THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.

The Synthesis and Characterization of High Molecular Weight Poly(phenylene sulfide/ether)

Poly（phenylene sulfide/ether） （PPSE） was synthesized from 4,4＇-dihydroxydiphenyl sulfide and 4,4＇-dichlorodiphenyl sulfide in solution by nucleophilic substitution reaction. The resulting polymer was characterized by viscosity measurement, elemental analysis, FT-IR, ^1H NMR, X-ray diffraction and thermal analysis. The results showed that the viscosities of the resulting polymer were above 0.68 dL/g, and the linear chain structure of product was confirmed. PPSE had the same reflex indices as poly（p-phenylene sulfide）, an orthorhombic crystalline with unit cell a=0.853, b=0.562, c=1.026nm. The melting temperature, glass transition temperature and initial decomposition temperature were found to be 228℃, 85℃ and 325℃, respectively. The product was soluble in common organic solvents such as NMP, N, N＇-dimethylformamide, N, N＇-dimethylacetamide and 1,2-dichloroethane.

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.

SYNTHESIS AND MORPHOLOGICAL STRUCTURE OF POLY (PHENYLENE SULFIDE AMIDE)

Poly(phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as S source which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure. The polymer structures were determined by elemental analysis, FT-IR and H-1-NMR. It is shown that the yielded polymer has linear structure and its structure unit is -p-C6H4-CONH -p-C6H4-S-. The polymer morphology was studied by X-ray diffraction and polarized microscopy. The results show that PPSA is a crystalline polymer and its spherulites are the aggregation of nontwisting lamella or micro-thread structure. Under shearing force, these crystals are dispersed to form micro-fibrillar structure. The decomposition kinetics of PPSA was also studied at different heating rates. The decomposition energy of PPSA is higher than that of PPS.

Preparation of Poly (Phenylene Sulfide Amide) by Sulfur Solution Route

A new process for preparing poly(phenylene sulfide amide, PPSA), which is by reaction of sulfur instead of sodium sulfide as S source with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure (called sulfur solution route), is reported in the present paper. The influences of polymerization time, molar ratio of precursors, catalyst and solvent upon the polymer were investigated. To seek the best parameters of polymerization, orthogonal design was employed in the experiments. The results indicate that the molar ratio of precursors is the most significant effect on both of viscosity and yield of the polymer. The suitable parameters for preparing the related polymer are presented. The polymer was characterized by IRspectrum, 1HNMRspectrum and Raman spectrum, etc.

EFFECT OF SOLVENT COMPOSITION ON THE SULFONATION DEGREE OF POLY(PHENYLENE OXIDE) (PPO)

This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.

多巴胺对碳纤维增强聚苯硫醚复合材料界面性能的影响

碳纤维增强聚苯硫醚复合材料(CF/PPS)因其具有优异的综合性能被广泛关注,但实际应用中发现碳纤维与聚苯硫醚的界面结合并不理想,因此,改善CF/PPS界面结合强度来提升其宏观力学性能就有着深远的理论意义和应用价值。文中基于微球脱粘技术,将具有优良黏附性的多巴胺水溶液作为界面改性剂,对纤维进行表面改性,采用微球脱粘实验和宏观拉伸等实验测试探究了不同多巴胺浓度对CF/PPS界面性能的影响。结果表明,当多巴胺浓度为2 g/L时,聚多巴胺在碳纤维表面均匀黏附,形成较好的微纳结构,涂覆效果最佳,表观界面剪切强度最大为36.09 MPa,较未改性前增加13.50%;PDA-CF2/PPS拉伸试样的断面呈现凹凸不平的形态,拔出的碳纤维上残留树脂基体最多,具有良好的界面改性效果。

