基于氢化端羟基聚丁二烯和儿茶酚基团的聚氨酯的自修复及粘接性能研究
（1.郑州大学化工学院，河南郑州 450001；2.郑州大学化学学院，郑州市弹性密封材料重点实验室，河南郑州 450001)
【摘 要】采用3,4-二羟基苯甲醛（DBA）和丝氨醇合成出含有儿茶酚基团的扩链剂，与氢化端羟基聚丁二烯（HHPB）、异佛尔酮二异氰酸酯（IPDI）合成了线型聚氨酯（HHPB-DS）。研究结果表明：聚烯烃性质的HHPB比聚四亚甲基醚（PTMEG）使微相分离程度更高，HHPB-DS的黏流转变温度为81℃，既表现出自修复特性又能用于热熔粘接；儿茶酚基团的引入赋予该材料对多种基材的良好粘接，尤其是对提升钢板粘接强度的效果显著；HHPB低表面能的特性起到保护硬段相作用，降低水分子对儿茶酚基团和氨基甲酸酯基间氢键的干扰作用，使得浸泡水3 d的粘接基材仍然能保持其粘接强度。
【关键词】儿茶酚；氢化端羟基聚丁二烯；耐水；自修复；粘接
新型扩链剂及其改性水性聚氨酯丙烯酸酯的制备与性能研究
罗青宏1，吴淑芳1,2，张羽舒1，莫兆宏1，文鑫宇1，刘晓暄1
（1.广东工业大学，广东广州 510006；2.广东深展实业有限公司，广东揭阳 522061）
【摘 要】以乙二胺和丙烯酸异冰片酯合成了一种带环状侧链的扩链剂，并通过红外和核磁氢谱对其结构进行了表征。用合成的扩链剂对聚氨酯丙烯酸酯进行改性，制备了一系列改性水性聚氨酯丙烯酸酯。探究了不同光引发剂（JRCure500、1173和L-TPO）对改性水性聚氨酯丙烯酸酯固化动力学的影响，发现光引发剂JRCure500具有相对较高的双键转化率和光聚合速率。研究了扩链剂用量对改性水性聚氨酯丙烯酸酯乳液的粒径大小、固化膜的拉伸强度、玻璃化转变温度、吸水率和热失重等方面的影响。研究结果表明：随着扩链剂用量的增加，乳液的粒径逐渐增大，固化膜的拉伸强度逐渐增大，玻璃化转变温度逐步提高，吸水率逐渐降低，最大热失重速率的温度逐渐降低。
杨海冬1，王 帅2，王德志1，李洪峰1，肖万宝1，赵立伟1，曲春艳1，康文双1
（1.黑龙江省科学院石油化学研究院，黑龙江哈尔滨 150080；2.中国运载火箭技术研究院，北京 100076）
【摘 要】对新型环氧芳胺结构胶膜进行了固化工艺、耐热性能及微观形貌的研究。研究结果表明：该胶膜的玻璃化转变温度（tanδ法）约为202 ℃，TGA曲线表明固化后的胶膜质量损失5%的温度约为372 ℃，DTG曲线表明胶膜的最快热失重速率约为400 ℃；扫描电镜照片显示，胶膜断面呈现韧性破坏模式。用此胶膜开展了耐磨型聚四氟乙烯薄片和铝合金的胶接研究，分析了固化时间、压力及铝合金表面处理方法对二者胶接强度的影响。研究结果表明：当采用固化工艺为180℃/3 h、压力为0.3 MPa时，耐磨型聚四氟乙烯薄片和铝合金胶接强度较佳，常温（23 ℃）剪切强度为12.7 MPa，高温（177 ℃）剪切强度为5.6 MPa；该胶膜在航空发动机上具有潜在的应用价值。
【关键词】耐磨型聚四氟乙烯薄片；铝合金；耐热性能；胶接强度
木材用单组分湿固化聚氨酯胶粘剂的制备及最优R值选取
【摘 要】采用一步法将聚醚多元醇、扩链剂与异氰酸酯反应，制备了木材用单组分湿固化聚氨酯胶粘剂。对样品性能进行分析，探究较优的—NCO/—OH（R值）。研究结果表明：R值为10.38时，胶粘剂应用在桦木上的粘接强度相对最佳，此时胶粘剂对桦木的润湿性、热稳定性和开放时间均较为优异。
【关键词】木材用胶粘剂；聚氨酯；粘接强度；单因素试验
(西南科技大学材料与化学学院，四川绵阳 621010)
