多功能梳状聚合物电解质的合成及其性能

以聚乙二醇单甲醚(PEGME)为侧链,马来酸酐/1-十八碳烯交替共聚物(PMAO)为骨架,制备出具有生物相容性的多功能梳状聚合物(PMAO-PEGME).该聚合物分别与 CH3OH 和LiOH 反应,制得梳状马来酸酐/1-十八碳烯交替共聚物多缩乙二醇酯(PMAO-PEGME-ME)和单离子聚合物电解质(即梳状马来酸酐/1-十八碳烯交替共聚物多缩乙二醇酯羧酸锂 PMAO-PEG-MELi),用FT-IR、1H-NMR、DSC、交流复阻抗谱等对得到的聚合物电解质进行了表征.结果表明:随着 LiClO4浓度的增加,PMAO-PEGME-ME/LiClO4 体系的电导率呈现先上升后下降的变化趋势,符合通常的聚合物电解质电导率与盐浓度的依赖关系.当每千克聚合物中含 1.5 mol Li-ClO4时,电导率达到最大值,室温下为 1.01×10-5S/cm.PMAO-PEGMELi 的室温电导率可达3.57×10-7S/cm.     

低相对分子质量苯乙烯-马来酸酐交替共聚物的合成

将引发剂偶氮二异丁腈(AIBN)、共聚单体苯乙烯(St)和马来酸酐(MA)溶解于甲苯中,采用沉淀聚合法合成苯乙烯-马来酸酐共聚物(SMA).分别研究了反应温度、引发剂用量、反应时间、单体配比和单体浓度对聚合物得率和酸酐含量的影响.采用正交实验确定最优反应条件为:单体浓度20%,单体物质的量比为1∶1,引发剂用量为0.60%,反应温度为86℃,反应时间2h,产物得率为86.86%,酸酐含量为50.28%.并利用傅里叶变换红外光谱(FTIR)、核磁共振碳谱(~(13)C NMR)、凝胶渗透色谱(GPC)和热分析法分别研究聚合物的分子结构、相对分子质量及相对分子质量分布和热稳定性.结果表明产物是苯乙烯-马来酸酐交替共聚物,相对分子质量分布较窄,具有良好的热稳定性.     

碳纤维电沉积处理对其复合材料结构与性能的影响

为了(1)研究共聚物在碳纤维表面的电沉积处理对复合材料剪切强度的改善;(2)寻找适用于工业生产的电沉积条件;(3)探求聚合物在碳纤维表面的电沉积机理;(4)分析电沉积对复合材料破坏模式的影响,本工作分别以苯乙烯-马来酸酐、醋酸乙烯酯-马来酸酐和甲基丙烯酸甲酯-马来酸酐共聚物的钱盐水溶液作为电沉积液, 取纤维前处理、电沉积电流密度和沉积时间三个因子, 各选三个水平排成拉丁方来优选处理条件。     

苯乙烯马来酸酐共聚物(SMA)化学改性制备荧光聚合物及其荧光性能研究

用自行合成的 2-氨基噻唑 (1)、2-氨基-4-苯基噻唑 (2)、2-氨基苯并噻唑(3)等荧光小分子化合物,与商品化的苯乙烯马来酸酐共聚物 (SMA)中的酸酐基团反应,制成聚苯乙烯马来酰亚胺 (SMI),实现了SMA化学改性.在获得荧光聚合物的同时,不仅保持了原SMA的可溶性、成膜性等优点,其热性能也得到了改善.通过示差扫描量热 (DSC)、凝胶色谱 (GPC)、红外、紫外及荧光光谱等手段表征了荧光聚合物的玻璃化转变温度、分子量及结构与荧光性能关系.     