聚芳硫醚砜及其制品的研究进展

通过文献归纳法总结无水硫化钠法(常压法、高压法)、含水硫化钠法(高压法、常压法)、硫磺法、硫氢化钠法、聚苯硫醚氧化法等合成聚芳硫醚砜的常用方法。含水硫化钠法可获得高分子量的聚芳硫醚砜,采用常压与高压含水硫化钠合成的聚芳硫醚砜分子量相当,其设备与工艺要求不高,生产稳定性好、周期短、成本低,该方法是一种理想的合成聚芳硫醚砜的方法。为提高聚芳硫醚砜的物理性能、化学性能,对其进行改性,通过相分离制膜法制备的聚芳硫醚砜膜可应用于染料等水体污染物的治理,通过静电纺丝法制备聚芳硫醚砜纤维膜可应用于油水分离、水体污染物治理及空气过滤净化。研究结果表明,聚芳硫醚砜高聚物及其膜制品具有重要的应用前景。

高活性聚苯硫醚树脂的制备及其性能研究

本文研究探讨了不同端基调节剂对聚苯硫醚(PPS)树脂实施端基处理后对其反应活性及熔融结晶温度(Tc2)的提升。通过对比分析,发现以含羟基芳香族硫醇化合物为端基调节剂时,PPS树脂的反应活性和Tc2提升更明显。后续洗涤纯化过程中增加酸洗步骤,可以进一步促进树脂反应活性与Tc2的提升,对于优化共混改性挤出过程中复合材料的整体性能尤为关键。

聚对苯乙烯磺酸微球的绿色制备及催化合成生物柴油

以水为介质、苯乙烯(St)为基体单体、二乙烯苯(DVB)为交联单体、对苯乙烯磺酸钠(Na SS)为功能单体、甲基丙烯酸(MAA)为水溶性单体、过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法制备了聚对苯乙烯磺酸微球(PSS)。利用FTIR、XPS、SEM、TGA和DSC对其进行了表征,并对其粒径、Zeta电位、比表面积、酸密度进行了考察,探讨了Na SS、DVB和KPS用量对PSS结构、性能的影响。当H_(2)O为90m L、St为76.9 mmol、MAA为9.3 mmol、NaSS为0.7mmol、DVB为7.7 mmol、KPS为0.7mmol时,制备的PSS-3粒径均匀且酸密度较高。然后,将PSS-3作为固体酸催化剂,用于催化油酸/甲醇酯化合成生物柴油(油酸甲酯)。结果表明,当甲醇/油酸的物质的量比为10∶1、PSS-3用量为油酸质量的2%、反应温度为80℃、反应时间为6h时,油酸的转化率可达86.4%。PSS-3作为固体酸催化剂具有较好的重复使用性能,循环使用4次后油酸转化率没有明显下降。

Preparation and Characterization of Multi-layer Poly(arylene sulfide sulfone) Nanofibers Membranes for Liquid Filtration

Owing to the excellent filtration performance and low energy cost,polymeric nanofibers microfiltration(MF)membranes have attracted increasing attentions.Poly(arylene sulfide sulfone)(PASS),as one of the structurally modified polymers based on poly-(phenylene sulfide)(PPS),has been selected as the raw material to fabricate nanofibers MF membranes via electrospun techniques.The effects of PASS solution and the electrospinning processing parameters on the structural morphology of nanofibers were investigated in detail.The average diameter of PASS nanofibers was(296±46)nm under the optimal condition:polymer concentration of 0.27 g·m L^–1 PASS/DMI,applied voltage of 20 kV,and speed of collector drum of 300 r·min^–1.And then the multi-layer PASS nanofibers MF membranes were fabricated from cold-pressing the optimized PASS nanofibers(as-prepared PASS nanofibers)membrane.The morphology,porosity,pore size,mechanical properties,and surface wettability of the multi-layer PASS nanofibers MF membranes could be tuned by the layers of as-prepared nanofibers membrane.The results demonstrated that the membrane with 6 layers(marked as PASS-6)exhibited the smallest porosity,smallest pore size,highest mechanical property,and best surface wettability.Meanwhile,the multi-layer PASS nanofibers MF membranes showed that the rejection ratio gradually increased,while the pure water flux decreased with increasing membranes thickness.The PASS-6 membrane exhibited large water flux of 747.76 L·m^–2·h^–1 and high separation efficiency of 99.9%to 0.2μm particles,making it a promising candidate for microfilter.

