【摘  要】随着柔性电子和可穿戴智能设备的快速发展，其重要组成之一柔性力学传感器已成为连接生物系统与传统电子器件的主要理想接口，因其可模拟人体皮肤感知特性，实现对人体多种多维度生理信号的稳定监测。作为这类传感器的核心材料，可拉伸柔性导体成为限制柔性力学传感器快速发展的关键，迫切需要克服内在弱点与突破发展瓶颈，以满足日益增长的需求。可拉伸柔性导体在应用中需要附着在皮肤或者各种基体上，因此稳固黏附性和自修复性是关键特性。作为一种新型柔性导体，全固态离子导电弹性体黏合剂由于解决了水/有机凝胶水蒸发和凝固、离子凝胶中液体经挤压易泄露以及难以兼顾电导率和力学性能等问题，已经成为智能柔性电子器件的理想候选核心材料之一。本文综述了离子导电弹性体黏合剂的黏附机理、自修复机理，以及近年来主要弹性体黏合剂的类型和合成方法，并对其在柔性电子等多个领域的代表性应用进行了介绍。同时，展望了弹性体黏合剂目前发展和实际应用存在的挑战和问题，为高性能弹性体黏合剂的分子设计以及在柔性电子产品的应用提供可行性依据和有益启示。

【关键词】离子导电弹性体；黏合剂；柔性电子；可拉伸柔性导体；自修复；聚合物固态电解质

环氧树脂胶粘剂化学改性方法研究进展

聂振宇，韩  璐，姜政阳，阚成友

（清华大学化学工程系，北京  100084）

【摘  要】环氧树脂是一种应用广泛的胶粘剂材料，但传统环氧胶粘剂往往达不到如今多样化的性能需求，需要改性后使用。本文从环氧胶粘剂固化关键成分的角度，分类综述了近十年来环氧胶粘剂化学改性方法，如新型环氧树脂和固化剂的合成、复合改性等。结合近几年的研究热点，对环氧胶粘剂未来的发展方向进行了分析和展望。

【关键词】胶粘剂；环氧树脂；化学改性方法

石蜡强韧化环氧树脂体系的试验结合分子动力学模拟研究

孙  怡¹，陈宏峰¹，李  言³，罗艳龙²，廉青松¹

（1.中北大学，纳米功能复合材料山西省重点实验室，山西太原  030051；2.南京林业大学理学院，江苏南京  210037；3.中国航空制造技术研究院材料应用研究部，北京  100024）

【摘  要】通过硫醇-烯点击化学合成了一种具有柔性烷基侧链的特种环氧树脂（D12），随后利用其作为增容剂，将正二十烷（C20，石蜡模型化合物）均匀混合到环氧树脂基体（DGEBA）中，固化得到一系列D12和C20协同增韧的环氧树脂体系（EP_DA-X体系）。通过结合试验和分子动力学模拟方法，系统研究了DGEBA/D12/C20三元体系的强韧化机理。研究结果表明：⑴当D12和C20的物质的量比为1∶2且二者在固化体系中的质量分数为2.5%时，体系具有最优异的综合性能，拉伸强度为99.3 MPa，拉伸模量为2.8 GPa，断裂伸长率为4.5%。三者均高于纯EP体系，实现了环氧树脂强度、模量和韧性的协同提升。⑵EP_DA-X体系中存在微相分离结构，且初步证明体系中的微相分离结构是由C20在D12侧链周围自组装引起的。自组装效应所形成的物理缠结结构可以为体系提供额外的物理交联点，从而可以实现环氧树脂强度、模量和韧性的协同提升。⑶使用分子动力学模拟计算了所有体系的杨氏模量，发现EP_DA-X体系的模量均高于纯EP体系。EP_DA-X体系径向分布函数的计算结果表明，C20与D12的主链相互作用很弱，但与D12的侧链相互作用很强。这进一步证明了C20在D12的侧链周围发生了自组装效应，从而在分子和原子尺度上证明了C20和D12自组装协同强韧化环氧树脂的机理。

