核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制

核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制张会轩戴英杨海东＊冯之榴（吉林工学院化工系长春１３００１２）（中国科学院长春应用化学研究所１３００２２）关键词聚丙烯酸酯，增韧剂，制备，种子乳液聚合１９９６－０８－２８收稿，１９９７－０１－０６修回国家自...     

核／壳结构聚丙烯酸酯增韧剂改性PVC的研究

用核／壳结构聚丙烯酸酯增韧剂对ＰＶＣ进行了抗冲击改性，研究了增韧剂的组成结构与增韧效果之间的关系，通过实验发现在本工作所考察的范围内，增韧剂粒径越大，其增韧效果越好．电镜观察证实共混体系的形态为弹性体粒子均匀地分散在ＰＶＣ基体中．     

ZSM－5（核）／AlPO4－5（壳）双结构分子筛的合成与催化裂化性能

 采用X射线衍射、扫描电镜、X射线能量散射谱、红外光谱和核磁共振等多种物化方法对合成的ZSM－5（核）／AlPO4－5（壳）双结构分子筛进行了表征，证明这种材料具有以ZSM－5为核层、以AlPO4－5为壳层的双结构特征．考察了合成条件对ZSM－5（核）／AlPO4－5（壳）分子筛形貌的影响，发现ZSM－5分子筛的加入方式对产物的形貌有较大影响．重油裂化反应结果表明，ZSM－5（核）／AlPO4－5（壳）双结构分子筛的催化性能比ZSM－5和ZSM－5／AlPO4－5机械混合分子筛样品好，表现为原油转化率和低碳烯烃、汽油及柴油收率提高．     

四元胶乳互穿聚合物网络的组成对其性能的影响

用分步乳液聚合法合成了具有核壳结构的胶乳互穿聚合物网络ＬＩＰＮ（ＰＭＭＡ－ＰＳ）／（Ｐｎ－ＢＡ－ＰＡＡ）；讨论了ＬＩＰＮ组成对乳液与膜性能的影响，提出了四元ＬＩＰＮ核壳结构的基本轮廓，探讨了软硬单体最佳配比及丙烯酸单体用量。     

锂离子电池负极碳材料的表面改性与修饰Ⅱ.具有“核壳”结构的碳及其对电池性能的影响

以具有气相碳化形式的精制煤焦油沉积碳为壳层材料、人造石墨（ＡＧ）及中间相石墨微球（２８００℃）为核材料制备了核壳结构的碳及碳电极．核壳结构碳及核壳结构碳电极的充放电研究表明碳负极的稳定充放电容量及首次充放电效率都得到了较大的改善,循环伏安研究表明在０．７Ｖ（ｖｓＬｉ＋／Ｌｉ）左右用于形成碳电极表面钝化膜的溶剂的还原分解峰显著减小,显示了核壳结构碳材料电极对电极表面钝化膜的影响作用,Ｘ射线衍射研究揭示了石墨及石墨电极上的无定形碳壳层的存在     

锂离子电池负极碳材料的表面改性与修饰：Ⅱ.具有“核壳”结构的碳及其对…

以具有气相碳化形式的精制煤焦油沉积碳为壳层材料、人造石墨及中间相石墨微球为核材料制备了核壳结构的碳及碳电极。核壳结构碳及核壳结构碳电极的充放电研究表明碳负极的稳定充放电容量及首次充放电效率都得到了较大的改善，循环伏安研究表明在０．７Ｖ（ｖｓ Ｌｉ＾＋／Ｌｉ）左右用于形成碳电采表面钝化膜的溶剂的还原分解峰显著减小，显示了核壳结构碳材料电极对电极表面钝化膜的影响作用，Ｘ射线衍射研究揭示了石墨及石墨电极     

丁腈羟增韧环氧树脂固化反应

丁腈羟增韧环氧树脂固化反应李绍英＊＊韩孝族＊刘振海张庆余（中国科学院长春应用化学研究所长春１３００２２）关键词丁腈羟，增韧环氧树脂，固化反应动力学，ＤＳＣ１９９６－０５－０４收稿，１９９６－０９－１７修回＊＊现在河北轻化工学院化工设计研究所工作环氧树...     

氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒结构形态

以氯丁胶乳（Pa）为种子乳液,甲基丙烯酸甲酯（Pb）为第二单体,采用种子乳液聚合法,制备了氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒。 热力学分析表明,当Pb的体积分数Φb＜0.69时,可同时形成Pa-Pb型正核-壳和（Pa＋Pb）分离型乳胶粒,当Φb＞0.69时,形成Pb-Pa型翻转型核壳结构乳胶粒,并伴有Pa-Pb型正核-壳结构乳胶粒的形成。 动力学分析表明,引发剂类型、第二单体的加入方式、种子乳胶粒的交联、单体/聚合物质量比是影响乳胶粒形态的主要因素。 采用水溶性引发剂过二硫酸钾（KPS）,以饥饿态方式加入单体,氯丁胶乳 聚甲基丙烯酸甲酯(PCR-PMMA)复合乳胶粒呈现正核-壳结构,以充溢态方式加入单体则不能形成明显的核-壳结构;而以油溶性偶氮二异丁腈（AIBN）为引发剂时,单体无论以充溢态方式加入还是饥饿态加入均倾向于形成翻转核-壳型粒子。 在种子乳胶粒中加入一定量交联剂二缩三乙二醇二甲基丙烯酸酯,有利于形成明显的正核壳结构。 以饥饿态进料,KPS为引发剂时,随着单体用量增加,壳层变厚,仍呈正核-壳结构,与热力学分析结果相吻合;以AIBN为引发剂时,随着单体用量增加,PCR-PMMA复合乳胶粒逐渐由翻转核壳型结构变为互穿结构。     

核—壳结构聚丙烯酸酯—聚氨酯微乳液膜的相行为

用动态力学、红外光谱和差热分析方法研究了非交联核－壳结构聚丙烯酸酯－聚氨酯（ＰＡＣ－ＰＵ）微乳液膜的相行为．结果表明：核壳间的氢键增强了壳层软硬段间的相分离，同时破坏了硬段相中的短程有序结构，但增强了核壳相容性     

聚丙撑碳酸酯增韧环氧树脂的研究

研究了聚丙撑碳酸酯（ＰＰＣ）对环氧树脂（ＥＰ）的改性作用、加入２０～３０Ｐｈｒ的ＰＰＣ，环氧树脂力学性能可以大幅度提高，粘接剪切强度为１２３３ＭＰａ，冲击强度为１６．７８ｋＪ／ｍ２；而纯环氧树脂固化物，其剪切强度为９．３６ＭＰａ，冲击强度为９．９９ｋＪ／ｍ２。ＳＥＭ和ＤＳＣ观测表明ＰＰＣ／ＥＰ体系呈两相结构。     

新型环氧丙烯酸树脂增韧剂的合成

用马来酸酐和聚乙二醇1000合成具有反应活性端基的聚乙二醇,用红外与核磁共振进行了表征,并用其对环氧丙烯酸树脂进行改性;研究反应温度、反应时间对反应及产物性能的影响;用红外对反应性聚乙二醇和环氧丙烯酸树脂的固化物进行分析.结果表明,反应性聚乙二醇参与了环氧丙烯酸树脂的固化反应,可在交联网络中构成不同长度的柔性链段,显著地提高了环氧丙烯酸树脂的冲击强度.     

