二元胺/环氧树脂增韧BMI树脂的研究

以4,4＇-二氨基二苯甲烷型双马来酰亚胺为基体,用二元胺和环氧树脂进行增韧,利用红外光谱、示差扫描量热仪及热失重分析仪研究了改性树脂的结构、反应程度和热稳定性．结果表明,二元胺和环氧树脂固化双马来酰亚胺体系中,随固化温度的提高,产物的交联密度升高．与纯组分的双马来酰亚胺固化体系相比较,改性后体系的分解温度降低,柔韧性增加。     

Non-isothermal curing kinetics and thermal properties of benzoxazine-phenolic copolymers

Using novolac phenolic resin, aniline and formaldehyde as raw materials, benzoxazine-phenolic copolymers with different percentages of benzoxazine rings were prepared. FT-IR was adopted to characterize the molecular structure of the novolac-type phenolic resin and the benzoxazine-phenolic copolymer BP31. In order to understand the curing process of the copolymers, the curing behavior and curing kinetic characteristics were studied by differential scanning calorimetry (DSC), and the catalytical effect of phenolic hydroxyl on the curing behavior of copolymers was investigated. To investigate the thermal properties of this resin, the thermal degradation behaviors of the cured samples were studied by thermal gravimetric (TG) method, and glass-transition temperatures (T _g) of the cured copolymers were also evaluated by DSC. The dynamic Ozawa method was adopted to determine the kinetic parameters of the curing process as well. The activation energy is 78.8 kJ/mol and the reaction rate constant is in the range from 40.0 to 5.2 (K/min) ⁿ according to reaction temperatures. The Ozawa exponent decreases from 2.4 to 0.7 with the increase of reaction temperature, and curing mechanism is expounded briefly according to the results. TG result shows that the highest char yield of copolymers is 50.3%. The highest T _g of copolymers is 489 K, which is much higher than that of pure benzoxazine resin. Foundation item: Project (20050106) supported by the Key Science and Technology Item of Guangdong Province, China     

双马来酰亚胺与环氧改性氰酸酯固化工艺研究

研究了双酚A型二氰酸酯树脂（BCE）与双马来酰亚胺树脂（BMI）、环氧树脂（EP）的共聚反应；通过差示扫描量热法（DSC）对其性能进行了研究和表征。实验发现，BMI与BCE的反应性不如EP与BCE的反应性好，故采用先使BMI与BCE反应，然后再加入EP的方法得到了较为良好的树脂浇铸体样品。用FTIR对树脂的固化进行跟踪分析。研究结果表明，体系的固化反应中包含BMI自聚合反应、BCE自聚合反应、BCE与BMI共聚反应、BCE与EP共聚反应等。     

含硅环氧树脂的制备及其固化动力学研究

采用二苯基硅二醇与邻甲酚醛环氧树脂在SnCl₂ 催化作用下合成了含硅环氧树脂(CNE - Si),并用FT - IR、1 H - NMR对产物进行了结构表征,采用 TGA分析了含硅环氧树脂的热稳定性。结果表明,- Si -基团的引入大大提高了环氧树脂的热稳定性。采用非等温 DSC方法探讨了含硅环氧树脂的固化反应过程,用T -矱外推法确定了含硅环氧树脂在线性酚醛树脂固化剂作用下的固化工艺参数,即：起始固化温度为 110℃,最快的固化反应温度为125℃,后固化温度在170℃附近。用Kissinger和Ozawa法进行了动力学研究,得到了其固化反应活化能、反应级数等动力学参数,为含硅环氧树脂的应用提供了基础数据。     

聚酯增韧双马来酰亚胺的研究

采用不饱和聚酯和双马来酰亚胺反应,合成了一种改性双马来酰亚胺树脂。该树脂体系具有较好的成型工艺性能及韧性好、易于固化成型等特点。讨论了原料配比对改性树脂冲击韧性和耐热性的影响,通过不同升温速率下的ＤＳＣ图谱确定了该体系的固化工艺参数,测定了固化树脂的热性能、机械性能,也初步测出改性树脂的单向纤维复合材料的力学性能。     

