环氧树脂基多孔光学增透膜的制备及其性能研究

利用低分子量环氧树脂(DGEBA)在固化后和与之共混的聚氯乙烯(PVC)之间产生的相分离,用丁酮抽提其中的PVC组分,制备了环氧树脂基多孔增透膜。测试结果表明,当mDOEBA／mPVC=30／70、膜厚为110nm时,增透膜的透过率最高,达96％以上。薄膜在水或甲苯中煮沸不发生收缩、脱落,表现良好的粘附力和机械强度。     

固化条件对环氧树脂/丙烯酸酯橡胶共混体系结构与性能的影响

利用丙烯酸酯橡胶(ACM)提高热固性环氧树脂(EP)的韧性,系统研究共混体系固化条件对材料结构和性能的影响.研究表明,固化前环氧树脂与丙烯酸酯橡胶在整个组成范围内为均相体系,固化过程中两组份分子量不断增大,部分组成环氧树脂/丙烯酸酯橡胶共混体系(80/20及50/50)发生反应诱导相分离现象(RIPS).在发生反应诱导相分离的体系中,分相后的环氧树脂和丙烯酸酯橡胶两相彼此包含对方的组分,是一种不彻底的相分离.同时,固化后材料的结构与性能强烈依赖于所用固化条件(包括固化时间、固化温度及固化剂含量等).因此,可以通过调节体系固化条件实现对环氧树脂/丙烯酸酯橡胶共混体系结构和性能的调控.     

环氧树脂共混物相结构的调控方法研究

研究了环氧树脂(E51)/聚砜(PSF)共混物相结构的控制方法.通过抑制相分离、控制预固化的反应程度控制环氧树脂的分子量,固化后可获得不同的共混物相结构.依据红外测定的固化反应程度设定固化程序,可有效控制共混物的相结构.加入促进剂三氟化硼-乙基胺(BTF-EA)可提高固化反应速度,使相分离结构在早期被抑制,以获得小微区的相结构.     

固化剂对环氧树脂/聚砜共混物层状结构形成的影响

不同含量的聚砜(PSF)对环氧树脂(EP)/PSF共混物相结构有重要影响,通过对反应分相后的样品进行断面观察,发现一定PSF含量时,体系形成了层状结构.这种层状结构通常为3层,包括上下2个外层、由聚砜和环氧树脂的颗粒-基体结构组成,以及1个双连续结构形成的中间层.研究表明,这种层状结构由反应诱导相分离开始之初形成的双连续结构发展而来,由于反应和相分离的进一步发展热塑性树脂富集相的体积分数逐渐减小、以及组分间的动力学不对称而最终形成的.在一定PSF浓度范围内,不同温度固化样品时均得到了这种层状结构.改变固化剂类型,层状结构的形貌受到影响,当固化剂活性较高时,外层变薄中间层增厚.当组分间的相容性较好时,双连续结构甚至不能演化发展到层状结构.     

聚合物共混物的相容性及相分离

综述了聚合物共混物相容性和相分离的研究现状。介绍了聚合物共混物的相容性理论,影响相容性的因素及改善和相容性的方法和表征相容性的手段。聚合物共混物的相分离机理制约着材料的性能,旋节分离和成核－增长相分离分别形成不同的形态结构。旋节分离和成核－增长相分离所对应的动力学过程是不同的,散射光强与相分离时间分别满足指数和幂指数关系。     

聚醚链段长度对氨基聚醚-环氧树脂力学性能的影响

以柔性端氨基聚醚(BATPE)和双酚A环氧树脂(DGEBA)为原料, 制备了无微相分离结构的无定型AB交联热固性树脂. 测试了3种不同聚乙二醇(PEG)链段长度(M_PE)的BATPE-DGEBA环氧树脂固化产物的应力-应变曲线、动态力学温度谱和冲击断面形貌. 结果表明, 在环氧树脂交联网络中引入两端与DGEBA化学连接的PEG链段能避免微相分离结构的生成, 有利于提高DGEBA链段的应变松弛速率. 增加M_PE, 一方面能降低环氧树脂固化产物的玻璃化转变温度和室温下的刚度和拉伸强度, 增加韧性(包括冲击强度和拉伸韧性)、断裂应变和模量损耗因子; 另一方面也能提高固化产物在低温下的储存模量. 优化M_PE可制备出在中低温下同时具有优异的拉伸强度、模量、断裂应变和冲击性能的BATPE-DGEBA环氧树脂.     

