间规聚苯乙烯/尼龙6/磺化间规聚苯乙烯/蒙脱土纳米复合材料的研究

以磺化间规聚苯乙烯（SsPS)为增容剂，将间规聚苯乙烯（sPS)和尼龙6／改性蒙脱土纳米复合物（PA6－MTA）共混，得到综合性能优良的新型多组分聚合物／蒙脱土纳米复合材料（sPS/PA6/SsPS/MTA)。用DSC、DMA、WAXD及力学性能测试仪研究了纳米复合材料的结构与性能。TEM测定证明了蒙脱土在基体中的层厚分布为10－50nm。     

Orientation of Syndiotactic Polystyrene Crystallized in Cylindrical Nanopores

Syndiotactic polystyrene (sPS) nanorods with different diameters have been prepared by using anodic aluminum oxide templates, and the orientation of the sPS crystals in the nanorods has been investigated by FT‐IR spectroscopy. It is found that the c axis of the β′ crystals preferentially oriented perpendicular to the axis of the nanorod, and the degree of orientation is lower as the diameter of the nanorod decreases. This unexpected result is attributed to nuclei formed at the surface of the nanopores and their subsequent growth, in addition to the preferential growth compatible with the pore direction by the nuclei formed in the bulk film and in the nanorods.

     

用广角X光衍射测定不同晶型间规聚苯乙烯结晶度

多晶型;用广角X光衍射测定不同晶型间规聚苯乙烯结晶度     

Synthesis of Syndiotactic Polystyrene with Novel Titanocene Catalysts Activated by Modified Methylaluminoxane

Thesynthesisofsyndiotacticpolystyrene(sPS)hasattractedmuchinterestforitspropertiesandapplications.Half-sandwichtitanoceneandmethylaluminoxane(MAO)catalystshavebeenfoundtobethefavourprecursorstocatalyzesyndiospecificpolymerizationofstyrene'-,'.MAOascocatalystsalwayscontainssomeamountoffreetrimethylaluminum(TMA)bothinaformcoordinatedtoMAOandasfreeTMA".However,therolesoftheTMAcoexistinginMAOarestillnuclear.Inthispaper,severalmodifiedmethylaluminoxanes(m-MAO)whichcontaineddifferentpercen…     

间规聚苯乙烯的改性研究

间规聚苯乙烯(sPS)问世以来,这种新的热塑性聚合物在不同领域的应用得到广泛关注。介绍了sPS的结构与性能,综述了其发展、改性及应用情况。     

Crystalline Organization in Syndiotactic Polystyrene Gels and Aerogels

The crystalline structure of syndiotactic polystyrene gels and aerogels has been investigated by using x-ray diffraction. Results show that, depending on the solvent, the crystalline structure of the junction zones of the gels is a clathrate phase or the solvent free orthorhombic β-form. For aerogels obtained from gels with a clathrate phase, the aerogel crystalline phase consists of the nanoporous δ-form while for aerogels obtained from gels with the β-form, the original crystalline structure is maintained.     

Three‐Dimensionally Ordered Macroporous Syndiotactic Polystyrene: Preparation and Characterization

Summary: Three‐dimensionally ordered macroporous (3DOM) syndiotactic polystyrenes with pore size in the range of 71–286 nm were fabricated by means of silica templates using (dbm)₂Ti(OPh)₂/MAO catalytic system. The resulting materials were characterized by NMR, SEM, powder X‐ray diffraction, GPC and DSC. The results indicated that the 3DOM syndiotactic polystyrenes were highly syndiotactic, and the pore contraction increased when the average pore diameter decreased. Compared with bulk syndiotactic polystyrenes, 3DOM syndiotactic polystyrene possessed lower molecular weight, narrower molecular weight distribution, and lower crystallinity and melting temperature.

SEM image of 3DOM syndiotactic polystyrene, the inset shows the detail of the cavities.     