【关键词】分子动力学模拟；增韧机理；环氧树脂；石蜡；自组装

增塑剂在丙烯酸酯压敏胶中的扩散行为与影响

吴季鸿¹，周启艳¹，张晓辉¹，石一峰²，钱  军¹

（1.华东理工大学材料科学与工程学院，上海  200237；2.上海宏顶房科技有限公司，上海  200237）

【摘  要】为研究增塑剂邻苯二甲酸二辛酯（DOP）在丙烯酸酯压敏胶中的扩散行为，制备了丙烯酸异辛酯（2-EHA）、丙烯酸甲酯（MA）和丙烯酸（AA）体系的压敏胶。采用分子量分布(GPC)、动态力学分析(DMA)、热失重分析(TG)和力学测试等方法，考察了引发剂用量、不同增塑剂浓度下交联剂用量，以及同一交联剂用量下不同增塑剂和增黏树脂用量对压敏胶性能的影响。研究结果表明：随着胶样分子量的增加，增塑剂DOP的扩散行为会减缓并趋于平衡；随着胶样交联程度的提高，增塑剂DOP的扩散行为会明显减缓；同时改变交联剂与DOP用量时，交联剂和DOP均会使初粘力和剥离强度降低；DOP进入含增黏树脂体系丙烯酸酯胶层后，粘接升降行为还会随增黏树脂含量而改变。

【关键词】增塑剂；压敏胶；扩散

无机填料改性小麦蛋白/单宁复合胶粘剂的制备及性能研究

程增会，王基夫，张代晖，王春鹏，储富祥

（中国林业科学研究院林产化学工业研究所，江苏省生物质能源与材料重点实验室，国家林业和草原局林产化学工程重点实验室，林木生物质低碳高效利用国家工程研究中心，江苏省林业资源高效加工利用协同创新中心，江苏  南京    210042）

【摘  要】以小麦蛋白（WG）和缩合单宁(CTs)为原料，制备了无甲醛的生物基木材胶粘剂。利用蒙脱土、高岭土、重质碳酸钙、轻质碳酸钙和羟基磷灰石为填料进行改性，采用共混的方式制备填料改性复合胶粘剂。考察了无机填料种类对WG/CTs复合胶粘剂性能的影响，并进行耐水胶合强度、扫描电子显微镜（SEM）、热重分析仪、沸水煮不溶率、黏度等测试分析。研究结果表明：加入填料后，WG/CTs复合胶粘剂的黏度均有不同程度的增大，胶粘剂的热稳定性也比对照组胶粘剂有所提高；不同无机填料改性胶粘剂的耐水性存在显著差异，但胶合板的湿态强度均超过0.7 MPa，达到国家II类胶合板标准的要求；沸水煮不溶率测试结果显示，轻质碳酸钙改善了胶粘剂的耐水性；SEM图和胶层裂纹评估显示，重质碳酸钙、轻质碳酸钙与胶粘剂具有良好的相容性，表明碳酸钙填料对胶层的韧性没有影响，是较好的填料选择。

【关键词】小麦蛋白；缩合单宁；无机填料；胶粘剂；胶合强度

长开放期EPI木材胶粘剂的制备与性能表征

余桂勋，黄    鹤

（苏州大学材料与化学化工学部，先进功能高分子材料国家地方联合工程实验室，江苏  苏州    215123）

【摘  要】通过特定的乳液聚合工艺，制备了一款苯丙乳液(SAEP2)，并将其应用于木材胶粘剂。系统地考察了聚乙烯醇的聚合度和浓度、异氰酸酯固化剂用量以及钙粉用量对胶粘剂开放期及粘接强度的影响。研究结果表明：胶粘剂开放期会随着聚乙烯醇的聚合度和浓度、异氰酸酯固化剂用量、碳酸钙粉末用量的增大而缩短；当m(SAEP2)∶m(10%的BP17水溶液)∶m(钙粉)=1∶1∶1，且异氰酸酯固化剂用量为13%时，制备的SAEP2胶粘剂湿强度达标（可达5.4 MPa），而开放期长达150 min。

【关键词】木工胶粘剂；开放期；苯丙乳液；聚乙烯醇

纳米二氧化硅微球表面接枝嵌段聚合物的制备及其在丙烯酸结构胶体系中的性能研究

黄  冰，孙一童，李海平，葛于晶

[康达新材料（集团）股份有限公司，上海  201419]

【摘  要】以二氧化硅微球为模板，将其表面修饰上活性官能团。通过表面引发可控/“活性”自由基聚合，连续引发苯乙烯和甲基丙烯酸2-羟基乙酯聚合，得到表面接枝嵌段聚合物的纳米二氧化硅微球，并对其进行表征。将表面修饰的二氧化硅微球用于丙烯酸结构胶体系，并和未修饰二氧化硅微球的体系进行对比。研究结果表明：通过结构表征证明了目标产物合成成功；将表面修饰的二氧化硅微球用于丙烯酸结构胶体系，聚合物改性的纳米二氧化硅在拉伸强度、断裂伸长率和剪切强度等性能的表现均优于未改性的纳米二氧化硅；纳米二氧化硅在固化体系中具有增强增韧的作用，表面接枝聚合物改性后，其性能表现更优。

