含磷胺类固化剂／环氧树脂固化体系性能研究

研究了含磷胺类固化剂/环氧树脂体系的阻燃性、反应活性及其固化过程。结果表明,含磷脂肪胺及芳香胺固化的环氧树脂均具有较好的阻燃性,其中含磷芳香胺在环氧树脂中尤具有提高相容性及较显著地降低固化温度的特点。此外,含磷胺类固化剂与环氧树脂的固化过程具有明显的阶段性,本文对不同温度阶段的反应机制作了讨论。     

芳胺固化双酚S环氧树脂动态力学性质的研究

用高分子材料动态力学谱仪研究了芳香二胺固化双酚S环氧树脂（BPSER）的固化过程,讨论了固化时间,固化温度及固化剂的摩尔比等因素对固化物玻璃化温度的影响,结果表明在理论固化剂用量条件下采用变温固化过程有利于反应的控制,并可以有效提高固化产物的玻璃化温度,文中进一步研究了利用双酚S环氧树脂对双酚A环氧树脂（BPAER）／芳胺体系的改性作用,表明BPSER与BPAER／芳胺固化体系能在较宽的比例范围内很好地相容,并能显著提高固化物的玻璃化温度。     

低熔点固化剂对环氧树脂性能的影响

研究低熔点固化剂(MOEA)对环氧树脂性能的影响,并和以4,4′-二氨基二苯甲烷(DDM)为固化剂的环氧树脂的性能进行对比。通过流变仪研究固化剂对环氧树脂体系的黏度-温度特性的影响;采用差示扫描量热法(DSC)研究固化剂对环氧树脂固化行为的影响;并通过万能材料试验机、动态热机械分析仪(DMA)和热失重分析仪(TGA)研究环氧树脂固化物的力学性能和热性能。结果表明,以MOEA为固化剂的环氧树脂(MOEA40)比以DDM为固化剂的环氧树脂(DDM30)具有更好的黏度-温度特性,在宽的温度区间(60~140℃)表现出低的黏度(0.2~3.5Pa·s)。固化工艺处理后,MOEA40的固化物表现出了优异的力学性能,其弯曲强度为147MPa,拉伸强度为89MPa,比DDM30的固化物的弯曲强度(134MPa)和拉伸强度(80MPa)分别提高了9.7%和11.2%。此外,MOEA40的固化物还具有高的玻璃化转变温度(168℃)和初始分解温度,在氮气条件下,其失重5%的温度为367℃。     

溴化丙烯酸松香环氧树脂的合成及固化物的阻燃性

以丙烯酸松香和液溴为原料,合成了溴化丙烯酸松香;再与环氧氯丙烷进行酯化反应、闭环反应,合成了溴化丙烯酸松香环氧树脂。采用固化剂4,4′-二氨基二苯砜(DDS)对产物进行了固化。用红外光谱(FT-IR)、核磁共振谱(1H-NMR)等对产物进行了表征。在适宜的条件下,合成的环氧树脂的环氧值为0.26mol/100g。燃烧实验、热失重和阻燃性实验证明,溴化丙烯酸松香环氧树脂/DDS固化物具有较好的阻燃性。     

用DSC技术研究环氧树脂体系的固化反应

本文用差示扫描量热法(DSC)研究了九种环氧树脂与六种固化剂的反应性。分析了环氧树脂的结构和固化剂的结构对各环氧树脂体系的固化反应的影响,并结合热失重分析(TG)研究了间苯二胺(m-PDA)和二氨基二苯基砜(DDS)与各种环氧树脂固化物的分解温度。      

降解废弃聚酯制备环氧树脂固化剂结构和性能的表征

研究了采用降解废弃聚酯产物制备的环氧树脂固化剂的结构和性能,并对其固化效果进行测试:用红外光谱表征了固化剂及固化产物的结构,探讨了环氧基团的反应过程;用热重分析对比了环氧树脂固化前后,热稳定性能的变化;在此基础上,对环氧树脂固化剂的固化效果进行对比测试,测定固化涂膜的抗冲击性能和铅笔硬度擦伤性能;并对比了固化膜的耐酸碱性能。研究表明,利用降解废弃聚酯制备的环氧树脂固化剂符合一般固化剂的要求,固化效果优良。     

膜组件浇铸用室温固化环氧树脂耐热胶粘剂的研究

针对耐高温膜组件的浇铸,研制了可室温固化环氧树脂耐热胶粘剂.探讨了环氧树脂、固化剂的种类以及固化剂和稀释剂添加量对胶粘剂性能的影响.考察了胶粘剂的粘接性能,并通过差示量热扫描仪(DSC)分析了固化反应过程中的放热情况及固化产物的耐热性.结果表明:双酚F树脂与A105固化剂配制的胶粘剂耐热性好,黏度低,粘接性能优良,当固化剂质量分数为28%时,固化物的玻璃化温度Tg可达91℃.     

