环氧化山桐子油的制备及其对双酚A型环氧树脂增韧改性研究

双酚A型环氧树脂（DGEBA）面临的主要问题是韧性较差。为了有效解决该问题,以山桐子油为原料制备环氧化山桐子油（EPIO）,以EPIO为增韧改性剂对DGEBA进行增韧改性,制备改性双酚A型环氧树脂（DGEBA/EPIO）,分别以甲基六氢苯酐（MHHPA）或聚醚胺D-400为固化剂对改性环氧树脂进行固化。采用傅里叶变换红外光谱（FTIR）、热重分析仪（TG）、动态机械性能分析仪（DMA）、万能力学试验机、全自动接触角仪和扫描电子显微镜（SEM）,对改性环氧树脂固化物的热学性能和力学性能进行表征。结果表明：EPIO可以明显提高双酚A型环氧树脂的韧性。当EPIO用量为DGEBA用量的5%,MHHPA固化后的DGEBA/EPIO的断裂伸长率可由纯树脂的2.73%提升至13.15%。添加EPIO也可以有效提升DGEBA的耐热性和疏水性。     

双酚A及端羧基丁腈橡胶对环氧树脂的增韧作用

以2-乙基-4-甲基咪唑为固化剂,分别以端羧基丁腈橡胶(CTBN)、CTBN/双酚A(BPA)或BPA为增韧剂增韧环氧树脂,研究了环氧树脂增韧体系的微观形貌和力学性能,考察了不同混料方式对CTBN增韧环氧树脂性能的影响。结果表明:CTBN增韧环氧树脂能使其固化物的冲击韧性有所提高,但其他力学性能降低;采用环氧树脂先与其进行预聚反应再经固化剂固化的方法能提高CTBN对环氧树脂的增韧效果;用CTBN/BPA为增韧剂不仅可以大幅度提高材料的冲击强度和扯断伸长率,而且可以提高弯曲强度与模量,克服了CTBN单一增韧导致材料强度下降的不足。BPA的加入可使环氧树脂固化物体系的弯曲强度、冲击强度和扯断伸长率有较大幅度的提高。     

PVC/MPOE/无机填料体系性能的研究

采用两步法制备了“核（刚性无机填料）-壳（热塑性弹性体）”结构的粒子，初步研究了PVC／MPOE（改性POE）／无机填料复合体系的力学性能。结果表明，当填充母料中滑石粉或碳酸钙的质量分数为70％时，PVC／MPOE／无机填料体系综合性能最好；CPE增加了PVC和MPOE的相容性，当其用量为11phr时．复合体系的冲击强度增加4．2倍，拉伸强度比PVC／POE体系增加2倍；流动改性剂改善了填充母料的加工性能，当其质量分数为2％时．填充母料的扭矩比不加流动改性剂的降低了25％，PVC／MPOE／无机填料复合体系的力学性能最佳。两步法比一步法改性的复合体系的冲击强度增加60％左右，而拉伸强度降低了10％。     

碳酸钙晶须表面改性研究

采用不同改性剂对碳酸钙晶须表面进行改性研究,研究了改性剂种类、改性剂加入时间、改性剂用量等因素对碳酸钙晶须改性效果的影响。结果表明,采用单一改性剂时以硬脂酸钠的改性效果最佳;采用复合改性剂（硬脂酸钠和十二烷基硫酸钠）时,其改性效果优于采用单一改性剂硬脂酸钠;改性剂在碳化反应前加入效果较好;改性剂最佳用量为4%（质量分数）。最优改性产品的活化指数为98%,沉降体积为4.41 mL/g。对比碳酸钙晶须改性前后的红外光谱图,发现改性后出现了明显的亚甲基,说明改性剂已经牢固地键合在碳酸钙上。     

碳纳米管改性醚酐型聚酰亚胺复合材料的制备和表征

采用固相机械共混方法利用碳纳米管（CNT）对醚酐型聚酰亚胺（PI）模塑粉进行改性,然后通过热模压工艺制备CNT改性PI复合模压材料（PI/CNT）,考察了不同CNT含量对材料力学性能、热稳定性能及导热性能的影响。测试结果表明,随着CNT质量分数的增加,在10%～40%范围内,PI/CNT复合材料主要力学性能呈现先增加后降低的趋势,但仍明显优于纯PI材料。当CNT质量分数为30%时,复合材料主要力学性能达到最佳,弯曲性能和拉伸性能提升至201和139 MPa,相比未改性PI分别提高了29%和10%;添加40%CNT后PI/CNT-40导热系数提高至0.83 W/（m·K）,是未改性PI材料的3.32倍;氮气氛围中PI/CNT-40材料5%热失重温度（T5%）提升至569℃,玻璃化转变温度（Tg）提高到282℃,显示出优异的导热性能、热稳定性和力学性能。     