【关键词】纳米二氧化硅微球；改性；接枝；胶粘剂

有机硅密封胶用纳米碳酸钙的电阻率研究

田  伟¹，吴佳伟²，李  华³，汪丽红¹

（1.浙江天石纳米科技股份有限公司，浙江杭州  311600；2.上海回天新材料有限公司，上海 201600；3.杭州市建德生态环境监测站，浙江杭州  311600）

【摘  要】通过碳化法合成纳米碳酸钙(NCC)，考察了原料产地、晶形控制剂、表面处理剂种类及用量、工艺水质等对纳米钙电阻率的影响。研究结果表明：表面处理剂种类及用量对纳米钙电阻率的影响最为显著，原料产地次之，晶型控制剂和工艺水质影响较小。这是因为纳米钙颗粒吸附或夹杂的离子种类及浓度是影响纳米钙电阻率的主要因素。影响机理是：在电场作用下，由工艺引入的Na⁺、OH^-通过纳米钙颗粒间形成的毛细管定向迁移和输送，发生贯通材料基体的离子隧穿，较高的浓度和摩尔电导率加剧了纳米钙电阻率的衰减；由原料引入Mg²⁺、Fe²⁺、Ca²⁺以及CO₃^2-等离子浓度低，难以发生离子隧穿，只能溶解于微量自由水形成分布稀疏的“盐池”，依靠相互接连而迁移导电，对电阻率的影响较小。

【关键词】有机硅密封胶；纳米碳酸钙；电阻率

Progress and application of ionic conductive elastomer adhesive

Zhang Qing, Huang Jijun

(College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China)

【Abstract】With the rapid development of flexible electronics and wearable smart devices, one of their important components, flexible mechanical sensors have become the main ideal interface for connecting biological systems with traditional electronic devices. Due to their ability to simulate the perception characteristics of human skin, they can achieve stable monitoring of various multi-dimensional physiological signals in the human body. As the core material of such sensors, stretchable flexible conductors have become the key limiting factors for the rapid development of flexible mechanical sensors. It is urgent to overcome inherent weaknesses and break through development bottlenecks to meet the growing demand. In practical applications, stretchable flexible conductors often need to be attached to the skin or various substrates, and thus stable adhesion and self-healing are key characteristics. As a new type of flexible conductors, all-solid ionic conductive elastomer adhesive has become one of the ideal candidate core materials for intelligent flexible electronic devices because it solves the problems of hydro/organogel water evaporation and solidification, possible liquid leakage in ionic gel through squeezing, as well as the difficulties in balancing the conductivity and mechanical properties. In this paper, the adhesion mechanism and self-healing mechanism of ion conductive elastomer adhesive, as well as the types and synthesis methods of main elastomer adhesive in recent years were reviewed, and their representative applications in multiple fields such as flexible electronics were introduced. At the same time, the challenges and problems in the current development and practical application of elastomer adhesive were discussed, providing feasible basis and beneficial insights for the molecular design of high-performance elastomer adhesive and their application in flexible electronic products.

【Keywords】ionic conductive elastomer; adhesive; flexible electronics; stretchable flexible conductor; self-healing; solid-state polymer electrolyte

Research progress on chemical modification methods of epoxy adhesive

Nie Zhenyu, Han Lu, Jiang Zhengyang, Kan Chengyou

(Department of Chemical Engineering, Tsinghua University, Beijing 100084, China)

【Abstract】Epoxy resin is a widely-used adhesive material, but the traditional epoxy adhesive often fails to meet various performance requirements of today, and needs to be modified before application. In this paper, the chemical modification methods of epoxy adhesive in the recent ten years, such as the synthesis of new epoxy resins and curing agents, composite modification, etc. were categorized and summarized. Based on the research hotspots in recent years, the future development direction of epoxy adhesive was analyzed and prospected.