分子结构对环氧树脂性能影响的分子模拟研究

采用分子动力学方法建立了二乙基甲苯二胺/双酚A缩水甘油醚环氧树脂体系(DETDA/DGEBA体系)和间苯二胺/双酚A缩水甘油醚环氧树脂体系(mPDA/DGEBA体系)的交联模型,在此基础上,分析了固化剂分子结构的差异对树脂性能的影响,研究发现mPDA/DGEBA体系的玻璃化转变温度、模量以及阻碍水分子的扩散性能均高于DETDA/DGEBA体系。为了进一步揭示交联环氧树脂分子结构与性能之间的关系,研究了上述两体系的自由体积和内聚能密度。结果表明,与DETDA/DGEBA体系相比,mPDA/DGEBA体系具有较小的自由体积和较高的内聚能密度。较小的自由体积和较高的内聚能密度是造成mPDA/DGEBA体系玻璃化转变温度、模量以及阻碍水分子的扩散性能均高于DETDA/DGEBA体系的原因。     

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′)     

聚酰亚胺对多官能团环氧树脂的增韧作用

本文选择不同比例的聚酰亚胺(PEI)与多官能团的环氧树脂(MY0510)和 NovoIak 树脂(DEN431)共混,以3,3′—二氨基二苯亚砜(DDS)为固化剂,制备一系列的共混物样品。通过三点弯曲试验、扫描电镜和动态力学热分析分别测定共混物的应力强度因子(K_(1c))和临界应变能松驰速率(G_(1c))、形态结构和玻璃化转变温度。当加入 PEI 时,共混物的 K_(1C)和 G_(1C)都有显著的提高,即增加了环氧树脂的韧性。虽然所有共混物只有一个Tg 峰,但电镜的观察结果说明为两相结构。当 PEI 的含量为10%时,PEI 开始从分散相转变为连续相。后固化作用使 Tg 提高了6—20℃,同时也有利于 K_(1C)和 G_(1C)。     

Epoxy/Rectorite自由体积分布温度特性的正电子谱学研究

采用正电子寿命谱(PLA)技术,通过探测聚酰胺固化环氧树脂(Epoxy)及环氧树脂/累托土(Epoxy/Rectorite)复合材料分别在不同温度点自由体积分布特性的变化,结果表明:在低温T=30K时,分子链段被冻结,自由体积分布变窄;温度在T_g及以上时,聚酰胺固化DGEBA环氧树脂中出现微相分离情况,观测到两种大小不同的自由体积孔洞的存在;纳米复合材料中累托土片层与高分子链段相互作用,同时片层促进了环氧树脂的交联,阻碍了复合材料的微相分离.     

Epoxy/poly(benzyl methacrylate) blends: miscibility, phase separation on curing and morphology

Diglycidyl ether of bisfenol-A (DGEBA)/polybenzyl methacrylate (PBzMA) blends cured with 4,4’-diaminodiphenylmethane (DDM) were studied. Miscibility, phase separation, cure kinetics and morphology were investigated through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Non-reactive DGEBA/PBzMA blends are miscible over the whole composition range. The addition of PBzMA to the reactive (DGEBA+DDM) mixture slows down the curing rate, although the reaction mechanism remains autocatalytic. On curing, initially miscible (DGEBA+DDM)/PBzMA blends phase separate, arising two glass transition temperatures that correspond to a PBzMA-rich phase and to epoxy network. Cured epoxy/PBzMA blends present different morphologies as a function of the PBzMA content.     

Effect of structure on thermal behaviour of epoxy resins

The paper deals with the curing behaviour of diglycidyl ether of bisphenol-A (DGEBA) using three novel multifunctional aromatic amines having phosphine oxide and amide-acid linkages. The amines were prepared by reacting tris(3-aminophenyl)phosphine oxide (TAP) with 1,2,4,5-benzenetetracarboxylic acid anhydride (P)/4,4^′-(hexafluoroisopropylidene)diphthalic acid anhydride (F)/3,3^′,4,4^′-benzophenonetetracarboxylic acid dianhydride (B). Amide-acid linkage in these amines is converted to thermally stable imide linkage during curing reaction. Curing temperatures of DGEBA were higher with phosphorylated amines than the conventional amine 4,4^′-diamino diphenyl sulphone (D). A decrease in initial decomposition temperature and higher char yields were observed when phosphorus containing amide-acid amines were used as curing agents for DGEBA.     