动态固化聚丙烯/环氧树脂共混物的研究

将动态硫化技术应用于热塑性树脂 热固性树脂体系 ,制备了动态固化聚丙烯 (PP) 环氧树脂共混物 .研究了动态固化PP 环氧树脂共混物中两组分的相容性、力学性能、热性能和动态力学性能 .实验结果表明 ,马来酸酐接枝的聚丙烯 (PP g MAH)作为PP和环氧树脂体系的增容剂 ,使分散相环氧树脂颗粒变细 ,增加了两组分的界面作用力 ,改善了共混物的力学性能 .与PP相比 ,动态固化PP 环氧树脂共混物具有较高的强度和模量 ,含 5 %环氧树脂的共混物拉伸强度和弯曲模量分别提高了 30 %和 5 0 % ,冲击强度增加了 15 % ,但断裂伸长率却明显降低 .继续增加环氧树脂的含量 ,共混物的拉伸强度和弯曲模量增加缓慢 ,冲击强度无明显变化 ,断裂伸长率进一步降低 .动态力学性能分析 (DMTA)表明动态固化PP 环氧树脂共混物是两相结构 ,具有较高的储能模量 (E′)     

Polyfunctional imide-containing oligomer as effective modifier of epoxy 4,4′-isopropylidenediphenol compounds

The possibility of using a soluble polyfunctional imide-containing oligomer, oligomaleimidohydroxyphenylene, as a modifier of E-41r epoxy 4,4′-isopropylidenediphenol resin was examined. Introduction of this modifier in an amount from 1.0 to 3.0 wt % enhances the hardness, impact strength, adhesion, and corrosion resistance of imide-containing epoxy 4,4′-isopropylidenediphenol coatings on steel surfaces, i.e., improves their operation characteristics.     

Effect of poly(arylene ether ketone)s of different chemical constitutions on adhesion properties of epoxyamine binder

The adhesive strength at the bipolymer blend/fiber interface was determined by the pull-out method. Epoxy resin blends with heat-resistant linear thermoplastics, poly(arylene ether ketone)s of different molecular masses and chemical compositions, were used as adhesives, and a steel wire of 150 μm diameter was used as a substrate. It was found that the addition of 5–20 wt % poly(arylene ether ketone) to epoxy resin results in a 10–20% increase in the adhesive strength; a sharp gain in the adhesive strength (by 50–80%) is observed at a modifier content of 30%. The introduction of nanoparticles (Na⁺-montmorillonite) into the epoxy resin-poly(arylene ether ketone) blend increases the strength of adhesive bonding to steel wire. Possible reasons for the observed changes in the adhesive strength are discussed.     

端羟基丁腈橡胶增韧环氧树脂研究

本文研究了端羟基丁腈橡胶(HTBN)对环氧树脂的增韧作用。加入10—20phr的HTBN,环氧树脂性能可以大幅度提高,粘接碳钢剪切强度30MPa,冲击强度9×10~(-2)J/cm~2,浇注试样抗张强度61MPa,伸长10％,玻璃化温度115℃;不加HTBN的环氧树脂固化物,剪切强度24MPa,冲击强度34×10~(-2)J/cm~2,抗张强度30MPa,伸长5％,玻璃化温度124℃。 本文还通过DSC、SEM研究观察到增韧环氧树脂的两相结构。     

含磷有机硅杂化环氧树脂固化体系性能研究

通过磷酸与γ-环氧丙氧基三甲氧基硅烷反应得到含磷有机硅氧烷,并加入到环氧树脂/4,4'-二氨基二苯基甲烷体系中混合,通过溶胶-凝胶的方法制备了含磷有机硅杂化环氧树脂固化物.对固化体系进行了玻璃化转变温度、热失重、阻燃、拉伸强度、冲击强度测试分析.结果表明,该固化体系的阻燃性得到提高,极限氧指数在25.8～29.3,玻璃化转变温度得到提高,在161～179℃;虽然初始分解温度比纯环氧树脂固化物低,但800℃残炭率可以达到26.5%,提高了36%;拉伸强度得到提高,在71～94 MPa,冲击强度可以达到14.36 kJ/m2,提高了14%.该固化体系具有较好的阻燃性能和热性能,同时具有较好的力学性能.     