【摘 要】通过将聚乙二醇(PEG1000)与1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺离子液体([BMIM]TFSI)引入环氧胶粘剂，制备了一种通电可快速剥离的高强度离子导体环氧结构胶(I-EP)。其初始粘接强度达21.65 MPa，通电60 V/60 s后残余强度仅为0.02 MPa，剥离效率可达99.91%。重点研究了温度为55℃、相对湿度为95%RH的老化环境对I-EP粘接强度的影响。研究结果表明：在此环境下老化48 h后，I-EP的粘接强度衰减了49.28%；对其环境可靠性的失效机制研究发现，在高温、高湿环境下，I-EP本体中的[BMIM]TFSI容易向粘接界面发生物理迁移，与粘接基材发生自发的电化学腐蚀，导致胶粘剂与基材之间的强相互作用被破坏，进而导致粘接强度明显下降。
朱晓霞1，梁国星1,2，吕 明1,2，赵 建1,2，杨 坡1，岳春雨1
(1.太原理工大学机械与运载工程学院，山西太原 030024；2.精密加工山西省重点实验室，山西太原 030024)
【摘 要】为了实时监测环氧树脂系统在固化过程中的黏度，建立了一种基于相似理论和落球法的动态黏度预测模型。首先，结合影响黏度的主要因素，利用量纲分析法，推导出无量纲的黏度方程；其次，通过分析实测黏度数据，得出不同粒径骨料在不同的反应时间条件下的黏度预测方程；最后，对比分析方程预测结果与实测黏度。研究结果表明：采用该方法能够在不同粒径骨料条件下预测树脂系统固化过程的实际黏度；预测黏度在树脂系统固化反应前期和后期的置信度高于固化反应中期；当骨料粒径在4.75~6.00 mm时，实测黏度与预测黏度吻合度相对最高。
【关键词】树脂系统；固化过程；预测模型；相似理论；落球法
[1.三棵树（上海）新材料研究有限公司，上海 201100；2.三棵树涂料股份有限公司，福建莆田 351100]
【摘 要】以邻苯二甲酸二烯丙酯(DAP)为预交联单体，以乙烯基三乙氧基硅烷(VTES)为后交联单体，采用半连续种子乳液聚合法制备了双交联单体改性的聚醋酸乙烯酯（PVAc）乳液。研究了两种单体使用量对乳液聚合稳定性的影响，并通过多种手段对所得乳液进行性能表征。研究结果表明：当VTES与DAP的质量分数分别为4%和2.5%时，聚合反应可稳定进行；改性乳液胶膜的吸水率最低至8.3%，静态接触角最大为80.2°，与木材粘接的湿剪切强度最高可达2.53 MPa，乳液胶膜的Tg达到28.76 ℃，初始分解温度达到307.78 ℃，表明此双交联单体改性的PVAc乳液的耐水性、热稳定性均得到了大幅提高。
【关键词】聚醋酸乙烯酯；双交联单体；有机硅改性；耐水性
【摘 要】采用一系列银粉制备了不同种类的导电胶。通过不同的配方来调配导电胶的黏度，并结合导电胶的相关性能，最终调试得到了A、B、C三种导电胶。对其黏度、热稳定性、固化性能、导电导热性和力学性能进行了研究。研究结果表明：三种导电胶的触变性均较好，热分解温度在390℃左右，耐温性较佳，固化温度都在220℃左右；三种导电胶的导热系数分别为27.31、31.93、29.23 W/(m·K)，远超企标要求[>2 W/(m·K)]；制备的三种导电胶在高温时的拉伸剪切强度相比传统导电胶要高50%，可充分满足导电胶的高温使用条件。综上所述，三种导电胶的常规性能均能满足企业标准，性能稳定，可应用于对热导率要求较高的高精密半导体封装领域。
[1.哈尔滨工业大学(深圳)材料科学与工程学院，广东深圳 518055；2.工业和信息化部电子第五研究所，广东广州 511370]
【摘 要】导电胶在电子封装领域虽受到广泛关注，但由于导电胶性能的一些限制，仍不能完全用导电胶代替焊料。这主要与导电胶的可靠性有关，例如不稳定的接触电阻、有限的抗冲击性、低附着力和导电性。本文介绍了导电胶的分类、各类导电填料以及导电胶可靠性的研究现状，旨在阐述导电胶的综合性能，展望未来导电胶的发展趋势。
姚淑芳1,2，曾 兵1,2，王先前3，安绍都1,2
（1.中国建筑科学研究院有限公司，北京 100013；2.建研院检测中心有限公司，北京 100013；3.深圳市市政设计研究院有限公司，广东深圳 518037）
【摘 要】综述了预制节段胶接技术的发展历程以及预制混凝土胶接缝的基本特性。重点阐述了该类环氧树脂胶粘剂的老化机理和胶接缝耐久性的研究方法和成果，主要包括预制节段拼接胶的耐久性和胶接缝的耐久性。在此基础上，指出了目前研究的不足，提出了研究方向的建议。