Thermoreversible Gelation of Syndiotactic Polystyrene in Naphthalene

Investigation into syndiotactic polystyrene/naphthalene systems of concentrations ranging from 0 to 78% (w/w) have been carried out by electron microscopy, DSC, and neutron diffraction. It is found that a fibrillar morphology is produced in this solvent, similar to that observed for thermoreversible gels. The temperature-concentration phase diagram suggests the existence of two compounds of differing stoichiometries. Neutron diffraction experiments confirm the existence of compounds in this system.     

O-(4-喹唑啉)羟肟酸硫代酯(酰胺)类化合物的合成及生物活性

用差示扫描量热分析研究了间规聚苯乙烯（ｓＰＳ）的非等温结晶及其动力学，并分别用Ｏｚａｗａ和Ｊｅｚｉｏｒｎｙ两种方法来处理ｓＰＳ的非等温结晶数据．结果表明，在２５～４０℃／ｍｉｎ的冷却速率范围内，ｓＰＳ的半结晶时间随冷却速率增大而呈指数式下降，ｓＰＳ非等温结晶过程遵循Ｏｚａｗａ动力学方程，但不符合Ｊｅｚｉｏｒｎｙ方法中的Ａｖｒａｍｉ动力学方程．所得到的ｓＰＳ非等温结晶Ａｖｒａｍｉ指数ｎ在３６～４１之间，高于等温结晶时的ｎ值     

Multiple Melting Endotherms of Syndiotactic Polystyrene in β Crystalline Form

Multiple melting behaviors have been studied extensively. Syndiotactic polyStyrene(SPS), in 6 crystalline form exhibited such phenomena. It was suggested that arecrystallization process occurred since it has been clarified that no other modificationswere observed during the DSC heating scanl. In this study, a series of SPS samples in 0form were prepared by cooling from the melt at various cooling ratesl and the factors thatinfluence the multiple melting behavior of SPS in 0 form were exam…     

弹性散射法研究间规聚苯乙烯的冷结晶行为

用弹性光散射方法研究了间规聚苯乙烯(s-PS)的非等温冷结晶行为和等温结晶动力学.结果表明,弹性散射信号对s-PS的冷结晶过程中的构象变化非常敏感.弹性散射法所得的大分子链玻璃化转变温度Tg以及冷结晶温度Tc与DSC的测量结果一致.此外,通过散射强度随温度的变化可以更为清晰地分辨出冷结晶过程中各个阶段,包括晶体成核期,晶核生长期以及二次结晶期.通过等温弹性散射测试,同时结合Arrhenius方程,计算得到s-PS冷结晶表观活化能Ea为309 kJ/mol.     

Effect of Sulfonation on the Crystallization Behaviour of Syndiotactic Polystyrene

Syndiotactic Polystyrene (sPS) was sulfonated to different levels in a mixture of 1,1,2–trichloroethane and chloroform. Sulfonation levels were determined by nonaqueous titrations using phenolphthalein indicator. Thermal properties of sulfonated sPS (SsPS) ionomers depend on the sulfonation level. Incorporation of sulfonic acid groups in to the syndiotactic polystyrene backbone was found to affect the crystallization behavior of sPS. DSC data indicated that the melting temperature (T_m), heat of fusion, crystallization temperature (T_c), crystallization rate and degree of crystallization were lowered by the incorporation of sulfonic acid group on the syndiotactic polystyrene backbone. Thermal and FTIR data indicated that the sulfonic groups did not enter into the crystal lattice but remained in the amorphous phase.     

Syndiotactic Polystyrene / Fullerene Composites: Elucidation of Structural Aspect

Summary: Syndiotactic polystyrene (sPS), an attractive polymer due to its wide range of application, forms polymer-solvent intercalates with a large variety of solvent molecules ranging from liquids to solids. Recently, it has been realized that sPS intercalate prepared from SPS/naphthalene gel is more promising of making mesoporous materials. Here, the composite of sPS/fullerene have been prepared by taking advantage of sublimation of naphthalene. The different techniques as like XRD, SEM, HRTEM, FT-IR, DSC, TGA etc have been employed to characterized sPS/fullerene composite. XRD investigation shows the presence of δ form sPS in the composite. SEM and HRTEM reveal the fibrillar network with fringe like structure in presence of fullerene only and the average diameter of fibril has increased as compared to pure sPS fibrils. The conductivities of these fibrils have been increased with increasing amount of fullerene.     