【Keywords】adhesive; epoxy resin; chemical modification method

Strengthening-toughening epoxy resin system with paraffin: an experimental and molecular dynamics simulation study

Sun Yi¹, Chen Hongfeng¹, Li Yan³, Luo Yanlong², Lian Qingsong¹

(1. Shanxi Province Key Laboratory of Functional Nanocomposites, North University of China, Taiyuan  030051, Shanxi, China; 2.College of Science, Nanjing Forestry University, Nanjing  210037, Jiangsu, China; 3.Department of Materials Application Research, AVIC Manufacturing Technology Institute, Beijing  100024, China)

【Abstract】A special epoxy resin (D12) with flexible alkyl side chains was synthesized through thiol-ene click chemistry, and then using it as a compatibilizer, n-eicosane (C20, paraffin model compound) was uniformly mixed into the epoxy resin matrix (DGEBA). A series of D12 and C20 synergistic toughening epoxy resin systems (EP_DA-X systems) were obtained by curing. The strengthening-toughening mechanism of DGEBA/D12/C20 ternary system was systematically studied by combining experimental and molecular dynamics simulation methods. The research results showed that, ⑴When the mass ratio of D12 and C20 was 1∶2 and their mass fraction in the curing system was 2.5%, the system had the best comprehensive performance, with the tensile strength of 99.3 MPa, the tensile modulus of 2.8 GPa, and the elongation at break of 4.5%. All three were higher than the pure EP system, achieving a synergistic improvement in the strength, modulus, and toughness of epoxy resin.⑵There was a microphase separation structure in the EP_DA-X system, and it had been preliminarily proven that the microphase separation structure in the system was caused by the self-assembly of C20 around the D12 side chain. The physical entanglement structure formed by the self-assembly effect could provide additional physical crosslinking points for the system, thereby achieving a synergistic improvement in the strength, modulus, and toughness of epoxy resin.⑶Molecular dynamics simulation was used to calculate the Young's modulus of all systems, and it was found that the modulus of EP_DA-X system was higher than that of the pure EP system. The calculation results of the radial distribution function of EP_DA-X system indicated that the main chain interaction between C20 and D12 was weak, but the side chain interaction with D12 was strong. This further confirmed the self-assembly effect of C20 around the side chains of D12, thereby proving the mechanism of synergistically strengthening-toughening of epoxy resin by C20 and D12 self-assembly at the molecular and atomic scales.

【Keywords】molecular dynamics simulation; toughening mechanism; epoxy resin; paraffin, self-assembly

Diffusion behavior and effect of plasticizer in acrylate pressure sensitive adhesive

Wu Jihong¹,Zhou Qiyan¹, Zhang Xiaohui¹, Shi Yifeng²,Qian Jun¹

(1.School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China; 2.Shanghai Hongdingfang Technology Co., Ltd., Shanghai  200237, China)

【Abstract】In order to investigate the diffusion behavior of plasticizer dioctyl phthalate (DOP) in acrylate pressure sensitive adhesive, the pressure sensitive adhesive system consisting of 2-ethylhexyl acrylate (2-EHA), methyl acrylate (MA), and acrylic acid (AA) was prepared. Using methods such as molecular weight distribution (GPC), dynamic mechanical analysis (DMA), thermogravimetric analysis (TG), and mechanical testing, the effects of initiator content, crosslinking agent content at different plasticizer concentrations, and different plasticizer and tackifying resin contents under the same crosslinking agent content on the performance of pressure sensitive adhesive were investigated. The research results showed that when the molecular weight increased, the diffusion behavior of plasticizer DOP slowed down and tended towards equilibrium. As the crosslinking degree of adhesive sample increased, the diffusion behavior of plasticizer DOP would be significantly slowed down.When the contents of crosslinking agent and DOP were changed simultaneously, both crosslinking agent and DOP would reduce the initial tack and peel strength. After DOP entered the acrylate adhesive layer containing the tackifying resin system, the adhesion behavior would also change with the content of the tackifying resin.

【Keywords】plasticizer; pressure sensitive adhesive; diffusion

Preparation and properties of inorganic filler modified wheat protein/tannin composite adhesive

Cheng Zenghui, Wang Jifu, Zhang Daihui, Wang Chunpeng, Chu Fuxiang

(Institute of Chemical Industry of Forest Products, CAF; Key Lab of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, Jiangsu, China)

【Abstract】Formaldehyde-free bio-based wood adhesive was prepared by using wheat protein (WG) and condensed tannin (CTs) as raw materials. Using montmorillonite, kaolin, heavy calcium carbonate, light calcium carbonate and hydroxyapatite as fillers for modification, the filler-modified composite adhesive was prepared by the blending method. The influence of inorganic filler type on the properties of WG/CTs composite adhesive was investigated, and water-resistance bonding strength, scanning electron microscopy (SEM), thermogravimetric analysis, insolubility in boiling water, viscosity and other tests were analyzed. The research results showed thatafter adding fillers, the viscosity of WG/CTs composite adhesive increased to varying degrees, and the thermal stability of adhesive was also improved compared to the control group adhesive. There were significant differences in the water resistance of adhesive modified with different inorganic fillers, but the wet strength of plywood all exceeded 0.7 MPa, meeting the requirements of the national standard  of Class II plywood.The test results of insolubility in boiling water showed that light calcium carbonate improved the water resistance of adhesive.SEM images and crack assessment of adhesive layer showed that heavy calcium carbonate and light calcium carbonate had good compatibility with the adhesive, indicating that calcium carbonate filler had no effect on the toughness of adhesive layer and was a good filler choice.