新型改性水性聚苯胺-环氧树脂涂料的制备

通过化学结构改性法分别在环氧树脂E-44的一端引入双键,另一端引入羟基,用不饱和有机酸中和,得到水性环氧树脂.研究了单体配比、反应温度对反应转化率的影响,确定了水性环氧树脂制备的最佳条件为：n（N-甲基烯丙基胺）∶n（二乙醇胺）∶n（E-44）=1.00∶1.05∶1.00;反应温度60℃;反应时间4 h.同时研究了水性环氧树脂及固化剂不同配比对涂层性能的影响,确定了水性环氧树脂乳液和固化剂的最佳质量比为2∶1.     

环氧树脂/纳迪克酸酐/乙酰丙酮铬体系固化反应动力学研究

以环氧树脂为主体树脂,酸酐为固化剂,乙酰丙酮铬( Cr(acac)3)为促进剂,通过不同升温速率测定固化体系的DSC曲线来研究该体系的反应动力学历程.运用Kissinger、Ozawa方法计算出固化体系在不同促进剂用量下的表观活化能Ea及指前因子A,结合Crane公式求出反应级数n值近似为1.结果表明:适量的Cr(ac...     

磷氮阻燃固化剂对环氧树脂阻燃性能的影响

为了提高环氧树脂固化体系的阻燃性能,以1,3-丙二胺(DPAN)和苯膦酰二氯(PPDC)为主要原料合成一种新型磷氮反应型阻燃固化剂(PPDPA),对合成化合物的组织结构和热性能进行了表征.以不同比例PPDPA为固化剂,制备一系列具有不同磷含量的阻燃环氧树脂,并对其进行热性能分析和阻燃性能测试.结果表明,添加PPDPA的环氧树脂体系的500 ℃残炭明显高于EP/DPAN体系,且残炭表面磷碳层具有明显的发泡现象.当磷的质量分数达到2.12%时,EP-2样品成功通过UL94 V-0阻燃等级测试,LOI值达到28.3%,PPDPA在环氧树脂材料中表现出了良好的阻燃性能.     

环氧树脂／粘土纳米复合材料固化反应动力学及其性能的研究

用十六烷基三甲基溴化铵直接处理钙基蒙脱土（MMT）,采用非等温DSC法研究了E-51/MMT/DDM体系的固化反应动力学,并用Kissinger方法求得其表观活化能（△E）为49．66kJ／mol,根据Crane理论计算得到反应级数为0．88,确定了使用DDM作为固化剂的固化反应条件,并且测定了复合材料的力学性能,最后又采用非等温DSC法研究了环氧树脂,粘土纳米复合材料的热性能,研究结果表明纳米复合材料具有较高的玻璃化转变温度。     

三氧化二铝对环氧树脂固化动力学及 热降解动力学的影响

采用热分析法研究了高含量Al₂O₃填料对环氧树脂（E51）/二氨基二苯甲烷（DDM）体系的固化表观活化能、热降解动力学和性能的影响.非等温差式扫描量热法（DSC）固化动力学研究表明,加入Al₂O₃体系的反应活化能由51.49 kJ/mol降低至48.12 kJ/mol;用n级非等温动力学法分析获得了固化反应的动力学参数.利用热重分析研究了环氧固化物体系的热降解动力学,用FWO方法计算固化物降解活化能结果表明,Al₂O₃粉体对E51/DDM体系初始分解活化能影响不大,当降解率达到30%时,Al₂O₃粉体对E51/DDM体系分解有明显的抑制作用.热重红外联用测试结果表明,甲烷、羰基化合物、胺和双酚A是E51/DDM热分解过程中的主要产物,Al₂O₃粉体能提高E51/DDM体系的热稳定性.动态热机械研究表明,Al₂O₃的加入增大了环氧树脂固化产物的储能模量.DSC测试结果表明,Al₂O₃加入后,体系的玻璃化转变温度由114.16℃提高到121.51℃.     