亲/疏水不对称空心聚合物微球制备及磁性粒子装载研究

首先将(马来酸酐-醋酸乙烯酯共聚物)核/(马来酸酐-二乙烯基苯共聚物)壳微球的壳层外表面酐基烷基溴化,然后将核溶蚀、壳层内表面酐基水解,制得内表面含亲水羧基、外表面含烷基溴、具有微孔(Barrett-Joyner-Halenda平均孔径14.9nm)的空心聚合物微球.以此空心微球为微反应器,使Fe2+和Fe3+通过球壁...     

羧酸共聚物与方解石晶体相互作用的MD模拟

用分子动力学方法, 模拟计算了丙烯酸-丙烯酸甲酯共聚物(AA-MAE)、丙烯酸-丙烯酸羟丙酯共聚物(AA-HPA)、丙烯酸-马来酸共聚物(AA-MA)及水解马来酸酐(HPMA)四种聚羧酸类阻垢剂与方解石晶体(110)晶面的相互作用. 结果表明, 聚羧酸与(110)晶面结合能的大小排序为AA-MA＞HPMA＞AA-HPA＞AA-MAE; 对体系各种相互作用以及径向分布函数的分析表明, 结合能主要由库仑作用(包括离子键)提供, 并含少量氢键成分. 与方解石晶面结合的聚合物发生扭曲变形, 但形变能远小于相应的非键作用能. 聚合物中不同位置羧基的动力学行为差别很大, 链端羧基的运动翻转比链中部羧基剧烈得多, 故后者与晶面的结合比前者更牢固而具有更强的阻垢能力.     

苯乙烯马来酸酐共聚物化学改性研究进展

苯乙烯-马来酸酐共聚物具有优异的乳化、成膜、增稠等特性,是一种重要的功能化聚合物.从酯化、胺化、苯环接枝、带上电荷、引入功能性基团和引入第三单体等方面对于苯乙烯-马来酸酐共聚物化学改性进行了全面的总结,简评了各种化学改性的方法及改性共聚物的优点,报道了化学改性方法近年来出现的新进展.     

双亲性无规共聚物自组装胶束结构及其乳化性能

以不同交联度、溶胀程度的双亲无规共聚物聚[(苯乙烯-alt-马来酸酐)-co-(7-对乙烯基苄氧基-4-甲基香豆素-alt-马来酸酐)](PSMVM)胶束作为聚合物胶束乳化剂稳定甲苯/水体系, 重点研究光交联度对胶束结构及其乳化性能的影响. 结果表明, 胶束交联度、溶胀度和荷电性对胶束结构及乳化性能有较大影响.     

二氧化碳/环氧丙烷/马来酸酐三元共聚物对PPC/PHB共混物力学性能的影响

采用稀土三元催化剂制备了二氧化碳-环氧丙烷-马来酸酐三元共聚物(PPCMA).用红外和核磁谱图确定了PPCMA的结构及马来酸酐单元的含量,3 wt％马来酸酐投料量的PPCMA(共聚物中马来酸酐单元含量4.1％)的玻璃化转变温度(Tg)和起始热分解温度(Td-5％)分别为13.4℃和217℃,拉伸强度为2.88 MPa,断裂伸长率为1669％,与二氧化碳-环氧丙烷共聚物(PPC)相比,引入少量马来酸酐的PPCMA有望成为一种韧性材料,并可对PPC和聚3-羟基丁酸酯(PHB)共混体系进行改性.当在PPC/PHB共混体系中添加10 wt％的PPCMA时,所得共混材料的拉伸强度为18.2 MPa,断裂伸长率则提高到85％,较没有添加PPCMA的样品提高了4.25倍,因此PPCMA的加入能有效提高PPC/PHB共混体系的韧性,改善PPC/PHB共混体系的力学性能.偏光显微镜的研究表明PPC/PHB共混体系加入PPCMA后,很快形成大量尺寸小的PHB球晶,且结晶速度大幅度提高,因此PPCMA在一定意义上可视为一种特殊的“成核剂”.     