【关键词】预制节段；胶接缝；环氧树脂；拼接胶；耐久性
（东莞优邦材料科技股份有限公司，广东东莞 523837）
【摘 要】阐述了近年来反应型聚氨酯（PUR）热熔胶的研究进展，系统讨论了不同种类PUR热熔胶的固化机理、材料结构设计以及性能调控方法等。此外，阐述了PUR热熔胶在电子产品组装方面的应用。最后对PUR热熔胶在电子组装方面的应用和挑战提出了展望。
【关键词】反应型聚氨酯热熔胶；电子组装；硅烷改性；光-湿双固化
Scientific Research Report
Research on self-repair and bonding properties of polyurethane based on hydrogenated hydroxyl-terminated polybutadiene and catechol group
Zhu Jun1,Chang Chun1, Wei Liuhe2, Li Yuhan2
(1.College of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China; 2. College of Chemistry, Zhengzhou University, Zhengzhou Key Laboratory of Elastic Sealing Materials, Zhengzhou 450001, Henan, China)
【Abstract】Chain extender containing catechol group was synthesized from 3,4-dihydroxybenzaldehyde (DBA) and serinol, and then linear polyurethane (HHPB-DS) was synthesized with hydrogenated hydroxyl-terminated polybutadiene (HHPB) and isophorone diisocyanate (IPDI). The research results showed that the polyolefinic HHPB had a higher degree of microphase separation than that of polytetramethylene ether (PTMEG). The viscous flow transition temperature of HHPB-DS was 81 ℃, which not only exhibited self-repair properties but also could be used for hot melt bonding. The introduction of catechol group endowed the material with good bonding to a variety of substrates, especially to improve the bonding strength to steel plate. The HHPB with low surface energy played a role in protecting the hard segment phase and reducing the interference of water molecule on the hydrogen bond between carbamate group and catechol group so that the bonding strength of substrate could still be maintained even after immersed in water for 3 d.