低粘度环氧树脂固化剂的合成和性能研究

按照不同配比合成两种低粘度环氧树脂固化剂802、804,再分别与市售环氧固化剂5505配制成两种不同的混合固化剂806、901。分别与环氧树脂制备成环氧树脂固化物,测试其力学性能和硬度。讨论了不同的固化剂对树脂固化物力学性能的影响。并讨论了固化剂用量对固化物力学性能的影响,得出最佳固化剂用量。     

大体积环氧树脂的固化制备与性能研究

采用双酚A型E-51环氧树脂与三乙烯四胺固化剂进行固化反应,研究了大体积环氧树脂固化反应的温升变化规律及性能。结果表明:固化反应温度越高,环氧树脂胶液的固化时间越短且胶液黏度会随着固化反应温度的升高而降低;固化反应温度为49.2℃时,环氧树脂胶液黏度最低,为194mPa·s,流动性最好。大体积环氧树脂最佳实验配方为环氧树脂120kg、邻苯二甲酸二丁酯14.4kg、丙酮9.6kg、三乙烯四胺4.98kg、2,4,6-三(二甲胺基甲基)苯酚(DMP-30)0.24kg。     

表面官能团化多壁碳纳米管对环氧树脂固化过程的影响

以4,4‘-二胺基二苯砜(DDS)为固化剂,将表面化学修饰的MWNT作为填料加入到环氧树脂中,制备了MWNT/环氧树脂复合材料,采用非等温DSC研究了MWNT对环氧树脂固化过程的影响.结果表明,表面化学修饰的MWNT能促进环氧树脂的固化,降低固化反应的起始温度和峰顶温度;根据Kissinger公式和Crane经验方程推出了固化反应的表观活化能、反应级数、频率因子和速率常数;根据不同升温速率下的DSC固化反应放热曲线确定了固化工艺参数.     

Characterization of double network epoxies with tunable compositions

This article reports the processing and characterization of epoxy resins with near constant molar cross-link density prepared from sequentially reacted amine cross-linking agents. Stoichiometric blends of curing agents with compositions ranging from all polyetheramine to all diaminodiphenylsulfone (DDS) are reacted with an epoxy monomer in a staged curing procedure. The low reactivity of the aromatic amine permits the selective reaction of the aliphatic amine in the first stage. The residual aromatic amine and epoxide functionality are reacted in a second stage at higher temperature. Above approximately 50% DDS content the first stage produces sol glasses which have not reached the gel point. The glass transition temperatures of the partially cured networks decrease monotonically with increasing DDS content. The partially cured networks can be characterized thermally and mechanically above their respective glass transitions without significantly advancing the reaction of the residual DDS and epoxide functionality. The networks formed after the second stage of the cure exhibit thermal and mechanical properties intermediate between those of the two individual amine cured networks, according to composition. The blends do not show any evidence of phase separation across the entire composition range in either the partially cured or fully cured state.     

Acrylonitrile-capped poly(propyleneimine) dendrimer curing agent for epoxy resins: Model-free isoconversional curing kinetics,thermal decomposition and mechanical properties

Acrylonitrile-modified aliphatic amine adducts are often used as curing agents for room-temperature epoxy formulations (coatings, adhesives, sealants, castings, etc.), yet the curing reaction and properties of resultant epoxy systems still remain less fundamentally understood. Herein we systematically investigate our newly-developed acrylonitrile-modified multifunctional polyamine curing agent for bisphenol A epoxy resin (DGEBA): an acrylonitrile-capped poly(propyleneimine) dendrimer (PAN4). The impact of the molecular structure of PAN4 and a controlled poly(propyleneimine) dendrimer (1.0GPPI) on the curing reactivity, reaction mechanisms, thermal stability, viscoelastic response and mechanical properties of the epoxy systems are highlighted. Differential scanning calorimetry (DSC) confirms DGEBA/PAN4 shows markedly lower reactivity and reaction exotherm than DGEBA/1.0GPPI, and the model-free isoconversional kinetic analysis reveals that DGEBA/PAN4 has the generally lower reaction activation energy. To be quantitative, the progress of the isothermal cure is predicted from the dynamic cure by using the Vyazovkin equation. The isothermal kinetic prediction shows that DGEBA/PAN4 requires about 10 times longer time to achieve the same conversion than DGEBA/1.0GPPI, which agrees with the experimentally observed much longer gel time of DGEBA/PAN4. Subsequently, dynamic mechanical analysis shows that PAN4 results in the cured epoxy network with the lower β- and glass-relaxation temperatures, crosslink density, relaxation activation energy, enthalpy, entropy, but the higher damping near room temperature than 1.0GPPI. Finally, thermogravimetric analysis (TGA) demonstrates cured DGEBA/PAN4 is thermally stable up to 200 °C, and mechanical property tests substantiate that PAN4 endows the cured epoxy with much higher impact and adhesion strengths than 1.0GPPI. Our data can provide a deeper insight into acrylonitrile-modified aliphatic amine curing agents from the two good model compounds (PAN4 and 1.0GPPI).     

