基于动态受阻脲键的可修复环氧树脂的制备及性能

以大位阻仲胺和异氰酸酯为原料,合成了基于大位阻脲键的环氧固化剂,并以4, 4’-二氨基二苯甲烷为交联剂,制得了基于大位阻脲键的热可逆结构稳定性自修复环氧热固性树脂。对合成的含大位阻脲键的环氧树脂进行了进行拉伸性能测试、热机械性能测试（DMA）、热重测试（TG）、可修复性能和可再加工性能测试。结果表明,拉伸强度达到68.62 MPa,断裂伸长率达到了6.93%,有效解决了环氧树脂的脆性难题,并且能够保持相对优异的力学性能,从而具有实际应用价值。同时,这种新型材料可以在120℃下10 min内实现快速愈合,大位阻脲键赋予了环氧热固性材料优异的再加工性、自愈合性、焊接性、可重塑性、可循环性和形状记忆性。因此,将大位阻脲键引入热固性环氧树脂,为以经济高效的方式制备具有高机械强度和自愈合效率的环氧热固性树脂提供了一种可行的策略。     

可循环回收利用的本征导热聚六氢三嗪树脂研究

采用多聚甲醛(PFA)和含有芳香酰胺特殊结构的4,4'-二氨基苯酰替苯胺(DABA)为原料,通过利用分子链间氢键强相互作用向树脂固化网络中引入局域微观有序结构增大声子传播自由程,合成一种新型本征导热聚六氢三嗪热固性树脂(DABA-PHT).通过对树脂预聚过程和机理、固化工艺、导热性能、降解性能及循环回收利用性能的研究表明:水能够作为催化剂有效加速预聚反应、大幅缩短预聚时间,且酰胺N-H键未参与交联反应;DABA-PHT树脂易于合成和加工,且具有良好的力学、耐热、降解和循环回收利用性能,热导率达到0.38 W·m~(-1)·K~(-1),接近普通环氧树脂的2倍,有望用来制备可循环回收利用的高热导率热固性树脂基复合材料.     

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′)     

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.     

高性能环氧树脂/碳纳米管复合物的热分析研究

用差示扫描量热仪(DSC)、热失重分析仪(TGA)和动态力学热分析仪(DMTA)研究了多壁碳纳米管(MWNTs)/高性能4,4′-二氨基二苯甲烷四缩水甘油环氧树脂(TGDDM)/4,4′-二氨基二苯基砜(DDS)复合物的热性能.Kissinger和Flynn-Wall-Ozawa的非等温固化动力学研究发现,随着MWNTs含量的增加,复合物固化反应的活化能先减小后增大.TGA研究表明,MWNTs的添加对环氧树脂热稳定性影响很小.碳纳米管填充到TGDDM/DDS体系后,复合物的储存模量随着MWNTs含量的增加而增大,而玻璃化温度却随之减小.     

吸水过程对环氧树脂的动态松弛行为的影响

以酚醛树脂和乙酸、正丁酸和苯乙酸酯化的酚醛树脂固化邻甲酚环氧树脂.应用称重法、示差扫描量热法(DSC)和动态机械分析法(DMA)等手段研究吸水过程对环氧树脂的动态松弛行为的影响.结果表明,吸水过程对酚醛树脂和酯化酚醛树脂固化体系的动态松驰行为有显著的影响,这是由于两种体系中侧基对吸水过程及与水分子的相互作用不同所致.     

双氨基邻苯二甲腈/环氧树脂固化物的制备及性能研究

本文合成出了一种双氨基邻苯二甲腈(DPN)单体,采用红外和核磁共振表征了DPN及其中间体含双氨基的酚类单体(DHTM)的分子结构,利用差示扫描量热证明了DPN的自催化性能及其对环氧树脂(EP)的固化作用。将DHTM与DPN分别与EP制得共混体系,然后将其固化。热失重和动态热机械性能测试表明,DPN-EP固化物的各项性能都要优于DHTM-EP固化物。其在氮气和空气下的初始分解温度(T_(5%))分别提高了27和68℃,计算得到的极限氧指数达到36.36,提高了9.12,其玻璃化温度为202℃,展现出了良好的耐热和阻燃性能。     

一种新型室温固化、耐高温环氧树脂体系及其性能

采用1-己基-3-甲基咪唑四氯化铁盐([C₆mim]FeCl₄)与混合胺复配室温(20 ℃)固化双酚A型环氧树脂E-51,并与其它脂肪胺类室温固化E-51体系在力学性能、热性能、耐老化性能方面的数据进行了比较,同时分析了[C₆mim]FeCl₄不同添加量对固化体系性能的影响,结果显示:[C₆mim]FeCl₄/混合胺复配室温固化E-51体系的室温拉伸强度可达90 MPa,高温(120 ℃)下也保持了良好的力学性能,热失重(5%)分解温度为310 ℃,200 ℃老化7 d后,拉伸强度为28 MPa,是一种可在高温下使用的新型环氧树脂室温固化体系。     