纳米氧化铝纤维改性酚醛树脂及性能

采用原位法成功合成了摩擦材料用纳米氧化铝纤维改性酚醛树脂.利用示差扫描量热分析（DSC）对合成树脂的固化反应及其动力学进行了研究,结果表明：纳米氧化铝纤维可降低酚醛树脂的固化温度和表观活化能.通过热重分析（TGA）对合成树脂的热性能进行了研究,结果显示,纳米氧化铝纤维对酚醛树脂热性能的影响较小.通过冲击强度测试和断口形貌分析研究了合成树脂的韧性,结果表明,纳米氧化铝纤维对酚醛树脂韧性有显著影响;随着纳米氧化铝纤维含量的增加,改性树脂的冲击强度先增大,后减小,在含量为1.8%时,达到最大值,与纯酚醛树脂相比,提高了约91%.     

Cure behaviors and water up-take evaluation of a new waterborne epoxy resin

Cure behaviors and water up-take evaluation of a low cost, ecofriendly and water soluble epoxy resin prepared by reaction between epichlorohydrin and PEG400, PEG600 and PEG1000, respectively, were investigated using non-isothermal differential scanning calorimetry (DSC) and gravimetrical method, respectively. Factors affecting the cure behaviors as well as water up-take of waterborne epoxy resins, such as amount of triethylenetetramine (TETA) and triethylene diamine (TEDA), PEG molecular weight, curing temperature, were systematically investigated. The prepared water soluble epoxy resins can be cured under room temperature with the shape of the curing curves similar to that expected for an autocatalytic reaction.     

间甲苯胺改性双氰胺固化环氧树脂的DSC研究

采用化学改性合成的间甲苯胺改性双氰胺衍生物作为环氧树脂潜伏性固化剂，通过差示扫描量热法（DSC）研究了间甲苯胺改性双氰胺／环氧树脂E-44体系的固化反应。结果表明，间甲苯胺改性双氰胺与双氰胺相比，具有较高的固化反应活性，显著降低了固化反应的温度，而且间甲苯胺改性双氰胺／环氧树脂E-44体系也具有较好的贮存稳定性。同时间甲苯胺改性双氰胺／E-44环氧树脂体系的动力学研究也表明该固化体系的活化能明显降低，固化反应活性与未改性前相比，有很大程度的提高。     

COMPARISON OF THE E44 EPOXY RESINS IN DIFFERENT CONTENTS OF CURING AGENT BY MICROWAVE AND THERMAL CURING METHODS

This paper discusses the fundamental principle of microwave heating, and based on the advantages of microwave heating, use maleic anhydride as curing agent. The technology of microwave curing E44 epoxy resins is investigated, the mechanical properties of cured epoxy resin samples in different contents of curbing agent by microwave and thermal curing methods are measured respectively, and then some experimental results for which are obtained. At last, this paper analyses why microwave curing can improve mechanical property of epoxy resin.     

聚醚胺/环氧树脂固化体系的动力学研究及性能

以聚醚胺类化合物作为环氧树脂的固化剂,得到的固化体系相对脂肪胺及简单二胺为固化剂的固化体系具有良好的弯曲强度和抗冲击性能。并采用DSC测试方法研究了环氧树脂与聚醚胺的固化进程动力学参数,由Kissinger方程得出固化反应的活化能E为51.91kJ/mol,频率因子A为3.214×106 s-1,由Crane方程得出固化反应级数n=0.887 9,并得到固化反应的动力学方程,-dα/dt=k（1-α）0.887 9,其中k=3.214×106exp（-6 243.7/T）。     