混合型固化剂对环氧树脂室温和低温力学性能的影响

研究了一种刚性和柔性胺混合型固化剂（芳香胺DETD和聚醚胺D-400）固化环氧树脂浇铸体的力学性能、材料断裂表面的微观形貌和玻璃化转变温度等性能。结果表明:当D-400加入量占固化剂总量的40%时,其室温拉伸强度呈现最大值,为82.52 MPa,弹性模量为2.30 GPa,与未加D-400的体系相比分别提高了6.3%和14.4%,其低温冲击强度提高了14%。对冲击断面形貌进行扫描电子显微分析表明:D-400的加入致使断口形貌变得粗糙,抗开裂能力得到提高。热分析实验结果显示,体系的玻璃化转变温度随着D-400含量的增加而降低。此外,还探讨了环氧树脂体系低温增韧机制。      

Prestressed double network thermoset: preparation and characterization

An innovative scheme to prepare Prestressed double network (PDN) epoxies is presented using a judicious combination of tetrafunctional curatives that have similar molecular weights but different reaction kinetics. A diglycidyl ether of bisphenol A epoxy monomer was reacted stoichiometrically and sequentially with various molar ratios of an aliphatic polyetheramine curing agent and an aromatic curing agent. Deformation was imposed on the partially cured resins after the formation of the first network, and postcuring was conducted at 50% compressive strain. Physical properties of the resulting PDN epoxies were examined using thermomechanical analysis, dynamic mechanical analysis, uniaxial tensile test, and plane-strain fracture toughness test. The application of prestress resulted in no changes in glass transition temperature, coefficient of linear thermal expansion, and Young’s modulus. However, a marked increase in fracture toughness is observed, accompanied by strong birefringence and visible roughness on the fracture surface.     

Effect of carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) concentration on thermal and mechanical properties of binary blends of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin

Six blend samples were prepared by physical mixing of epoxy resin with varying concentrations of liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer having 27% acrylonitrile content. The blend samples were cured with aromatic amine. A comparative study of Fourier-transform infrared (FTIR) spectra showed the modification as a result of chemical reactions between epoxide group, curing agent and CTBN. The tensile strength of cured blend samples decreased slightly from 11 to 46% where as the elongation-at-break showed an increasing trend with increasing rubber content, i.e., up to 25 phr, in the blend samples. Appreciable improvements in impact strength were also observed in the prepared blend systems. The glass transition temperature (T_g) of the epoxy resin matrix was slightly reduced on the addition of CTBN. The cured resin showed a two-phase morphology where the spherical rubber domains were dispersed in the epoxy matrix.     

端氨基树枝状大分子PAMAM/环氧树脂体系固化物的性能

以端氨基树枝状大分子PAMAM作为环氧树脂固化剂, 通过拉伸试验、 冲击试验、 DSC、 TGA研究了配比和固化温度对PAMAM与环氧树脂E-44的固化物性能的影响。 结果表明, 最佳固化温度为140℃, 但随着固化温度升高, 配比的影响表现出不同的规律: 80℃固化时, 最佳配比为0.47, 此时拉伸强度和冲击强度最佳, 玻璃化转变温度最高, 交联密度最大; 而在80℃以上固化时, 最佳配比逐渐向低配比方向移动, 140℃固化时, 最佳配比为0.28, 此时拉伸强度和冲击强度最佳, 玻璃化转变温度最高, 交联密度最大。固化物的密度和体积收缩率都是配比为0.47时最大, 而热稳定性都是配比为0.28时最佳。利用滴定法测定了固化物的固化度, 结果表明, 随着固化温度的升高, 低配比体系的固化度迅速提高并接近化学计量点配比体系的固化度。      

MOCA/环氧树脂体系的固化行为

采用FT-IR、DSC等方法研究了亚甲基双邻氯苯胺(MOCA)/环氧树脂体系的固化行为,并对其固化动力学行为进行了研究。结果表明,体系固化行为与固化温度、固化时间及固化剂的用量有密切关系。其中固化剂的用量以MOCA质量分数在26%~33%为宜。当MOCA含量在28.6%时,最佳固化条件为:由最佳起始固化温度165℃左右缓慢升温到208℃左右恒温固化,最后在258℃左右恒温一段时间使树脂充分固化。其固化反应方程为:-dα/dt=k(1-α)1.15。     

耐高低温环氧有机硅胶黏剂的力学性能研究

介绍了一种研制的室温固化、耐高温、耐低温环氧有机硅胶黏剂.通过对胶黏剂的剪切强度分析,探讨了原料配比,偶联剂等因素对环氧有机硅胶黏剂力学性能的影响.研究表明:增韧剂在胶黏剂中含量适当时(质量比25%),能与固化剂充分反应,有机硅与环氧树脂也能获得较好的相溶性,制备的环氧有机硅胶黏剂的综合性能较优;硅烷偶联剂能改善胶膜界面层的胶接强度,提高环氧有机硅胶黏剂的剪切强度.