环氧/酸酐/DMPA体系固化动力学与溶解性研究

在环氧/酸酐固化体系中引入4-二甲氨基吡啶(DMPA)作为酯交换反应催化剂和固化反应促进剂,以制备具有动态交联网络的环氧树脂。用差示扫描量热仪(DSC)对环氧/酸酐/DMPA体系的固化行为进行了研究,考察了催化剂的含量和固化剂比例对环氧/酸酐/DMPA体系固化行为的影响和固化动力学。通过乙二醇溶解实验,研究交联网络中的可交换键。结果表明反应体系中有高温和低温两种固化机理发生反应,催化剂和固化剂含量较少时,固化反应温度高,固化反应中含较多环氧自聚反应,不利于酯交换反应,溶解效果差;反之,固化反应温度向低温移动,利于酯键的形成,样品的溶解速度就越快。当环氧/酸酐为1:1.5,催化剂用量为3%时,具有较好的溶解性能。     

热可逆交联环氧树脂的动态结构与性能研究

通过双马来酰亚胺与侧链带有呋喃官能团线性环氧树脂间的Diels-Alder反应,制备了热可逆交联的环氧树脂(DAERs),通过热分析、固体核磁共振技术和力学性能测试详细研究了该热可逆交联聚合物中的热可逆转变过程、动态化学键演化以及交联度对力学性能的影响.示差扫描量热法(DSC)和动态热机械分析(DMA)等热分析结果表明,可逆共价键的化学交联作用提高了材料的玻璃化转变温度,随着交联度的增大,热可逆共价键断裂及玻璃化转变协同作用导致材料软化温度显著提高,进而提高了材料的耐热性.通过变温13C固体NMR实验原位监测DA/retro-DA反应过程,发现DAERs中通过DA反应形成的交联网络结构可以在高温解交联而生成呋喃与马来酰亚胺小分子化合物,而低温时呋喃与马来酰亚胺化合物又再次反应得到DA加成结构,进而从分子水平上为材料的热可逆交联特性提供了关键的实验证据.而原样品和溶液法再加工样品的拉伸实验结果表明,可逆交联DA反应不但使样品具有较高的力学强度,而且使交联聚合物具有了再加工的能力.     

Synthesis and thermal characterization of phosphorus containing siliconized epoxy resins

Siliconized epoxy matrix resin was developed by reacting diglycidyl ethers of bisphenol A (DGEBA) type epoxy resin with hydroxyl terminated polydimethylsiloxane (silicone) modifier, using γ-aminopropyltriethoxysilane crosslinker and dibutyltindilaurate catalyst. The siliconized epoxy resin was cured with 4, 4-diaminodiphenylmethane (DDM), 1,6-hexanediamine (HDA), and bis (4-aminophenyl) phenylphosphate (BAPP). The BAPP cured epoxy and siliconized epoxy resins exhibit better flame-retardant behaviour than DDM and HDA cured resins. The thermal stability and flame-retardant property of the cured epoxy resins were studied by thermal gravimetric analysis (TGA) and limiting oxygen index (LOI). The glass transition temperatures (T_g) were measured by differential scanning calorimetry (DSC) and the surface morphology was studied by scanning electron microscopy (SEM). The heat deflection temperature (HDT) and moisture absorption studies were carried out as per standard testing procedure. The thermal stability and flame-retardant properties of the cured epoxy resins were improved by the incorporation of both silicone and phosphorus moieties. The synergistic effect of silicone and phosphorus enhanced the limiting oxygen index values, which was observed for siliconized epoxy resins cured with phosphorus containing diamine compound.     

EPOXY RESINS TOUGHENED WITH CARBOXYL TERMINATED POLYETHERS

Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn, the mechanical properties of the cured resin. Carboxyl terminated polytetrahydrofurans have a low glass transition temperature, and in appropriate amount they do not affect the thermal resistance of the resin. These advantages make them preferable as toughener for epoxy resins.     

Synthesis and characterization of epoxy resins containing imine group and their curing processes with aromatic diamine

The epoxy resins containing imine bonding were prepared from hydroxyl substituted Schiff base monomers in two steps. At the first step, hydroxyl substituted Schiff base monomers were synthesized via condensation reaction. At the second step, epoxy resins were synthesized from the reaction between Schiff base monomers and epichlorohydrine (EPC). Then curing processes of epoxy resins were achieved by p-phenylenediamine compound. The structures of resulting compounds were confirmed by FT-IR, UV-Vis and ¹H-NMR. TG-DTA and DSC measurements were performed for thermal characterizations of the compounds. Chemical resistances of the cured epoxy-amine systems were determined for coating applications in acidic, alkaline and organic solvents. HCl (10%, aqueous solution), NaOH (10%, aqueous solution), DMSO, DMF, N-methylpyrrolidone, ethanol, THF and acetone were used for corrosion tests. Chemical resistance data of the synthesized epoxy resins demonstrated that they have good chemical resistance against various acid, alkaline and common organic solvents. Surface morphologies of epoxy resin and the cured epoxy resin were determined with scanning electron microscopy (SEM) measurements. Also, optical band gap (E_g) values of Schiff base monomers and epoxy resins were calculated from UV-Vis measurements.     