间规聚苯乙烯的多晶型和结晶行为概述

综述间规聚苯乙烯四种稳定的晶型（α、β、δ和γ）结构特点及各种晶型的制备方法。详述间规聚苯乙烯结晶和熔融行为等方面的研究进展。     

Structural Evolution Process in Solvent-Induced Crystallization Phenomenon of Syndiotactic Polystyrene

Structural change has been traced in the solvent-induced crystallization phenomenon of syndiotactic polystyrene through the time-resolved measurements of infrared and Raman spectra and X-ray diffraction. Immediately after the solvent is supplied to the glassy sample, the random coils start a micro-Brownian motion and locally change to short regular helical segments after some induction time. These segments grow longer and gather together to form the crystal lattice. This crystallization occurs even at room temperature far below the original glass transition temperature (Tg = ca. 100°C), because Tg is shifted to ca. −90°C (in the case of chloroform) due to the plasticizing effect, as revealed by the temperature-dependent infrared spectral measurement and the molecular dynamics calculation. The thus-created sPS-solvent complex was found to show a fast and reversible solvent exchange phenomenon between the originally-existing solvent (toluene, for example) and the newly-supplied different type of solvent (chloroform, for example). The time-dependent measurement of wide-angle and small-angle X-ray scatterings using a synchrotron radiation source revealed that the solvent exchange occurs with keeping both the columnar structure of the crystal and the stacked lamellar structure, and that the solvent exchange rate is in the order of chloroform > benzene > toluene, reflecting the difference in diffusion rate of solvent molecules and polymer-solvent interaction.     

Polyelectrolyte Membranes Based on Sulfonated Syndiotactic Polystyrene in Its Clathrate Form

Recently, more and more attention has been focused on new techniques for energy production also in view of environmental problems. A noticeable device is small fuel cell that converts chemical energy into electric energy by electrochemical reaction of hydrogen with oxygen, and exhibits a high-energy efficiency. Conventional small fuel cells have been classified into phosphoric acid-type fuel cells, molten carbonate-type fuel cells, solid oxide-type fuel cells, solid polymer type fuel cells, etc., according to the type of electrolyte used. The target of this work is the development of a new process to build up polyelectrolyte membranes, for polymer type fuel cell (PEM), by sulfonating syndiotactic polystyrene in its clathrate form. The polyelectrolyte membranes of this paper are inexpensive and exhibit good long-term stability and ion exchange capability.     

复合茂钛催化剂制备宽分子量分布间规聚苯乙烯的研究

采用新型茂钛化合物Cp^*Ti(O-Ph-OCH3)3(A)／CpTi(O-Ph-OCH3)3(B)和Cp^*Ti(O-Ph-OCH3)3(A)／Cp^*Ti(O-Ph-F),(C)作为复合催化剂,在甲基铝氧烷(MAO)、三异丁基铝(TIBA)激活下进行苯乙烯间规聚合。采用A／B复合催化剂可通过调节两种茂钛催化剂的摩尔配比,得到宽分子量分布的间规聚苯乙烯(s-PS);而采用A／C复合催化剂得到的产物分子量分布基本不变。对不同聚合条件下得到的s-PS产物进行了GPC分析。     

Crystalline Complex of Syndiotactic Polystyrene with Poly(ethylene Glycol) Dimethyl Ethers

It has been clarified that syndiotactic polystyrene (sPS) forms co‐crystalline structures with polyethylene glycol dimethyl ethers (PEGDMEs) with molecular weights ranging from 178 to 1 000 g · mol⁻¹ through a guest exchange procedure assisted by a plasticizing agent. The PEGDME molecules are incorporated into the spaces between sPS polymer sheets consisting of (T₂G₂)₂ helices. The results of X‐ray diffraction and gravimetric measurements suggest that one or less molecules are included per unit cell for PEGDME with average molecular weight of 1 000 g · mol⁻¹, which indicates the possibility that longer polymeric molecules can be introduced into sPS lattices with multiple site occupation.