高密度聚乙烯／废橡胶胶粉共混物的改性研究

采用新的改性体系三元乙丙橡胶（EPDM）、硅油、过氧化二异丙苯（DCP）对高密度聚乙烯／胶粉（HDPE／SRP）共混物进行了研究，探讨了各改性剂用量对共混物力学性能的影响。结果表明：EPDM用量为10－15份，硅油用量为4份，DCP用量为0.2份，共混物具有较好的力学性能。与未改性HDPE／SRP共混物相比，改性后共混物（EPDM为10份，硅油为4份，DCP为0.2份）的冲击强度和断裂伸长率分别可以大幅度提高，并且胶粉含量越少，提高的幅度越明显。扫描电镜观察结果表明：改性共混物中弹性体的分散和包覆结构是韧性提高的主要原因。     

羧基丁腈橡胶增韧改性环氧树脂复合材料的性能研究

采用反应性羧基丁腈橡胶(CTBN)对环氧树脂E-51(EP)进行了增韧改性,并制备了 CTBN/EP复合材料,研究了不同用量CTBN增韧改性环氧树脂复合材料的性能.结果表明,采用15份CTBN对EP进行增韧改性,并以2-乙基-4-甲基咪唑作固化剂在100℃下制备的CTBN/EP复合材料综合性能满足要求.     

端羧基丁腈橡胶改性酚醛树脂的性能研究

采用端羧基丁腈橡胶（CTBN）对酚醛树脂进行改性,研究CTBN用量对改性酚醛树脂力学性能的影响。酚醛树脂的拉伸强度、断裂伸长率随CTBN用量的增大而呈上升趋势,当CTBN用量为10％时,拉伸强度、断裂伸长率达到最大值,并利用扫描电子显微镜（SEM）、傅立叶转换红外光谱（FTIR）和热重法（TGA）对改性前后酚醛树脂的结构和热性能进行分析。结果表明,CTBN与酚醛树脂之间发生了化学反应,并且改性酚醛树脂的热性能有所下降。     

端羧基丁腈橡胶改性环氧树脂的结构与性能

以液体端羧基丁腈橡胶(CTBN)作为环氧树脂(EP)的增韧改性剂,制备了CTBN/EP预聚体和共混物。采用红外光谱(FT-IR)法对两者的结构进行了表征,并着重探讨了CTBN含量对预聚体和共混物力学性能的影响。研究结果表明:预聚体中EP的环氧基开环,并与CTBN反应,生成了酯键;随着CTBN含量的不断增加,CTBN/EP预聚体和共混物的杨氏模量、拉伸强度降低,冲击强度和断裂伸长率呈先升后降态势,说明适量CTBN的引入对EP具有良好的增韧效果;当固化温度较低时,CTBN/EP预聚体的冲击强度明显优于CTBN/EP共混物,而固化温度较高时两者的冲击强度无明显差异。     

羧基液体丁腈橡胶增韧改性环氧树脂研究

用羧基液体丁腈橡胶（CTBN）对环氧树脂（EP）进行改性,合成CTBN/EP预聚物。通过研究不同配比CTBN/EP体系的性能,确定CTBN对EP的增韧效果。     

Toughening of dicyandiamide-cured DGEBA-based epoxy resins by CTBN liquid rubber

Toughening of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin with liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer has been investigated. For this purpose six blend samples were prepared by mixing DGEBA with different concentrations of CTBN from 0 to 25 phr with an increment of 5 phr. The samples were cured with dicyandiamide curing agent accelerated by Monuron. The reactions between oxirane groups of DGEBA and carboxyl groups of CTBN were followed by Fourier-transform infrared (FTIR) spectroscopy. Tensile, impact, fracture toughness and dynamic mechanical analysis of neat as well as the modified epoxies have been studied to observe the effect of CTBN modification. The tensile strength of the blend systems increased by 26 % when 5 phr CTBN was added, and it remained almost unchanged up to 15 phr of CTBN. The elongation-at-break and Izod notched impact strength increased significantly, whereas tensile modulus decreased gradually upon the addition of CTBN. The maximum toughness of the prepared samples was achieved at optimum concentration of 15 phr of CTBN, whereas the fracture toughness (K _IC) remained stable for all blend compositions of more than 10 phr of CTBN. The glass transition temperature (T _g) of the epoxy resin significantly increased (11.3 °C) upon the inclusion of 25 phr of CTBN. Fractured surfaces of tensile test samples have been studied by scanning electron microscopic analysis. This latter test showed a two-phase morphology where the rubber particles were distributed in the epoxy resin with a tendency towards co-continuous phase upon the inclusion of 25 phr of CTBN.     