【Keywords】catechol; hydrogenated hydroxyl-terminated polybutadiene; water resistance; self-repair; bonding
Preparation and properties of novel chain extender and its modified waterborne polyurethane acrylate
Luo Qinghong1, Wu Shufang1,2, Zhang Yushu1, Mo Zhaohong1, Wen Xinyu1, Liu Xiaoxuan1
（1.Guangdong University of Technology, Guangzhou 510006, Guangdong, China; 2.Guangdong Shenzhan Industry Co., Ltd., Jieyang 522061, Guangdong, China）
【Abstract】A chain extender with cyclic side chain was synthesized from ethylenediamine and isobornyl acrylate, and its structure was characterized by infrared and nuclear magnetic hydrogen spectroscopy. A series of modified waterborne polyurethane acrylate were prepared by modifying polyurethane acrylate with the synthetic chain extender. The effects of different photoinitiators (JRCure500, 1173 and L-TPO) on the curing kinetics of modified waterborne polyurethane acrylate were investigated, and it was found that JRCure500 had relatively high double-bond conversion and photopolymerization rate. The effects of the amount of chain extender on the particle size of modified waterborne polyurethane acrylate emulsion, the tensile strength of cured film, the glass transition temperature, the water absorption and the thermal weight loss were studied. The research results showed that with the increase of the amount of chain extender, the particle size of emulsion gradually increased, the tensile strength of cured film gradually increased, the glass transition temperature gradually increased, the water absorption gradually decreased, and the temperature of maximum thermogravimetric rate gradually decreased.
【Keywords】waterborne UV curing; polyurethane acrylate emulsion; chain extender
Research on bonding of polytetrafluoroethylene thin sheet and aluminum alloy by epoxy adhesive film
Yang Haidong1, Wang Shuai2, Wang Dezhi1, Li Hongfeng1, Xiao Wanbao1, Zhao Liwei1, Qu Chunyan1, Kang Wenshuang1
(1.Institute of Petrochemistry Heilongjiang Academy of Sciences, Harbin 150080, Heilongjiang, China;2.China Academy of Launch Vehicle Technology, Beijing 100076,China)
【Abstract】The curing process, heat resistance and microscopic morphology of the new epoxy-arylamine structural adhesive film were studied. Theresearch results showed that the glass transition temperature (tanδ method) of the adhesive film was about 202 ℃. The TGA curve showed that the temperature of 5% mass loss of cured adhesive film was about 372 ℃, and the DTG curve showed that the fastest thermal weight loss rate of adhesive film was about 400 ℃. Scanning electron microscopy photos showed that the fracture surface of adhesive film was ductile failure mode. The adhesive film was used to study the bonding of wear-resistant polytetrafluoroethylene thin sheet and aluminum alloy. The effects of curing time, pressure and surface treatment of aluminum alloy on bonding strength of them were analyzed. The research results showed that when the curing process was 180℃/3h and the pressure was 0.3MPa, the bonding strength of wear resistant polytetrafluoroethylene thin sheet and aluminum alloy was relatively good, the shear strength was 12.7 MPa at room temperature (23 ℃) and 5.6 MPa at high temperature (177 ℃). The adhesive film had potential application value in aeroengine.
【Keywords】wear-resistant polytetrafluoroethylene thin sheet; aluminum alloy; heat resistance; bonding strength
Preparation of one-component moisture curing polyurethane adhesive for wood and selection of optimal R value
Gu Hao, Xu Zhen, Gu Jiyou
(Northeast Forestry University, Harbin 150000, Heilongjiang, China)
【Abstract】One-component moisture curing polyurethane adhesive for wood was prepared by one-step reaction of polyether polyol, chain extender and isocyanate. The properties of samples were analyzed, and the optimal —NCO/—OH (R value) was explored. The research results showed that when Rvalue was 10.38, the adhesive applied to birch wood had relatively best bonding strength, and at this time the adhesive had excellent wettability, thermal stability and open time performance on birch wood.
