磺化聚苯硫醚铑配合物催化剂初探

苯硫醚具有与三苯基磷相似的配位化学性能,膦类配体具有比苯硫醚强的络合能力,但毒性较大,热稳定性和抗氧稳定性不如苯硫醚类配体。能否以含有机硫的配体替代膦类配体,这是开发新型催化剂的一个值得探索的方向。聚苯硫醚经发烟硫酸磺化后,可制得水溶性的磺化聚苯硫醚。经XPS测定,磺化度为     

几种热塑性特种工程塑料的热分析研究

聚芳醚和聚芳硫醚两类聚合物都为热塑性的耐高温特种高分子材料 ,由于它们的加工性好、加工成型效率高 ,受到了世界各国的高度重视。这两类聚合物在结构上有许多相似之处 ,如它们的主链都含苯环、酮基或砜基 ,而聚芳醚类聚合物的柔性基团为醚键 ,聚芳硫醚类聚合物的柔性基团为硫醚键 ,但由于氧和硫在元素周期表中属于同一族元素 ,原子结构仍然相似 ,因而在某些方面具有一定的可比性。研究它们的性能差异对于改进聚合物性能以及进行进一步的结构设计将有一定的帮助。在这两类聚合物中 ,国内已商品化生产的品种有ＰＥＥＫ、ＰＥＳ和ＰＰＳ ,有…     

Thermodynamics of phenylated polyphenylene between 0 and 340 K

In an adiabatic vacuum calorimeter, the temperature dependence of the heat capacity C _p of phenylated polyphenylene and initial comonomer 1,4-bis(2,4,5-triphenylcyclopentadienone-3-yl)benzene was studied between 6 and 340 K with an uncertainty of about 0.2%. In a calorimeter with a static bomb and an isothermal shield their energies of combustion DUcomb were measured. From the experimental data, the thermodynamic functions C _p ⁰ (T), H ⁰(T)-H ⁰(0), S ⁰(T)-S⁰(0), G ⁰(T)-H ⁰(0) were calculated from 0 to 340 K, and standard enthalpies of combustion ΔH _comb ⁰ and thermodynamic parameters of formation-enthalpies ΔH _f ⁰, entropies ΔH _f ⁰, Gibbs functions ΔG _f ⁰ - of the substances studied were estimated at T=298.15 K at standard pressure. The results were used to calculate the thermodynamic characteristics (ΔH _f ⁰ ,ΔS _f ⁰, ΔG _f ⁰) of phenylated polyphenylene synthesis in the range from 0 to 340 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚苯硫醚熔体的压致凝固行为

采用施加压力的方法将聚苯硫醚熔体凝固,凝固后获得的聚苯硫醚样品经过降温和卸压后在常温常压下回收. X射线衍射和差示扫描量热分析表明:约20 ms时间的快速压缩过程可以抑制熔体结晶,制备出非晶态聚苯硫醚块材,样品的表面及中心都是非晶态.非晶态聚苯硫醚的玻璃化转变温度和晶化温度分别为318和362 K.常压下的退火实验表明,非晶态聚苯硫醚在425 K等温结晶的产物为正交相晶型.压致凝固法中熔体的凝固不是靠温度变化,而是靠压力变化,样品表面和内部处在一致的温度下同时受压凝固,避免了热传导对非晶尺寸的影响,因此非常有利于获得结构均匀的大尺寸非晶态材料.     

Post-polymerization modification of aromatic polyimides via Diels-Alder cycloaddition

We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials.     

Absorption spectra of the products of resorcin transformation in concentrated perchloric acid

Results of an investigation of the electronic absorption spectra of polymeric compounds spontaneously formed as a result of resorcin dissolution in 70% perchloric acid are reported. It is shown that acetone is the most convenient solvent for analytic purposes, since it allows specific detection of poly-m-phenylene oxide in a wide wavelength range. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 247–250, March–April, 1999.     

电容器薄膜等离子体表面改性实验研究

建立了一套辉光放电等离子体对电容器薄膜进行表面处理的装置。采用N2,O2及Ar三种气体对聚丙烯、聚酯和聚苯硫醚膜进行了表面处理。红外光谱分析表明:薄膜表面的生成物与薄膜种类、气体种类和处理强度密切相关。场扫描电镜显示了薄膜表面的刻蚀现象明显。处理过的薄膜,非晶相被去除,球晶暴露。能谱分析说明了薄膜中C元素下降,N,O元素增加,但总体改变量很小。处理前后薄膜的直流击穿电压没有明显改变,但刻蚀过程造成的薄膜表面粗化可帮助电容器的浸渍过程更充分,从而可提高电容器的使用场强与储能密度。     

Wear Performance and Mechanisms of Polyphenylene Sulfide/Polytetrafluoroethylene Wax Composite Coatings Reinforced by Graphene

Polyphenylene sulfide (PPS) composite coatings reinforced by graphene were prepared through a spraying method. Wear performance of the composite coatings were evaluated using a block-on-ring test rig, and the results showed that the wear life of the composite coatings were over seven times higher than that of a pure PPS coating. Wear mechanisms of PPS composite coatings reinforced by graphene are discussed. It was concluded that adhesive wear was the major wear mechanism of the pure PPS coating but the wear form of the composite coatings was dominated by abrasive wear due to the graphene filler that has high mechanical strength. In addition, fatigue wear appeared for composite coatings with higher content of graphene. The formation of a uniform thin transfer film on the counterpart ring and fine wear debris for the composites coatings during abrasion were consistent with the improvement of wear performance. The 3D morphology of the surface of the counterpart ring was also used to discuss the wear mechanism of PPS composite coatings.     

Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

Comparative Study of Tribological Properties of Polyphenylene Sulfide (PPS), Polyethersulfone (PES), and Polysulfone (PSU)

The tribological properties of polyphenylene sulfide (PPS), polyethersulfone (PES) and polysulfone (PSU), which have similar molecular structures, were investigated using an end-face contact tribometer and a reciprocating tribometer. The thermomechanical behavior of the polymers was analyzed using dynamic mechanical analysis (DMA). PPS exhibited a maximum friction coefficient with increasing load and sliding speed, while the friction coefficients of PES and PSU decreased only slightly. The wear rate of PPS was much lower than that of PES and PSU under high loads and speeds. It is suggested that the main factors influencing the friction and wear properties of the neat polymers are their condensed state and heat resistance. Amorphous PES and PSU showed liquid-like behavior and very low friction when the frictional surface was in the molten-flow state. The macromolecular crystals of crystallizable PPS give it some solid-like behavior and load-carrying capacity; hence PPS exhibited lower wear than PES and PSU.