环氧树脂的氨基硅油改性研究

利用氨基硅油对环氧树脂胶粘剂体系进行了改性,分析了氨基硅油与环氧树脂共聚反应温度、反应时间、环氧树脂与氨基硅油的配比、氨基硅油的氨值和黏度对改性胶粘剂力学性能的影响。结果发现,氨基硅油改性的环氧树脂其韧性大幅度提高。     

环氧/CTBN改性BPF胶粘剂的制备及性能研究

以BPF(硼酚醛)树脂为基体,经环氧树脂和CTBN(端羧基丁腈橡胶)化学接枝改性制备胶粘剂,并采用FT-IR(傅里叶红外光谱)、TGA(热重分析)等方法,研究了胶粘剂的结构和固化过程,考察了胶粘剂不同温度下的粘接强度和耐热性。研究结果表明:CTBN成功接枝到BPF上,改善了其韧性;经CTBN接枝改性后BPF胶粘剂的室温粘接强度由8.34 MPa提升至17.73 MPa,同时耐热性无明显下降;而环氧/CTBN/BPF三元体系胶粘剂的室温粘接强度可达26.21 MPa,但耐热性能有所下降。     

多孔材料用耐高温软质环氧胶粘剂的制备与性能

为实现有机硅多孔材料的软性粘接,以α,ω-二羟基聚二甲基硅氧烷(聚硅氧烷)和CTBN(端羧基液体丁腈橡胶)对双酚A型E-44环氧树脂进行化学改性,制备了一种新型的多孔材料用耐高温软质胶粘剂。研究结果表明:当m(聚硅氧烷)∶m(E-44)=1∶8且m(CTBN)∶m(聚硅氧烷改性环氧树脂)=1∶4时,胶粘剂剪切强度可达40.8 MPa,拉伸强度可达0.29 MPa,Td5%高达240℃,耐腐蚀性良好。在保证粘接强度的同时,该胶粘剂可使粘接处达到与基体相似的韧性与硬度,提高了长期使用性。     

动荷金属结构胶的研制及应用

同种或异种金属材料的粘接,用以补充铆焊工艺和机械装配,得到了越来越广泛的应用。本文从改性环氧树脂胶粘剂粘接机理入手,论述了主剂与改性剂的筛选,粘接工艺过程用正交表确定胶粘剂最佳配比以及结构胶的物理力学性能与应用等。系统试验表明:CTBN及DMP—30的引用是环氧结构胶粘剂改性至关重要的条件。     

低模量硫化硅橡胶粘接研究

采用sol—gel工艺自制的SiO2补强增韧环氧树脂作为胶粘剂,对低模量硫化硅橡胶与金属或复合材料进行粘接试验,分析胶粘剂中SiO2理论含量及粘接工艺对粘接性能的影响,并把硫化硅橡胶放在改性环氧树脂中进行溶张试验,探索胶粘剂对硅橡胶的粘接机理、结果表明,随着SiO2先驱体-有机硅烷含量的增加,硅橡胶的溶胀程度提高改性环氧树脂胶粘刺能浸入硅橡胶的表层,对硅橡胶具有良好的亲和力。用该胶粘剂对硅橡胶与金属或复合材料进行粘接时,取得了良好的粘接效果。     

新型增韧改性环氧胶粘剂问世

天津城建学院与河北大学联合攻关，采用液体丁腈-40橡胶对环氧树脂进行增韧，研制出可室温较快固化、剪切强度较高的改性环氧胶粘剂。环氧树脂与液体丁腈橡胶的最佳质量比为10：1，制得的结构胶粘剂室温24h固化后，具有良好的力学性能，室温剪切强度高达22．4MPa，一般的丁腈橡胶虽然也能增韧环氧树脂，但改性后的粘接强度提高不大。端羧基液体丁腈橡胶（CTBN）对环氧树脂增韧效果很好，可是原料价格太高，受到制约。而采用液体丁腈-40橡胶，对E-44环氧树脂／低分子聚酰胺体系进行增韧，可得到室温固化、剪切强度较高的改性环氧胶粘剂。     

低膨胀系数环氧胶粘剂的制备与性能研究

文章设计选用低膨胀环氧树脂和固化剂为胶粘剂主体成分,研究了CTBN、核壳粒子增韧剂、超细钨酸锆填料对粘接性和膨胀性的影响,分析测定了低膨胀胶粘剂的粘度特性、物理性能、粘接性能和热膨胀特性。结果表明, CTBN能显著提高胶粘剂韧性,但热膨胀系数(CTE)显著升高,而核壳粒子增韧剂在提高剥离韧性同时, CTE无显著升高。超细钨酸锆填料能大幅降低环氧胶粘剂的CTE。制备的低膨胀环氧胶粘剂固化后剪切强度17.4MPa,玻璃化转变温度以下CTE在12.1ppm/℃,具有良好的耐温度循环和湿热老化性能。     