【Keywords】wood adhesive; polyurethane; bonding strength; single factor test
Development and Application
Study on environmental reliability of ionic conductor structural adhesive
(School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China)
【Abstract】A kind of high-strength ionic conductor epoxy structural adhesive that could be quickly peeled off by electricity was prepared by introducing polyethylene glycol (PEG1000) and 1-butyl-3-methylimidazoliumbis[(trifluoromethyl) sulfonyl]imide ([BMIM]TFSI) into epoxy adhesive. The initial bonding strength reached 21.65 MPa, the residual strength was only 0.02 MPa after applying 60 V/60 s, and the peeling efficiency was 99.91%. The influence of aging environment with temperature of 55 ℃ and relative humidity of 95%RH on the bonding strength of I-EP was emphatically studied. The research results showed that the bonding strength of I-EPreduced by 49.28% after aging for 48 h in this environment. The study on the failure mechanism of its environmental reliability found that under high temperature and high humidity environment, [BMIM]TFSI in I-EP body was prone to physical migration to the bonding interface and spontaneous electrochemical corrosion with the bonding substrate, leading to the destruction of strong interaction between adhesive and substrate, which led to a significant decline in the bonding strength.
【Keywords】ionic conductor; structural adhesive; environmental reliability
Prediction of dynamic viscosity of epoxy resin system in curing process by using aggregate
Zhu Xiaoxia1, Liang Guoxing1,2, Lyv Ming1,2,Zhao Jian1,2, Yang Po1, Yue Chunyu1
(1.College of Mechanical and Transportation Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China; 2.Shanxi Provincial Key Laboratory of Precision Machining, Taiyuan 030024, Shanxi, China)
【Abstract】In order to monitor the viscosity of epoxy resin system in the curing process in real time, a dynamic viscosity prediction model based on similarity theory and immersed body (plummet) method was established. First, combined with the main factors affecting viscosity, the dimensionless viscosity equation was derived by using dimensional analysis method. Secondly, by analyzing the real measured viscosity data, the viscosity prediction equation of aggregates with different particle sizes under different reaction time conditions was obtained. Finally, the predicted results of the equation were compared with the measured viscosity. The research results showed that this method could predict the actual viscosity of resin system in the curing process under different particle sizes of aggregate conditions. The confidence level of predicted viscosity in the early and late stage of curing reaction of resin system was higher than that in the middle stage of curing reaction. When the aggregate particle size was 4.75-6.00 mm, the consistency between the measured viscosity and the predicted viscosity was relatively the highest.
【Keywords】resin system; curing process; prediction model; similarity theory;immersed body (plummet) method
Study on synthesis and properties of double-crosslinked monomer modified PVAc emulsion adhesive
Ren Jie1,2, Xu Gang1,2, Chen Changzhu2
[1.SKSHU New Materials (Shanghai) Co., Ltd., Shanghai 201100, China; 2.SKSHU Paint Co., Ltd., Putian 351100, Fujian, China]
【Abstract】The double-crosslinked monomer modified polyvinyl acetate (PVAc) emulsion was prepared by semi-continuous seed emulsion polymerization using diallyl phthalate (DAP) as the pre-crosslinked monomer and vinyltriethoxysilane (VTES) as the post-crosslinked monomer. The effects of the using amount of two monomers on the stability of emulsion polymerization were studied, and the properties of the obtained emulsion were characterized by various means. The research results showed that the polymerization reaction could proceed stably when the mass fraction of VTES and DAP was 4% and 2.5%, respectively. The water absorption of modified emulsion film was as low as 8.3%, the maximum static contact angle was 80.2°, the maximum wet shear strength with wood could reach 2.53 MPa, the Tg of emulsion film reached 28.76 ℃, and the initial decomposition temperature reached 307.78 ℃, indicating that the water resistance and thermal stability of PVAc emulsion modified by these double-crosslinked monomers had been greatly improved.