A DSC study of miscibility and phase separation in crystalline polymer blends of phenolphthalein poly(ether ether sulfone) and poly(ethylene oxide)

The miscibility of blends of phenolphthalein poly(ether ether sulfone) (PES-C) and poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. Differential scanning calorimetry (DSC) studies showed that the PES-C/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed a single, composition-dependent glass transition temperature (T_g), and thus that PES-C and PEO are miscible in the amorphous state at all compositions at lower temperature. At higher temperature, the blends underwent phase separation, and the PES-C/PEO blend system was found to display a lower critical solution temperature (LCST) behavior. The phase separation process in the blends has also been investigated by using DSC. Annealed at high temperatures, the PES-C/PEO blends exhibited significant changes of thermal properties, such as the enthalpy of crystallization and fusion, temperatures of crystallization and melting, depending on blend composition when phase separation occurred. These changes reflect different characteristics of phase structure in the blends, and were taken as probes to determine phase boundary. From both the thermal analysis and optical microscopy, the phase diagram of the blend system was established. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1383–1392, 1997     

Morphology,toughness mechanism,and thermal properties of hyperbranched epoxy modified diglycidyl ether of bisphenol A (DGEBA) interpenetrating polymer networks

New hyperbranched poly(trimellitic anhydride‐triethylene glycol) ester epoxy (HTTE) is synthesized and used to toughen diglycidyl ether of bisphenol A (DGEBA) 4,4′‐diaminodiphenylmethane (DDM) resin system. The effects of content and generation number of HTTE on the performance of the cured systems are studied in detail. The impact strength is improved 2–7 times for HTTE/DGEBA blends compared with that of the unmodified system. Scanning electron microscopy (SEM) of fracture surface shows cavitations at center and fibrous yielding phenomenon at edge which indicated that the particle cavitations, shear yield deformation, and in situ toughness mechanism are the main toughening mechanisms. The dynamic mechanical thermal analyzer (DMA) analyses suggest that phase separation occurred as interpenetrating polymer networks (IPNs) for the HTTE/DGEBA amine systems. The IPN maintains transparency and shows higher modulus than the neat epoxy. The glass transition temperature (T_g) decreases to some extent compared with the neat epoxy. The T_g increases with increase in the generation number from first to third of HTTE and the concentrations of hard segment. The HTTE leads to a small decrease in thermal stability with the increasing content from TGA analysis. The thermal stability increases with increase in the generation number from first to third. Moreover, HTTE promotes char formation in the HTTE/DGEBA blends. The increase in thermal properties from first to third generation number is attributed to the increase in the molar mass and intramolecular hydrogen bridges, the increasing interaction of the HTTE/DGEBA IPNs, and the increasing crosslinking density due to the availability of a greater number of end hydroxyl and end epoxide functions. Copyright © 2008 John Wiley & Sons, Ltd.     

环氧化聚丁二烯-聚苯乙烯嵌段共聚物对聚苯醚/环氧体系反应诱导相分离行为的影响

采用扫描电镜、光学显微镜和光散射仪研究了环氧化聚丁二烯一聚苯乙烯嵌段共聚物(EBs)对聚苯醚(PPO)/双酚A 型环氧树脂(DGEBA)/4,4二(2,6-二甲基苯胺基)甲烷(DIM-DDM)体系反应诱导相分离行为的影响.实验结果表明,EBS的加入对PPo/DGEBA/DIM-DDM体系反应诱导相分离的演化过程有阻滞作用.随着EBS加入量的增加,体系形成双连续相结构所需的PPO含量范围变宽,而对于相同PPO含量、形成双连续相的体系则相结构尺寸减小.     

环氧化聚丁二烯-聚苯乙烯嵌段共聚物对聚苯醚/环氧体系反应诱导 相分离行为的影响

采用扫描电镜、光学显微镜和光散射仪研究了环氧化聚丁二烯-聚苯乙烯嵌段共聚物(EBS)对聚苯醚(PPO)/双酚A型环氧树脂(DGEBA)/4,4’-二(2,6-二甲基苯胺基)甲烷(DIM-DDM)体系反应诱导相分离行为的影响. 实验结果表明, EBS的加入对PPO/DGEBA/DIM-DDM体系反应诱导相分离的演化过程有阻滞作用. 随着EBS加入量的增加, 体系形成双连续相结构所需的PPO含量范围变宽, 而对于相同PPO含量、形成双连续相的体系则相结构尺寸减小.     

