P(DBF-VA)型柴油低温流动性改进剂的研制

针对新疆地产柴油蜡含量较高的特点,以游离基聚合法合成了富马酸双链混合酯和醋酸乙烯酯共聚物型[P(DBF-VA)]柴油低温流动改进剂,利用正交实验研究了单体配比,引发剂用量,溶剂用量,聚合温度对聚合物降冷滤效果的影响。共聚物用IR进行表征,利用XRD初步探讨了该降凝剂的降凝机理。结果表明:该剂能使吐哈—10~#、0~#柴油冷滤点降低10℃和7℃;使独山子0~#柴油冷滤点下降12℃;使石化0~#柴油冷滤点下降8℃;使克拉玛依0~#柴油的冷滤点下降8℃。     

Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

由乙腈一步法制备乙酸丁酯的研究

以丁醇和制备丙烯腈的副产物乙腈为原料 ,采用一步法合成了乙酸丁酯。通过正交实验得到了影响反应的 4种因素。确定了最佳的工艺条件为 :催化剂的量为样品质量的 40 % ;n(CH3CN)∶ n(C4 H9OH) =1∶ 1 .0 5 ;反应温度为 1 0 5℃ ;反应时间为 8h。在此反应条件下 ,乙酸丁酯的收率为 88.8% ,纯度可达 99.5 %。并用气相色谱及红外光谱对产品的纯度进行了表征     

Complex formation of montmorillonite clay with polymers. Part 2: The use of montmorillonite clay–vinyl monomer complex as a comonomer in the copolymerization reaction of styrene–acrylonitrile monomers

The bulk copolymerization of styrene–acrylonitrile monomers using styrene‐N⁺–montmorillonite complex as a comonomer in the polymerization was studied. The X‐ray diffraction (XRD) analysis showed that part of the styrene‐N⁺–montmorillonite complex remained non‐dispersed (immiscible) and the copolymer was excluded from the interlayer of the immiscible part of the clay. The successive chemical extraction process revealed that a reasonable amount of the styrene–acrylonitrile copolymer was directly attached to the styrene‐N⁺–montmorillonite complex and enveloped the clay. Highly exfoliated clay lamella and nanospheres (3–5 nm) were observed by transmission electron microscopy (TEM). The montmorillonite clay assume two different morphologies, immiscible and exfoliated, on the basis of the XRD and TEM data. A simple method of calculation of the ratio of the exfoliated/immiscible amounts of the clay indicated that the amount of the styrene‐N⁺–montmorillonite complex exfoliated into separate lamella was 40 % (w/w) of the amount of the clay samples containing 2 % of the (styrene‐N⁺–montmorillonite complex) clay. This amount of exfoliated clay decreases with the increase of the concentration of the clay. The presence of the styrene‐N⁺–montmorillonite clay in the copolymerization reaction had a minor effect on both the copolymer composition and the molecular weight. Modification of the clay with the derivatized styrene monomer can achieve a nanocomposite using a percentage no more than 4 % (w/w) of complex in the copolymer. Copyright © 2004 Society of Chemical Industry     

Slow eroding biodegradable multiblock poloxamer copolymers

Biodegradable multiblock poloxamers (BMPs) with gel duration of 8 h to several weeks were prepared by varying their molecular weights from 4000 to 40 000 g mol^?1. The molecular weight of the BMP was controlled by changing the poloxamer to coupling agent ratio. Assuming a micelle packing model of the BMP gel, as in the case of a poloxamer gel, the micelle properties and critical gel concentration of BMPs were investigated on the basis of the scaling concept. The findings suggest that the control of molecular weight by hydrolyzable groups can be a facile approach to optimize the gel properties for biomedical applications. Copyright © 2005 Society of Chemical Industry     

Phase behavior in liquid crystallization for diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components

Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.     

Highly ordered microstructures of poly(styrene-b-isoprene) block copolymers induced by solution meniscus

Microstructures of hundreds of micron thick poly(styrene-block-isoprene) copolymer films solution-cast in a cylindrical tube with the solvent evaporation controlled were investigated by transmission electron microscope (TEM), small angle X-ray scattering (SAXS) and optical microscope (OM). In a block copolymer with cylindrical polyisoprene microdomains, the orientation of the cylinders was varied along radial direction of the cylindrical tube. Highly aligned hexagonal arrays of in-plane polyisoprene cylinders were formed with their cylindrical axis parallel to the circumference of the tube in the regimes close to the wall edge. In contrast randomly ordered microdomains were observed at the center of the tube. We have also found that the orientation depends on the solvent evaporation rate and an intermediate rate (∼2.3 nL/s) provides the best orientation. In the case of a block copolymer with a bicontinuous double gyroid structure, we obtained a globally ordered microstructure where [111] crystallographic direction was parallel to the circumference of the tube. For both block copolymers, the area of highly ordered arrays of nanoscopic domains is over 1 mm². Development of the orientation was explained by coupling two orthogonal fields: (1) The flow of a solution induced by strong capillary force at a meniscus between the cylindrical tube wall and the block copolymer solution and (2) the solvent evaporation.     

端羟基聚二甲基硅氧烯改性环氧树脂

用羟基封端的聚二甲基硅氧烷改性环氧树脂，得到具有两相结构的改性树脂，其耐热性明显提高．环氧树脂／有机硅（20／80）共混物涂层有很低的表面能，主要的机械性能则变化不大，可作为一种疏水性防护徐层．     

HIPS-g-MA共聚物对HIPS/PC共混物相容性、形态和拉伸性能的影响

研究了HIPS／PC共混物的相容性及HIPS－MA对HIPS（30）／PC（70）共混物的相容性、形态和拉伸性能的影响。DSC研究结果表明，HIPS／PC共混物中PS的玻璃化转变温度（Tg)不随组成而变化，而PC的Tg随其质量分数的降低逐渐向低温移动，说明HIPS／PC是部分相容体系。通过DSC、扫描电镜形态观察和拉伸性能测试结果发现，当HIPS－g-MA的含量低于7．5％时，共混物的相容性改善不明显，当其含量达到7．5％时，对共混物有明显的乳化作用，说明饱和的界面浓度在7．5％左右。HIPS－g-MA接枝共聚物在HIPS（30）／PC（70）共混物中的增容作用可能是酯交换反应原位生成的嵌段共聚物所致。     

高透明耐冲击聚氯乙烯接枝聚合研究

研究高透明耐冲击聚氯乙烯接枝聚合工艺，讨论了加料顺序、复合分散体系以及采用聚集粒子乳液、并用碱性物质调节其ｐＨ值等对接枝聚合物性能的影响，确定了接枝聚合最佳工艺条件。