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~C 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.

Electrical bistable characteristics of poly (phenylene sulfide) thin film deposited by thermal evaporation

Poly(phenylene sulfide) (PPS) is a well-known organic insulator. However, the PPS thin film, deposited by thermal evaporation in vacuum, showed electrical bistable characteristics. The structure of the PPS thin-film device was glass/ITO/PPS (300 nm)/Au. The thin film can be converted to a high conductance state by applying a pulse of 80 V (5 s), and brought back to a low conductance state by applying a pulse of 100 V (5 s). This kind of thin film is potential for active layer of a memory device. The critical voltage of the device is about 40 V, while the read-out voltage is 5 V. We tentatively ascribe the bistable phe-nomenon to the charge transfer from S to C atoms in the PPS molecule chains.

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) mm^(3)·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.

工业硫化钠法常压合成线型高分子量聚苯硫醚的研究

以精制工业硫化钠和对二氯苯为原料，采用多组分催化剂，在六甲基磷酰三胺（ＨＭＰＡ）中进行常压溶液缩聚，合成了线型高分子量的聚苯硫醚（ＬＨＰＰＳ）。研究了单体的配比、工业硫化钠的脱水和体系中含水量对聚合反应的影响，探索了聚合反应过程中分子量的增长状况。测定了合成产品的熔融粘度和溶液粘度，应用元素分析、傅里叶变换红外光谱对合成产品进行了分析表征。用ＤＳＣ和ＴＧＡ测定了树脂的熔点Ｔｍ和初始热失重Ｔｄ，通过熔融挤出考察了树脂的加工热稳定性。结果表明，合成的树脂为线型高分子量ＰＰＳ树脂，具有优良的热性能和加工热稳定性。

聚苯硫醚砜的合成及表征

探索了聚苯硫醚砜树脂在常压下的合成方法 ,得到了优化的合成工艺条件。在原材料的量之比 0 98～1 0 2、反应温度 160～ 2 2 0℃、时间 2～ 8h的条件下制得的高摩尔质量聚合物 ,其粘数可达到 3 5mL/g ;并通过元素分析、红外光谱、紫外光谱、X -衍射和热分析对其结构和性能进行了表征 ,证明合成的高聚物为线型非晶性聚苯硫醚砜树脂 ,是一种具有极高热稳定性和耐化学腐蚀性的高性能材料。

玻纤增强聚苯硫醚复合材料的增韧研究

针对玻纤增强聚苯硫醚材料韧性差的问题,对聚苯硫醚/玻璃纤维复合体系的增韧进行了研究,考察了玻纤、改性聚合物、有机超细粒子对复合材料力学性能的影响。采用基体增韧(预增韧)与有机超细粒子增韧技术,在保持复合材料拉伸强度和模量的同时,较大地提高了冲击强度,获得了综合力学性能优异的纤维增强聚苯硫醚材料。

ZnO晶须增强树脂基复合材料研究

对ZnO晶须/NR复合材料的实验研究表明,表面改性后的ZnO晶须对NR具有显著的增强和抗老化作用,其增强效果沿橡胶混炼剪切方向与垂直剪切方向几乎相同。对ZnO晶须/PPS复合体系的研究结果表明,偶联剂表面处理后的ZnO晶须对PPS有显著的增强作用。研究发现,经典的预测复合材料强度的理论公式可以较好地预测ZnO晶须/NR体系,但对ZnO晶须/PPS复合材料的预测则与实测值存在较大差异。分析认为其主要原因是该晶须特殊的空间四针状结构能有效地传递受力,尖端作用避免了端口应力集中引起的破坏。

聚苯硫醚的合成与结构研究Ⅰ.聚苯硫醚的合成与结构表征

用不同原料和方法制备了不同类型的聚苯硫醚树脂．通过元素分析、红外光谱、激光拉曼光谱及Ｘ射线衍射分析等手段，对各种产品的结构进行了表征．对不同类型产品的结构差异进行了初步研究．结果表明，用不同的原料和方法都可制备聚苯硫醚树脂，各种聚苯硫醚树脂的结构基本接近。