【Keywords】wheat protein; condensed tannin; inorganic filler; adhesive; bonding strength

Preparation and characterization of EPI wood adhesive with long opening period

Yu Guixun, Huang He

(College of Chemistry, Chemical Engineering and Materials Science of Soochow University, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Suzhou215123, Jiangsu, China)

【Abstract】A styrene-acrylate emulsion (SAEP2) was prepared by a specific emulsion polymerization process, and it was applied in wood adhesive. The influence of the polymerization degree and concentration of polyvinyl alcohol, the amount of isocyanate curing agent, and the amount of calcium carbonate powder on the opening period and bonding strength of adhesive was systematically investigated. The research results showed that the opening period of adhesive was shortened with the increase of the polymerization degree and concentration of polyvinyl alcohol, the amount of curing agent and calcium carbonate powder. Whenm(SAEP2)∶m(10% BP17 aqueous solution)∶m(calcium powder)=1∶1∶1, and the amount of isocyanate curing agent was 13%, the wet strength of the prepared adhesive SAEP2 met the standard (up to 5.4 MPa), and the opening period was as long as 150 min.

【Keywords】wood adhesive; opening period; styrene-acrylate emulsion; polyvinyl alcohol

Preparation of surface grafting block polymers onto nano silica microspheres and their performance study in acrylic structural adhesive

Huang Bing, Sun Yitong, Li Haiping, Ge Yujing

[Kangda New Material (Group) Co., Ltd., Shanghai 201419, China]

【Abstract】Using silica microspheres as templates, the surface was modified with active functional groups. By initiating controllable/"active" radical polymerization on the surface, and continuous polymerization of styrene and 2-hydroxyethyl methacrylate, nano silica microspheres grafted with block polymers on the surface were obtained, which were then characterized. The surface modified silica microspheres were used in acrylic structural adhesive system and they were compared with the unmodified silica microsphere system. The research results showed that the target product was synthesized successfully through structural characterization. The surface modified silica microspheres were used in the acrylic structural adhesive system, and the performance of polymer modified nano silica in tensile strength, elongation at break, and shear strength was superior to that of unmodified nano silica. Nano silica had the strengthening and toughening effect in the curing system, and its performance was better after surface grafting for polymer modification.

【Keywords】nano silica microsphere; modification; grafting; adhesive

Study on the electrical resistivity of nano calcium carbonate for silicone sealant

Tian Wei¹, Wu Jiawei² ,Li Hua³,Wang Lihong¹

(1. Zhejiang Tianshi Nanotechnology Co., Ltd., Hangzhou311600, Zhejiang, China; 2. Shanghai Huitian New Material Co., Ltd., Shanghai  201600, China; 3. Hangzhou Jiande Ecol-environmental Monitoring Station, Jiande 311600, Hangzhou, China)

【Abstract】Nano calcium carbonate (NCC) was synthesized by the carbonification method, and the effects of raw material origin, crystal shape control agent, type and content of surface treatment agent, process water quality on the electrical resistivity of NCC were investigated. The research results showed that the type and content of surface treatment agent had the most significant impact on the electrical resistivity of NCC, followed by raw material origin, and the influence of crystal shape control agent and process water quality was relatively small. This was because the type and concentration of ions adsorbed or entrapped in nano calcium particles were the main factors affecting the resistivity of nano calcium. The mechanism of influence was that, under the action of the electric field, Na⁺ and OH^-introduced by the process migrated and transported through the capillary tube formed between the NCC particles, causing ion tunneling through the material matrix. The high concentration and molar conductivity intensified the resistivity attenuation of nano calcium. The concentrations of Mg²⁺, Fe²⁺, Ca²⁺, and CO₃^2- introduced by the raw material were low, they were difficult to undergo ion tunneling migration, could only be dissolved in traces of free water to form a sparse distribution of the "salt pool", which relied on interconnection to migrate and conduct electricity, and thus had less impact on electrical resistivity.

【Keywords】silicone sealant; nano calcium carbonate; electrical resistivity