Correlation between stress-whitening and fracture toughness in rubber-modified epoxies

Fracture toughness of rubber modified epoxy systems was evaluated in relation to stresswhitening. The epoxy systems consisted of diglycidyl ethers of bisphenol A (DGEBA)-based epoxy resin, 4,4′ diaminodiphenyl sulphone (DDS) as curing agent, and carboxylterminated butadiene-acrylonitrile (CTBN) rubber. It was found that a peak value of fracture toughness occurs at a small amount of rubber content (∼ 4 phr) and closely corresponds to that of stress-whitening size. Other properties such as flexural strength and flexural modulus were also found to display maxima at a similar amount of rubber content. © 1996 John Wiley & Sons, Inc.     

Mechanical and tribological properties of epoxy modified by liquid carboxyl terminated poly(butadiene-co-acrylonitrile) rubber

Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin was modified using liquid carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) rubber. The liquid CTBN contents used ranged from 2.5 to 20 parts per hundred parts of resin (phr). Mechanical properties of the modified resins were evaluated and the microstructures of the fracture surfaces were examined using SEM technique. The changes in storage modulus and the glass transition temperature were also evaluated using dynamic mechanical analysis (DMA). The tribological tests were performed using a ball-on-disc tribometer. The worn surfaces and the ball counter-mates after tribological tests were investigated using optical microscope technique. The results revealed the influence of liquid CTBN content on mechanical and tribological properties, and also microstructure of the modified epoxy resins. Impact resistance increased whereas the storage modulus and the hardness decreased when the CTBN rubber was introduced to the epoxy network. The coefficient of friction of the CTBN-modified epoxy was lower than that of the neat epoxy. The CTBN content of lower than 10 phr was recommended for improving the wear resistance of epoxy resin. Changes in tribological properties of the CTBN-modified epoxy correspond well to those in mechanical changes, especially the toughness properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

促进剂ZBEC对天然胶乳胶膜的硫化及力学性能的影响

研究了二苄基二硫代氨基甲酸锌(ZBEC)、二乙基二硫代氨基甲酸锌(ZDC)以及氧化锌(ZnO)和硫化温度对天然胶乳配合胶膜的硫化及力学性能的影响。结果表明,随着促进剂ZBEC、ZDC、ZnO用量的增加和硫化温度的提高,天然胶乳配合胶膜的硫化速度显著提高,且与ZDC相比,ZBEC略快。当ZBEC用量从0.5份增加到1.5份时,定伸应力、拉伸强度、撕裂强度先增加后减小。当ZDC用量从0.5份增加到1.5份时,定伸应力、拉伸强度随之增大,撕裂强度先增大后减小。随硫化温度的提高,以ZBEC为促进剂的硫化体系及以ZDC为促进剂的硫化体系的硫化胶膜的定伸应力、拉伸强度及撕裂强度均先增大后减小。     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

Relationships between structure and mechanical properties of rubber-modified epoxy networks cure with dicyanodiamide hardener

Epoxy network systems based on DGEBA and dicyanodiamide (DDA) and modified with a low molecular weight rubber (CTBN) were prepared and characterized. The kinetics of the adduct formation is followed using GPC analysis. The phase separation of the rubber phase is evidenced with DSC and SEM for all samples up to 20% CTBN. The GPC analysis of the soluble fraction demonstrates a chemical modification of the network. The mechanical properties and specially the impact strength behavior are enhanced with CTBN, but exhibit a maximum for 15% CTBN. In connection with SEM of fracture surfaces, these results are discussed and both modification of the rubber morphology and decrease in crosslinking density are taken into account.     