4,4’-二氨基二苯砜固化环氧树脂/蒙脱土纳米复合材料反应动力学的研究

选择4,4’-二氨基二苯砜（DDS）作为固化剂,采用非等温DSC法研究了双酚A缩水甘油醚型环氧树脂（E-51）/有机蒙脱土（MMT）纳米复合材料的固化反应动力学,根据Kissinger方程计算出该反应的表观活化能（ΔE）为59.91 kJ/mol,基于Crane方程计算得到该反应的反应级数为0.89,表明该反应为一复杂反应,根据固化反应动力学测试结果确定了E-51/DDS/MMT体系固化成型工艺.     

聚合物基减摩耐磨复合材料研究

利用4，4’-二氨基二苯甲烷(DDM)、环氧树脂(E-51)和改性剂A对双马来酰亚胺(BMI)树脂进行增韧改性，通过分析比较浇铸体的力学性能和耐热性能确定了改性树脂的最佳配方。并将此改性树脂与超高分子量聚乙烯(UHMW-PE)粉末进行共混，加入减摩耐磨填料，采用模压成型工艺制备了减摩耐磨复合材料，确定了模压成型工艺参数。测试了材料在不同温度的摩擦磨损性能，表明在合适的使用温度下具有优良的耐摩擦磨损性能。并运用扫描电镜(SEM)对材料磨痕进行了观察，探讨了摩擦磨损机理。     

酚醛树脂固化的非模型拟合动力学研究

根据不等温差示扫描量热曲线,采用非模型拟合动力学法对酚醛树脂的固化动力学进行了研究。基于Fried-man,Flynn-Wall-Ozawa和Kissinger-Akahira-Sunose 3种模型计算得到了固化速率及活化能与固化度的关系,进而对此树脂体系的固化反应阶段及固化行为进行了分析,并对等温固化行为进行预测。结果表明,固化反应逐渐从自催化反应机理转变为n阶反应机理,与模型拟合法研究的结果基本吻合。对Friedman,Flynn-Wall-Ozawa,Kissinger-Akahira-Sunose 3种动力学方法进行比较发现,3种方法都显示了较好的拟合结果。其中,Flynn-Wall-Ozawa和Kissinger-Aka-hira-Sunose两种方法的结果十分接近,并能对固化行为进行准确地反映。     

Preparation and properties of Nano-SiO2/TDE-85/BMI/BADCy composites

A new type of the nanometer particles and epoxy/bismaleimide-triazine nanocomposites were prepared using a nanometer silica (nano-SiO2), a 4,5-epoxycyclohexane 1,2-dicarboxylic acid dilycidyl (TDE-85) epoxy resin, a 4,4’-bismaleimidodiphenymethane (BMI) and a bisphenol a dicyanate (BADCy). The properties of nano-SiO2/TDE-85/BMI/BADCy composites, such as mechanical and thermal properties, were systemically investigated in detail by mechanical measurement, scanning electron microscope (SEM), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). The experimental results showed that the addition of the appropriate amount of nano-SiO2 could improve the impact strength and the flexural strength of the nano-SiO2/TDE-85/BMI/BADCy composites. Simultaneously, the thermal stability of the blends was found to be higher than that of the TDE-85/BMI/BADCy copolymers.     

CHARACTERIZATION OF UP RESIN/GLASSFIBRE ADHERSIVE INTERFACE MICROSTRESS

A fibre-optic interface stress sensor was used to characterize the mechanical property of UP resin/ glass fibre adhersive interface. During the adhersion agent curing, the contract stress accompanies with dimension contracting, the thermal stress which is produced by the changes of environment temperature caused by curing heat and the procedure of interface stress transmitting were all traced and determined, the micro mechanical properties of UP resin/glass fibre adhersive interface are determined. Also, the longchain softness couple agent has effcet on decreasing the stress concentration of UP resin/glass fibre adhersive interface and enhance the interface adhersive strength is verified.