烯丙醇聚氧乙烯醚与马来酸酐的共聚合及竞聚率测定北大核心CSCD

以烯丙醇聚氧乙烯醚(APEG)和马来酸酐(MA)为单体,过硫酸钾(K2S2O8)为引发剂,蒸馏水为溶剂,在65℃下,自由基聚合合成共聚物P(APEG-co-MA)。利用凝胶渗透色谱仪对聚合物进行表征,计算得烯丙醇聚氧乙烯醚与马来酸酐共聚物的组成摩尔比,得到的实验数据利用FR法、KT法和YBR法进行竞聚率的计算。结果表明,在低转化率的条件下,烯丙醇聚氧乙烯醚与马来酸酐的竞聚率分别为r1=0.33090,r2=0.04761,说明与马来酸酐相比,烯丙醇聚氧乙烯醚更易倾向自聚,马来酸酐基本不发生自聚。     

聚氨酯醇酸的裂解气相色谱-质谱研究

人工合成聚氨酯醇酸,用裂解气相色谱－质谱（ＰＧＣ－ＭＳ）法详细研究其热裂解产物的化学组成,探索其热裂解机理。裂解的主要产物为合成所用的单体甲苯二异氰酸酯（ＴＤＩ）、邻苯二甲酸酐及油脂相应的脂肪酸。     

羧基化环氧丙烯酸酯合成及在光成像阻焊油墨中的应用

树脂;多元羧酸酐;光固化;碱显影;羧基化环氧丙烯酸酯合成及在光成像阻焊油墨中的应用     

Modification of PP by blending with PS and reactive polymers

In this paper a polypropylene (PP) resin with controlled rheology was selected as polymer matrix and modified by melt mixing with polystyrene (PS) which has certain processing compatibility with PP. The effect of the addition of polyperoxide (PPX), peroxide modified PS particles (PS‐PPX), and maleic anhydride (MAH) to the PP/PS blend during melt mixing on the rheological behavior and morphology of the PP/PS blends has been carefully studied.     

Nanocomposites based on epoxy resin and silicon dioxide particles

The cure of an epoxy resin (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate) in the presence of silica nanoparticles modified by 3-(triethoxysilyl)propylsuccinic anhydride has been studied. Optimal conditions for the preparation of optically transparent polymer nanocomposites with increased glass transition temperatures are determined. The glass transition temperatures of the above nanocomposites are 50–70°C higher than those of the unfilled epoxy resin synthesized under the same conditions (100°C).     

STUDY ON THE EPOXY RESIN TOUGHENED BY HYDROXY-TERMINATED BUTADIENE-ACRYLONITRILE COPOLYMER

Toughened epoxy resin with excellent properties was obtained by adding organic acid anhydride curing agent and hydroxy-terminated butadiene-acrylonitrile copolymer (HTBN), which is cheaper than CTBN. The anhydride reacts with both epoxy groups on epoxy resin and hydroxyl groups on HTBN. As a result the soft long chains of HTBN and the rigid chain of epoxy resin form one network, giving the resin toughness. Two-phase structure of the toughened resin was observed by SEM and TEM.     

Preparation and characterization of a novel thermally stable unsaturated poly(ester-imide) based on 1,4-bis[2′-trifluoromethyl-4′-(4″-carboxylic acid)trimellitimido phenoxy]benzene

A novel thermally stable unsaturated poly(ester-imide) (UPEI-50) was prepared by thermal polycondensation of a diimidodicarboxylic acid monomer, 1,4-bis[2′-trifluoromethyl-4′-(4″-carboxylic acid)trimellitimido phenoxy]benzene (BTTB), maleic anhydride and 1,2-propylene glycol. The poly(ester-imide) resin obtained was found to be easily dissolved in glycidyl methacrylate (GMA) to give a homogeneous resin composition with low viscosity, which was then thermally cured into thermosetting poly(ester-imide)/glycidyl polymethacrylate polymer composite (UPEI-50/GMA). Effects of curing processing parameters such as the curing temperature and curing time, the reactive monomer concentration and the initiator amount etc. on curing reaction were systematically investigated. Experimental results indicated that the thermally cured UPEI-50/GMA polymer composite exhibited outstanding thermal stability, mechanical and electrical insulating properties.     