Mechanical,thermal, and viscoelastic response of novel in situ CTBN/POSS/epoxy hybrid composite system

The present study focuses on the preparation of a novel hybrid epoxy nanocomposite with glycidyl polyhedral oligomeric silsesquioxane (POSS) as nanofiller, carboxyl terminated poly(acrylonitrile‐co‐butadiene) (CTBN) as modifying agent and diglycidyl ether of bisphenol A (DGEBA) as matrix polymer. The reaction between DGEBA, CTBN, and glycidyl POSS was carefully monitored and interpreted by using Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC). An exclusive mechanism of the reaction between the modifier, nanofiller, and the matrix is proposed herein, which attempts to explains the chemistry behind the formation of an intricate network between POSS, CTBN, and DGEBA. The mechanical properties, such as tensile strength, and fracture toughness, were also carefully examined. The fracture toughness increases for epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems with respect to neat epoxy, but for hybrid composites toughening capability of soft rubber particles is lost by the presence of POSS. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. The viscoelastic properties of epoxy/CTBN, epoxy/POSS, and epoxy/CTBN/POSS hybrid systems were analyzed using dynamic mechanical thermal analysis (DMTA). The storage modulus shows a complex behavior for the epoxy/POSS composites due to the existence of lower and higher crosslink density sites. However, the storage modulus of the epoxy phase decreases with the addition of soft CTBN phase. The T_g corresponding to epoxy‐rich phase was evident from the dynamic mechanical spectrum. For hybrid systems, the T_g is intermediate between the epoxy/rubber and epoxy/POSS systems. Finally, TGA (thermo gravimetric analysis) studies were employed to evaluate the thermal stability of prepared blends and composites. POLYM. COMPOS., 37:2109–2120, 2016. © 2015 Society of Plastics Engineers     

Si69在NR的低温长时间硫化配方中的应用研究

研究了Si69在天然橡胶（NR）的低温长时间硫化配方中对硫化胶硫化特性和力学性能的影响。结果表明：在不同的硫化温度下,随Si69用量的增加,硫化曲线平坦,返原率降低。在140℃正硫化时,硫化胶拉伸强度、定伸应力及撕裂强度较高。在145℃过硫化时,硫化胶力学性能及其保持率较高。当Si69用量为2.0份时,NR硫化胶综合性能较好。在不同硫化温度下,随硫化时间延长,NR硫化胶横向松弛时间缩短,交联密度提高。DMA结果表明,加入Si69后NR硫化胶的Tg升高。     

Morphology and mechanical properties of rubber modified aromatic-ether bismaleimide matrix resins

An aromatic ether bismaleimide (BMI) was modified by copolymerization with various CTBN and ATBN liquid elastomers. Dynamic mechanical (DMA), flexural, and SEM fractography studies indicate that cured specimens containing various amounts of the different elastomers have widely varying morphologies and properties. The experimental parameters of interest in this study included the type of elastomer reactive end group, elastomer acrylonitrile content, elastomer concentration, and cure reaction conditions. The ATBNs are clearly more compatible than CTBNs. CTBN modified compositions show a distinct, low temperature rubber phase mechanical loss dispersion, reduced modulus and ultimate strength values, and only slight improvements in elongation. Cured compositions with small amounts of ATBN elastomers (5 phr), however, show no reduction in modulus but improved elongation and ultimate strength values. The “rubber” domains in these systems are small, typically < 5 μm, and consist of copolymerized BMI and elastomer. DMA data for these systems show no distinct low temperature elastomer peak but a broad “interphase” loss dispersion covering a wide range of temperatures. Failure in the ATBN modified BMIs involves initiation of numerous microcracks with obvious crack deflection at the rubber particles. No cavitation of rubber particles occurs, as is frequently the case with the CTBNs.     

Preparation of a light color cardanol-based curing agent and epoxy resin composite: Cure-induced phase separation and its effect on properties

A light color cardanol-based epoxy curing agent (MBCBE) was synthesized from cardanol butyl ether, formaldehyde and diethylenetriamine. In comparison, a phenalkamine with a similar structure was also prepared. The chemical structures were confirmed by GC–MS and FTIR. The cure behaviors of diglycidyl ether of bisphenol A (DGEBA) with these two curing agents was studied by differential scanning calorimetry (DSC). The morphology, mechanical properties, thermal properties of the cured epoxies were also investigated. The DSC results indicated that MBCBE is less reactive than the phenalkamine. The morphology of the cured MBCBE/DGEBA consisted of cavities dispersed within a continuous epoxy matrix. The cavities markedly improved the lap shear strength and impact strength of the cured resin. Both the two cured resins indicated a two-stage decomposition mechanism. Compared with PKA/DGEBA, the weight loss of MBCBE/DGEBA at the first stage was mainly resulted from the dispersed phase in the epoxy matrix.