Effect of CTBN rubber inclusions on the curing kinetic of DGEBA-DGEBF epoxy resin

The curing kinetics of an epoxy resin matrix, based on diglycil ether of bisphenol A and F (DGEBA-DGEBF), associated with an anhydride hardener, at different carboxyl-terminated copolymer of butadiene and acrylonitrile liquid rubber (CTBN) concentration (0-10 phr) are studied using a differential scanning calorimetry (DSC) and a stress-controlled rheometer in isothermal and dynamic conditions. The aim of this work is to correlate the presence of the rubber phase with the transition phenomena that occur during the curing process. The CTBN rubber induces a catalytic effect on the polymerization of the pure resin clearly observed by a significant enhancement of the curing rate. Calorimetric and rheological analysis also evidences that gelation and vitrification times take place not punctually but in a wide range of time. Rheological data show that the presence of rubbery phase induces a higher rate of gel formation during the early stages of the reactions, confirming the calorimetric results. Finally the results are compared with theoretical models evidencing a good fitting between experimental and predictive data.     

氨基聚酯树脂固化过程的FTIR跟踪

用FTIR内标法跟踪氨基聚酯树脂的固化过程,选取815cm~(-1)的三嗪环面外振动峰作内标峰,913cm~(-1)处的甲氧基变形振动峰和3500cm~(-1)左右的羟基伸缩振动峰为特征吸收峰。结果表明,随着固化的进行,涂膜的羟基、甲氧基和羧基递减,醚键和羰基递增,说明固化过程是以交联反应为主,伴有自缩合反应和酯化反应的复杂过程。     

CURE OF A MICROGEL-EPOXY RESIN TWO-PHASE POLYMER WITH ETHYLENE DIAMINE

The curing of a microgel-epoxy resin two phase polymer prepared by in situ copolymerization of unsaturated polyester with acrylic monomer was studied. The unsaturated unit reacted with N—H during the cure of the resin with ethylene diamine. The Michael type reaction was ten times more rapid than the addition of N—H to epoxide.This was accounted for the lower apparent activation energy of the curing of the two phase resin.     

水性环氧树脂的制备和固化机理的探讨

探讨了以环氧树脂、甲基丙烯酸和丙烯酸丁酯为原料,由接枝的路线合成水可分散性环氧树脂的制备、乳化及固化成膜一系列的反应机理,对过程进行了分析,并讨论了有关因素对各步反应的影响。     

Curing of an epoxy resin modified with poly(methylmethacrylate) monitored by simultaneous dielectric/near infrared spectroscopies

Simultaneous dielectric and near infrared measurements have been performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4^′-diaminodiphenylmethane hardener and different amounts of poly(methylmethacrylate) as modifier. The effect of the modifier amount on the polymerisation reactions has been studied, as well as that of the curing temperature. Epoxy and amine conversions have been followed by near infrared spectroscopy (NIR), while changes in molecular mobility in the reaction mixture have been analysed by dielectric relaxation spectroscopy (DRS). Evolutions of ionic conductivity and α-relaxation have been analysed and vitrification times have been obtained. The relaxational behaviour has been analysed through curing in the frequency domain, being the change of the main relaxation indicative of the cure reaction advancement. DRS data are also presented as complex impedance Z(ω). Vitrification times, obtained by dielectrometry have been compared with those obtained by rheological measurements and gelation times obtained by NIR have been compared with those obtained by solvent extraction.     

电子束固化环氧树脂的物理特征及其分析

分析了环氧树脂电子束辐射固化的物理特征 ,电子束辐射固化过程受活性中心扩散控制 ,整个固化区域由片层状结构组成 .与电子能量沉积分布相对应 ,环氧树脂辐射固化度的最高值是在一定深度而不是在辐射表面出现 .对电子束辐射环氧树脂体系的固化过程进行了模型解释 ,固化区域大小主要由电子的能量传递范围和浓度决定 ,反应活性中心的扩散作用影响较弱     

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.     

2,4,6-三(羟基苯甲基氨基)-均三嗪的合成及其与双酚A型环氧树脂的固化行为研究

合成了一种含三嗪环结构的环氧树脂固化剂2,4,6-三(羟基苯甲基氨基)-均三嗪(MFP).用动态DSC和原位红外光谱对MFP/DGEBA(双酚A型环氧树脂)体系的固化行为进行了研究.动态DSC研究表明,由于MFP分子结构中存在两种活泼氢(酚羟基氢和仲胺氢),固化反应存在明显的两个峰,相对应的表观活化能分别为70.5 kJ.mol-1和86.5 kJ.mol-1(Kissinger法),通过与另一相似化合物固化DGEBA的比较可知,在MFP固化DGEBA的过程中,酚羟基与环氧基反应相对较难.原位红外动力学结果很好地支持了上述结论.     

2－乙基－4－甲基咪唑固化环氧树脂的固化反应机理、动力学及其反应活性

本文应用ＤＳＣ和ＦＴＩＲ对２－乙基－４－甲基咪唑固化双酚Ａ二缩水甘油醚型环氧树脂体系的固化反应机理和２－乙基－４－甲基咪唑固化双酚Ａ二缩水甘油醚型、缩水甘油酯与脂环型环氧树脂体系的固化反应特征、动力学及其反应活性进行了研究．结果表明，双酚Ａ二缩水甘油醚型环氧树脂／咪唑体系的固化反应是分两步独立进行的，第一步是加成反应，第二步是催化聚合反应．缩水甘油酯与脂环型环氧树脂（ＴＤＥ－８５）／咪唑体系的固化反应过程也分两步进行，第一阶段反应主要是缩水甘油酯型环氧基进行的加成反应和催化聚合反应，第二阶段主要是脂环型环氧基进行的加成反应．各体系第一阶段的表现反应活化能均低于第二阶段活化能．当ＴＤＥ－８５型环氧树脂中引入缩水甘油醚型环氧树脂后，固化反应速率均较ＴＤＥ－８５环氧树脂单独固化时快．     

金属螯合物催化环氧E-51/酸酐体系的催化活性及固化过程

Uri等曾对水杨酸铬系列金属螯合物催化环氧树脂与羧酸之间的固化反应进行了研究,但对呋喃甲酸铬系列金属整合物催化环氧树脂与酸酐之间的固化反应的研究,尚未见报道。我们在首次合成呋喃甲酸铬系列催化剂的基础上,对其催化环氧树脂/酸酐体系的催化活性、固化过程进行了研究,并与水杨酸系列金属螯合物及由不同金属元素配位中心、不同配位体组成的其它类型金属螯合物催化E-51/MTHPA体系的催化活性进行了比较;对不同配