Syntheses of flame-retarding 4-phosphonatomethyl-2,6-dibromophenyl trimellitate anhydrides and their reactivities toward epoxy resin

4-Phosphonatomethyl-2,6-dibromophenyl trimellitate anhydrides (HDBBP–TMA) were prepared by the condensation of 4-chloroformyl phthalic anhydride with corresponding 4-hydroxy-3,5-dibromobenzyl phosphonates (HDBBP). These materials could be used to produce excellent flame retardance in epoxy resins when the substances were chemically combined with the polymer. The reactive-type HDBBP–TMA showed much better phosphorus–bromine synergistic effects on the flame retardancy of epoxy resins than the additive-type compounds such as HDBBP or the mixture of bromo compound (such as 2,6-dibromo-p-cresol) and phosphorus compound (such as triphenyl phosphite). Meanwhile, the oxygen index of cured epoxy resin was proved to be relative to the extent of crosslinking. Reactivities of HDBBP–TMA toward epoxy were also studied by rheometer in comparison with those of trimellitic anhydride and its derivatives such as 4-methylphenyl trimellitate anhydride and 4-methyl-2,6-dibromophenyl trimellitate anhydride.     

Insights into phthalonitrile/epoxy blends modification system from non-competitive cure system based on alicyclic anhydride

A series of polymer blends were prepared from 1,3-bis(3,4-dicyanophenoxy)benzene (3BOCN) and epoxy resin with methyl tetrahydrophthalic anhydride as curing agent.The curing behavior and curing kinetics of the blends were studied by differential scanning calorimetry.The apparent activation energy of the blends with various contents of 3BOCN was higher than that of the blends without 3BOCN.A model experiment suggested that there is no obvious reaction between phthalonitrile and epoxy.The thermal and mechanical properties of the polymer blends were evaluated.The polymer blends exhibit high storage modulus and char yield compared with the neat epoxy.The polymer blends show ductile fracture morphology by scanning electron microscopy (SEM) images.     

偏苯三酸酐-环氧丙烷丁基醚合成超支化碱溶性聚酯

通过1,2,4-偏苯三甲酸酐(TA)和环氧丙烷丁基醚(BGE)合成超支化碱溶性聚酯,利用合成聚合物分子外围的羧基与烯丙基缩水甘油醚(AGE)反应,在超支化聚合物分子外围引入反应性烯丙基醚.研究了树脂组成对感光性和碱溶性的影响;结果表明:调整反应物料配比,可以获得较好的碱溶性和光固化性能,其树脂的反差γ可达到3.92.     

Branching kinetics of epoxy polymerization of 1, 4-butanediol diglycidyl ether with cis-1, 2-cyclohexanedicarboxylic anhydride

The copolymerization of an epoxy resin [1, 4-butanediol diglycidyl ether (DGEB) (Note a)] with an anhydride [cis-1, 2-cyclohexanedicarboxylic anhydride (CH)] in the presence of N, N-benzyldimethylamine (CA) as a catalyst produces a branched epoxy polymer. We show that the branching kinetics of the copolymerization reaction and the molecular weight distribution of the branched polymers can be approximated by using Smoluchowski's coagulation equation. In the simplest relevant application of this equation to our problem, the overall rate kernel w(u, v) that describes the branching probability in the equation turns out to be proportional to the sum of active sites on the two polymers with a time dependent coefficient. The molecular weight distribution (MWD) and the weight average molecular weight of the branched copolymers at different reaction stages before the gelation threshold are calculated theoretically. The calculated values are then compared with the experimental results obtained by using small angle X-ray scattering (SAXS), laser light scattering (LLS), and chemical analysis. Satisfactory agreement between experimental results and the use of the coagulation equation is attained when it is assumed that the distribution of epoxy polymer molecules is exponential in the number of branching points or, equivalently, active sites, at an early stage of the polymerization reaction.