【Keywords】polyvinyl acetate; double-crosslinked monomer; silicone modification; water resistance
Preparation and properties of electrically conductive adhesive with high thermal conductivity
(Shanghai Plastics Research Institute Co., Ltd., Shanghai 201702, China)
【Abstract】Different kinds of conductive adhesive was prepared by using a series of silver powder. Through different formulations to allocate the viscosity of conductive adhesive, and combined with the relevant properties of conductive adhesive, three kinds of conductive adhesive A, B and C were finally obtained through debugging. The viscosity, thermal stability, curing properties, electrical and thermal conductivity and mechanical properties were then studied. The research results showed that the thixotropy of three kinds of conductive adhesive was all good, the thermal decomposition temperature was about 390 ℃, the temperature resistance was excellent, and the curing temperature was all about 220 ℃. The thermal conductivity of three kinds of conductive adhesive was 27.31, 31.93 and 29.23 W/(m·K), respectively, which were far beyond the enterprise standard requirements [>2 W/(m·K)]. The tensile shear strength of prepared three kinds of conductive adhesive at high temperatures was 50% higher than that of traditional conductive adhesive, which could fully meet the high temperature use conditions of conductive adhesive. In summary, the conventional performance of three kinds of conductive adhesive could meet the enterprise standard with stable performance, and they could be applied to the high-precision semiconductor packaging field with high requirements for thermal conductivity.
【Keywords】high-filled silver powder; micronano silver powder; conductive adhesive; high thermal conductivity
Special Topics and Review
Research status and prospect ofconductive adhesive for electronic packaging
Zhang Weiwei1,Liu Hao1, Liu Jiahao2, Li Mingyu1, Chen Hongtao1
[1. Harbin Institute of Technology (Shenzhen) School of Materials Science and Engineering, Shenzhen 518055, Guangdong, China; 2. The Fifth Electronics Research Institute of Ministry of Industry and Information Technology, Guangzhou 511370, Guangdong, China]
【Abstract】Although conductive adhesive has received extensive attention in the field of electronic packaging, it can not completely replace solder with conductive adhesive because of some limitations of its performance. This is mainly related to the reliability of conductive adhesive, such as unstable contact resistance, limited impact resistance, low adhesion and electrical conductivity. In this paper, the classification of conductive adhesive, various conductive fillers and the research status of the reliability of conductive adhesive were introduced, aiming at revealing the comprehensive performance of conductive adhesive and prospecting the future development trend of conductive adhesive.
【Keywords】conductive adhesive; conductive filler; reliability; electronic packaging
Overview of durability of precast concrete segmental adhesive joint
Yao Shufang1,2, Zeng Bing1,2, Wang Xianqian3, An Shaodu1,2
(1.China Academy of Building Research, Beijing 100013, China; 2. CABR Testing Center Co., Ltd., Beijing 100013, China; 3.Shenzhen Municipal Design & Research Institute Co., Ltd., Shenzhen 518037, Guangdong, China)
【Abstract】The development history of precast segmental bonding technology and the basic characteristics of precast concrete segmental adhesive joint were summarized. The aging mechanism of this kind of epoxy resin adhesive and the research methods and achievements of the durability of adhesive joint were emphatically described, which mainly included the durability of precast segmental splicing adhesive and the durability of adhesive joint. On this basis, the shortcomings of current research were pointed out, and some suggestions for research direction were put forward.
【Keywords】precast segment; adhesive joint; epoxy resin; splicing adhesive; durability
Application of reactive polyurethane hot melt adhesive in electronic assembly
(Dongguan U-Bond Material Technology Co., Ltd., Dongguan 523837, Guangdong, China)
【Abstract】The research progress of reactive polyurethane (PUR) hot melt adhesive in recent years was reviewed. The curing mechanism, material design and performance optimization of different kinds of PUR hot melt adhesive were systematically discussed. In addition, the application of PUR hot melt adhesive in electronic assembly was described. Finally, the application and challenge of PUR hot melt adhesive in electronic assembly were prospected.
【Keywords】reactive polyurethane hot melt adhesive; electronic assembly; silane-modification; light-moisture dual-curing
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