飞机天线粘接密封用胶粘剂的研制

环氧树脂E-51和酚醛环氧树脂F-51以质量比1:1配制成混合树脂,以占环氧树脂15%的CTBN为增韧改性剂,制成预聚物,再与改性芳香胺固化剂、邻甲酚缩水甘油醚、耐高温填料等配合,配制成HT-737耐高温胶粘剂,满足了某军用飞机天线中聚苯硫醚与镀银黄铜板的粘接密封。     

高性能环氧树脂胶粘剂的研制

以MTHPA(甲基四氢苯酐)为固化剂,以活性稀释剂(CE-793)为稀释剂,分别以CTBN(端羧基丁腈橡胶)和聚硫橡胶为增韧剂,再辅以扩链剂(D-248)改性混合环氧树脂(JP-80/E-51),制得了两种高性能环氧树脂胶粘剂,分别命名为K胶和B胶;并对胶粘剂的变温拉伸剪切强度、凝胶化时间、吸水性、介电性能进行了测试。研究结果表明:以CTBN为增韧剂的胶粘剂综合性能更好。     

室温固化耐热环氧树脂结构胶粘剂

介绍了一种液体端羧基丁氰橡胶 (CTBN)改性环氧树脂为主体 ,以改性聚硫橡胶为固化剂的结构胶粘剂 ,强度高 ,韧性好 ,室温固化 10天 ,室温剪切强度 2 5 .9MPa ,12 0℃剪切强度为 14 .9MPa ,室温剥离强度 6 .0kN/m ,综合性能优异。用于航空、航天工业耐热结构部件的粘接     

端羧基液体丁腈橡胶改性环氧结构胶的研究

采用端羧基液体丁腈橡胶(CTBN)增韧环氧树脂,制备了双组分室温固化环氧结构胶。利用傅里叶变换红外光谱仪(FTIR)、微机控制万能材料试验机及扫描电镜(SEM)对固化过程、固化产物剪切强度及固化产物微观形态进行了表征。该胶树脂甲组分的最佳制备条件如下:环氧树脂与CTBN的质量比8∶1,反应温度200℃,保温时间2.5 h。该胶在室温下固化24 h,室温剪切强度可达29.24 MPa,耐介质性能良好,CTBN改性环氧树脂增韧效果显著。     

F-992抗蠕变光学结构胶

以改性环氧树脂为主粘料,用反应性端羧基丁腈橡胶（CTBN）为增韧剂,与改性多元胺端氨基聚醚固化剂配制成具有较高交联密度的光学结构胶。因较高的交联密度和使用耐热改性剂,提高了耐热性;CTBN与环氧树脂进行预反应,并加入气相法白炭黑,提高了胶液的贮存稳定性和粘接强度。制备的光学结构胶拉伸剪切强度15．7MPa,压缩剪切强度25．4MPa,常温条件下蠕变值小于2英寸,表现出良好的粘接强度和耐热、耐冲击振动及抗蠕变性。     

Carboxyl‐terminated butadiene acrylonitrile rubber/epoxy polymer alloys as damping adhesives and energy absorbable resins

Carboxyl‐terminated butadiene acrylonitrile (CTBN) liquid rubber/epoxy (diglycidyl ether of bisphenol‐A: DGEBA) / diamino diphenyl methane (DDM) resins, in which CTBN was 60 wt % as the major component, were formulated to evaluate the damping and adhesive properties. In cases where acrylonitrile (AN) was 10～18 mol % as copolymerization ratio in CTBN, the blend resins showed micro‐phase separated morphologies with rubber‐rich continuous phases and epoxy‐rich dispersed phases. The composite loss factors (η) for steel laminates, which consisted of two steel plates with a resin layer in between, depended highly on the environmental temperature and the resonant frequencies. On the other hand, in the case where AN was 26 mol % in CTBN, the cured resin did not show clear micro‐phase separation, which means the components achieve good compatibility in nano‐scale. This polymer alloy had a broad glass‐transition temperature range, which resulted in the high loss factor (η > 0.1) for the steel laminates and excellent energy absorbability as the bulk resin in a broad temperature range. Also the resin indicated high adhesive strengths to aluminum substrates under both shear and peel stress modes. The high adhesive strengths of the CTBN/epoxy polymer alloy originated in the high strength and the high strain energy to failure of the bulk resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of the addition of aramid-CTBN block copolymer on adhesive properties of cured epoxy resins modified with CTBN

To improve the bond strength of carboxy-terminated butadiene acrylonitrile (CTBN)-modified epoxy resin, aramid-CTBN block copolymer was used as an additive to a bisphenol-A-type epoxy resin modified with CTBN. With the addition of aramid-CTBN block copolymer, the fracture energy values of the adhesive joints were more than twice that of the CTBN-modified system and about twelve times that of the unmodified system. Observations of the adhesive layers using an optical microscope revealed that the width of the damage zone near the crack-tip in the double cantilever specimen increased with the addition of the aramid-CTBN block copolymer. TEM micrographs showed that the diameter of the CTBN-dispersed phases decreased and a number of fine CTBN phases were dispersed in the epoxy matrix with the addition of the block copolymer. It is concluded that addition of the block copolymer leads to an increase in the dispersibility of the CTBN elastomer into the epoxy matrix and thus the bond strength of the block copolymer-added system is increased due to the increase in the area of the damage zone and the occurrence of shear deformation of the epoxy matrix.     