Curing properties of novel curing agent based on phenyl bisthiourea for an epoxy resin system

Phenyl bisthioureas: 4,4′-(bisthiourea)diphenylmethane (DTM), 4,4′-(bisthiourea)diphenyl ether (DTE), and 4,4′-(bisthiourea)diphenyl sulfone (DTS) were synthesized and used as curing agents for the epoxy resin diglydicyl ether bisphenol A (DGEBA). Synthesized phenyl bisthioureas were characterized using FT-IR and ¹H-NMR analysis. For comparison studies the epoxy system was also cured using the conventional aromatic amine 4,4′-diaminodiphenyl ether (DDE). Curing kinetics of epoxy/amine system was studied by dynamic and isothermal differential scanning calorimeter (DSC). Curing kinetic was evaluated based on model-free kinetics (MFK) and ASTM E 698 model, and the activation energy was compared with DDE. Curing system of phenyl bisthiourea link (DGEBA/DTM, DGEBA/DTE, and DGEBA/DTS) shows two exothermic peaks, while that of the conventional aromatic amines showed only a single peak. The initial exothermic peak is due to the primary nitrogen of the thiourea group, and the exotherm at higher temperature is due to the presence of thiourea groups. Glass transition temperature (T _g) of DGEBA/DTM, DGEBA/DTE, and DGEBA/DTS cured resins were lowered by 323 K when compared to the widely used diaminodiphenyl ether (DDE) cured resin. Oxidation induction temperature measurement performed on DSC suggests that the DGEBA/DTM, DGEBA/DTE, and DGEBA/DTS system cured resins has better oxidative stability when compared to cured DGEBA/DDE resin system.     

Miscibility,morphology and fracture toughness of epoxy resin/poly(vinyl acetate) blends

Diglycidylether of bisphenol A (DGEBA)/poly(vinyl acetate) (PVAc) blends cured with 4,4-diaminodiphenylmethane (DDM) were prepared. The miscibility and phase behavior were investigated by means of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The study results indicate that the epoxy precursor (DGEBA)/PVAc blends are clearly miscible at the entire composition and theTg values experimentally obtained are in a good agreement with those predicted by Fox equation. Cured at elevated temperature, all the DDM-cured blends underwent phase separation and display two-phase morphology. When PVAc content is more than 10 wt%, the thermoplastics-modified resins began to show a co-continuous phase structure. It is the cocontinuous structure that leads to a significantly-improved toughness inK _ic. Morphologic investigation of the surfaces of fracture mechanic measurement specimens indicates that the toughening effect of the thermoplastics-modified epoxy resins may arise mainly from the ductile yielding of PVAc.     

Synthesis and characterization of liquid‐crystalline epoxy and its blend with conventional epoxy

Terephthaloyl chloride was reacted with 4‐hydroxy benzoic acid to get terephthaloylbis(4‐oxybenzoic) acid, which was characterized and further reacted with epoxy resin [diglycidyl ether of bisphenol A (DGEBA)] to get a liquid‐crystalline epoxy resin (LCEP). This LCEP was characterized by Fourier transform infrared spectrometry, ¹H and ¹³C NMR spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). LCEP was then blended in various compositions with DGEBA and cured with a room temperature curing hardener. The cured blends were characterized by DSC and dynamic mechanical analysis (DMA) for their thermal and viscoelastic properties. The cured blends exhibited higher storage moduli and lower glass‐transition temperatures (tan δ_max, from DMA) as compared with that of the pure DGEBA network. The formation of a smectic liquid‐crystalline phase was observed by POM during the curing of LCEP and DGEBA/LCEP blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3375–3383, 2003     

Mechanical properties and morphology of epoxy/poly(vinyl acetate)/poly(4-vinyl phenol) brominated system

Diglycidyl ether of bisfenol-A (DGEBA)/poly(vinyl acetate) (PVAc)/poly(4-vinyl phenol) brominated (PVPhBr) ternary blends cured with 4,4’-diaminodiphenylmethane (DDM) were investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). Homogeneous (DGEBA+DDM)/PVPhBr networks with a unique T _g are generated. Ternary blends (DGEBA+DDM)/PVAc/PVPhBr are initially miscible and phase separate upon curing arising two T _gs that correspond to a PVAc-rich phase and to epoxy network phase. Increasing the PVPhBr content the T _gof the PVAc phase move to higher temperatures as a consequence of the PVAc-PVPhBr interactions. Different morphologies are generated as a function of the blend composition.