Studies on thermal, mechanical and morphological behaviour of caprolactam blocked methylenediphenyl diisocyanate toughened bismaleimide modified epoxy matrices

Diglycidyl ether of bisphenol A epoxy resin (DGEBA, LY 556) was toughened with 5%, 10% and 15% (by wt) of caprolactam blocked methylenediphenyl diisocyanate (CMDI) using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The toughened epoxy resin was further modified with chemical modifier N,N′-bismaleimido-4,4′-diphenylmethane (BMI). Caprolactam blocked methylenediphenyl diisocyanate was synthesized by the reaction of caprolactam with methylenediphenyl diisocyanate in presence of carbon tetrachloride under nitrogen atmosphere. Thermal properties of the developed matrices were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), heat distortion temperature (HDT) and dynamic mechanical analysis (DMA). Mechanical properties like tensile strength, flexural strength and impact strength were tested as per ASTM standards. The glass transition temperature (T_g) and thermal stability were decreased with increase in the percentage incorporation of CMDI. The thermomechanical properties of caprolactam blocked methylenediphenyl diisocyanate toughened epoxy resin were increased by increasing the percentage incorporation of bismaleimide. The values of impact strength for epoxy resin were increased with increase in the percentage concentration of CMDI. The homogeneous morphology of CMDI toughened epoxy resin and bismaleimide modified CMDI toughened epoxy resin system were ascertained from scanning electron microscope (SEM).     

Development and characterization of a novel skeletal modified tetraglycidyl epoxy toughened DGEBA epoxy matrices

The present work investigates the improvement in mechanical properties observed for commercially available diglycidyl ethers of bisphenol-A (DGEBA) with the incorporation of a new type of skeletal modified tetra glycidyl epoxy resin TGBAPB as modifier. Varying weight percentages of TGBAPB have been blended with DGEBA and cured with diaminodiphenylmethane (DDM). The chemical structure of TGBAPB was confirmed by FTIR, NMR, and molecular weight determination was carried out by ESI-MS spectroscopic techniques. The thermal properties were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and mechanical properties like tensile strength, flexural strength, impact strength were also studied by universal testing machine (UTM). Scanning electron microscopy (SEM) investigates the morphological behavior of the neat and blend epoxy resins. The results from different studies indicate that the blend epoxy resin system “B” comprising 75% DGEBA/25% TGBAPB has shown improvements in both toughness and stiffness, despite the fact that it is often found that the enhancement of these two properties together in a material cannot be simultaneously achieved. These aspects of this work are novel.     

Novel toughened cyanate ester resin with good dielectric properties and thermal stability by copolymerizing with hyperbranched polysiloxane and epoxy resin

A novel toughened cyanate ester (CE) resin with good dielectric properties and thermal stability was developed by copolymerizing 2,2′‐bis(4‐cyanatophenyl)iso‐propylidene (BCE) with a combined modifier (HBPSiEP) made up of hyperbranched polysiloxane (HBPSi) and epoxy (EP) resin. HBPSi was synthesized through the hydrolysis of 3‐(trimethoxysilyl)propyl methacrylate. The effect of differing stoichiometries of HBPSiEP on the curing characteristics and performance of BCE resin is discussed. Results show that the incorporation of HBPSiEP can not only effectively promote the curing reaction of BCE, but can also significantly improve the toughness of the cured BCE resin. In addition, the toughening effect of HBPSiEP is greater than single EP resin. For example, the impact strength of modified BCE resin with 30 wt% of HBPSiEP is 23.3 KJ/m², which is more than 2.5 times of that of pure BCE resin, while the maximum impact strength of EP/BCE resin is about 2 times of pure BCE resin. It is worthy to note that HBPSiEP/BCE resins also exhibit improved thermal stability, dielectric properties, and flame retardancy, suggesting that the novel toughened CE resins have great potentiality to be used as a matrix for advanced functional composites or electronic packing resins. Copyright © 2009 John Wiley & Sons, Ltd.