Thermal and flame retardant properties of epoxy resin cured by a novel phosphorus-containing 4,4′-bisphenol novolac curing agent

A novel flame retardant curing agent for epoxy resin (EP), i.e., a DOPO (9,10-dihydro-9-oxa-10-phosphaphenan-threne-10-oxide)-containing 4,4'-bisphenol novolac (BIP-DOPO) was synthesized and characterized by Fourier transform infrared (FTIR), ¹H NMR, ³¹P NMR spectroscopy, and gel permeation chromatography. The epoxy resin cured by BIP-DOPO itself or its mixture with a commonly used bisphenol A-formaldehyde novolac resin (NPEH720) was prepared. The flame retardancy of the cured EP thermosets were studied by limiting oxygen index (LOI), UL 94 and cone calorimeter test (CCT), and the thermal properties by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results show that the cured epoxy resin EPNP/BI/3/1, which contains 2.2% phosphorus, possesses a value of 26.2% and achieves the UL 94 V-0 rating. The data from cone calorimeter test demonstrated that the peak release rate, average heat release rate, total heat release decline sharply for the flame retarded epoxy resins, compared with those of pure ones. DSC results show that the glass-transition temperatures of cured epoxy resins decrease with increasing phosphorus content. TGA indicates that the incorporation of BIP-DOPO promotes the decomposition of epoxy resin matrix ahead of time and leads to higher char yield. The surface morphological structures of the char residues reveal that the introduction of BIP-DOPO benefits to the formation of a continuous and solid char layer on the epoxy resin material surface during combustion.     

Epoxy-modified, unsaturated polyester hybrid networks

Hybrid polymer networks (HPNs) based on unsaturated polyester resin (UPR) and epoxy resins were synthesized by reactive blending. The epoxy resins used were epoxidised phenolic novolac (EPN), epoxidised cresol novolac (ECN) and diglycidyl ether of bisphenol A (DGEBA). Epoxy novolacs were prepared by glycidylation of the novolacs using epichlorohydrin. The physical, mechanical, and thermal properties of the cured blends were compared with those of the control resin. Epoxy resins show good miscibility and compatibility with the UPR resin on blending and the co-cured resin showed substantial improvement in the toughness and impact resistance. Considerable enhancement of tensile strength and toughness are noticed at very low loading of EPN. Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were employed to study the thermal properties of the toughened resin. The EPN/UPR blends showed substantial improvement in thermal stability as evident from TGA and damping data. The fracture behaviour was corroborated by scanning electron microscopy (SEM). The performance of EPN is found to be superior to other epoxy resins.     

活性酯固化环氧树脂物性的研究

主要对活性酯固化环氧树脂的吸水性、高耐湿性、电气特性等方面进行了研究,同时也对其树脂极性、交联结构、分子链运动等方面也进行了研究．     

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.     

含硅磷杂化物环氧树脂固化物性能研究

首先用γ-环氧丙氧基三甲氧基硅烷(KH-560)和亚磷酸二乙酯(DEP)反应的中间产物进行水解缩合反应,合成了一种含磷低聚硅氧烷杂化物.并用FTIR,NMR,GPC对其结构及分子量进行了表征.然后将含磷低聚硅氧烷引入到双酚A环氧树脂(E-54)制备硅磷杂化物环氧树脂的固化物.对这种含硅磷杂化物环氧树脂固化物的性能研究发现其极限氧指数为23～29,DSC分析结果玻璃化转变温度(Tg)可以达到204℃,失重5%的温度(Td)5%比纯E-54提高近20℃.该固化物具有阻燃性能,同时具有较好的热性能。     

Thermoanalytical study of an epoxy resin crosslinked with an aliphatic polyamine

Samples of the cured resins were prepared in the form of cast sheets. The concentration of the amine curing agent (triethylenetetramine) in the epoxy resin (bisphenol-A diglycidylether) was varied between 25 and 100% of the stoichiometric quantity. The cured resins were examined by differential scanning calorimetry, penetration under load as a function of temperature, and dynamic mechanical analysis. It is found that all of these methods provide a useful means of monitoring crosslinking through changes in the glass transition temperature. The dependence of some characteristic secondary relaxation temperatures, and the change in heat capacity at the glass transition, on the concentration of the amine were also investigated.