粘接聚苯硫醚膜室温固化耐高温环氧胶黏剂

以环氧E-51和环氧TDE-85为主体树脂,三乙烯四胺和三乙醇胺为固化剂,并加入双马来酰亚胺(BMI)、液体端羧基丁腈橡胶(CTBN)等试剂,研制了用于粘接聚苯硫醚膜(PPS)与石油输送管道的室温固化耐高温环氧胶黏剂。通过TG、DSC和耐介质性测试,结果表明:所研制的胶黏剂具有较好的热稳定性和优良的耐油性,适用于石油管道这种高温的油性环境,有望在石油工业中得到应用。     

环氧树脂胶在光学部件粘接中的应用

主要介绍以液体端羧基丁腈橡胶(CTBN)改性的环氧树脂为主体，配之以改性剂、偶联剂以及固化剂组成胶粘剂应用于光学部件上，并根据它的参数，运用有限元分析方法对光学件在使用此胶粘剂后的变形进行分析。     

挠性覆铜板用高剥离强度环氧胶的制备及性能

用液体端羧基丁腈橡胶(CTBN)对环氧树脂E-51进行改性,合成了CTBN/E-51预聚物。采用红外光谱、示差扫描量热仪、万能试验机及电子显微镜表征了产物结构,确定了固化工艺,研究了预聚反应温度、时间,CTBN含量对环氧胶剥离强度的影响,并观察了剥离断面的形貌。结果表明,CTBN质量分数为15%,预聚温度为90℃,反应时间2 h所制得环氧胶的剥离强度最高,其粘接强度随预聚时间的增加而增加。该胶可满足挠性覆铜板的生产需要。     

聚酰亚胺改性环氧树脂胶黏剂的研究

环氧树脂和聚酰亚胺的性能具有一定的互补性,用聚酰亚胺对环氧树脂进行改性可以综合两者的优点,得到具有良好机械性能和粘结强度的耐高温环氧胶黏剂。用聚酰亚胺中间体聚酰胺酸(PAA)对环氧树脂(EP)进行改性,加入一定量的端羧基丁腈橡胶(CTBN),用4,4’-二氨基二苯砜(DDS)做固化剂,先在一定温度下进行预反应,然后在一定的工艺条件下固化,通过调节不同的配比,得到具有较高耐热性的环氧树脂胶黏剂。具体研究了PAA用量、DDS用量、CTBN用量对胶黏剂力学性能的影响,筛选较好的配方。采用热重分析仪(TG)和差热扫描量热仪(DSC)等研究胶黏剂的耐热性能,并利用傅立叶变换红外光谱(FTIR)对各树脂进行结构表征,采用扫描电镜(SEM)对固化后胶黏剂的断面形貌进行了分析。     

Effect of elastomer modification on the adhesive characteristics of maleimide‐functional phenolic resins

The effect of addition of elastomeric modifiers on the adhesive properties like lap shear strength and T‐peel strength of an addition curable, maleimide functional novolac phenolic resin (PMF), self‐cured and cocured with a novolac epoxy resin, was studied using aluminium adherends. The modifiers used were (1) two grades of carboxyl terminated butadiene acrylonitrile copolymer (CTBN) of different molecular weights, (2) a low molecular weight, epoxidized hydroxyl‐terminated polybutadiene, and (3) a high molecular weight acrylate terpolymer containing pendant epoxy functionality. The adhesive properties, when examined as a function of the varying concentrations of the additives, ranging from 10 to 30 parts per hundred parts (phr) of the resin, were found to depend on the nature of the matrix being modified as well as on the nature and concentration of the elastomer. The adhesive properties at ambient temperature of the self‐cured, highly brittle PMF resin were dramatically improved by the inclusion of all the elastomers, the increase being substantial in the case of high molecular weight CTBN. For the more rigid, less ductile, epoxy‐cured PMF system, the adhesive properties were marginally improved by the high molecular weight CTBN, whereas the other elastomers were practically ineffective. For both self‐cured and epoxy‐cured PMF systems, the inclusion of these elastomers generally decreased the high‐temperature adhesive properties, implying impairment of thermal characteristics, evidenced also from their dynamic mechanical spectra. The presence of phase‐separated elastomer particles in the modified systems has been evidenced from scanning electron micrographs. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2321–2332, 1999