friction coefficient and wear rate are as low as ~0.3 and~10^-6 mm³·N^-1·m^-1, respectively, which break the record for neat PPS. These values are even better than those for PPS-based blends and comparable to PPS composites. Further studies show, for the first time, that wear rate decreases exponentially with increasing molecular chain orientation, prompting us to revise the classical Archard's law by including the effect of molecular chain orientation. These findings open the possibility of using neat PPS in highly demanding tribological applications.