何文诚1，阚雨菲1，阚浩峰1，刘泽顺1，舒焕然2，高振华1,3
(1.东北林业大学材料科学与工程学院，黑龙江 哈尔滨 150040；2.浙江衢州博蓝装饰材料有限公司，浙江 衢州 324000; 3.黑龙江省木质资源材料科学与技术重点实验室，黑龙江 哈尔滨 150040)
【摘 要】为了降低大豆蛋白胶的成本，提高其耐水性能和涂布性能，本研究以高温脱脂豆粕粉为主要原料，以环氧氯丙烷-聚酰胺多胺(PAE)为交联剂，并添加十二烷基硫酸钠(SDS)，制得豆粕基大豆蛋白胶粘剂。着重探讨了高温脱脂豆粕粉用量以及SDS用量对大豆蛋白胶粘剂的涂布性能、胶合强度和耐水性能的影响及其作用机制。研究结果表明：引入适当SDS可通过其乳化作用使大豆蛋白伸展，从而提升大豆蛋白胶粘剂的润湿性和交联活性，进而改善胶合性能和涂布挂胶性；当高温脱脂豆粕粉用量为70%、SDS用量为0.30%时，所制备的大豆蛋白胶粘剂的胶合性能和涂布挂胶性达到最好，其63 ℃水泡湿强度提高到1.45 MPa，比国家标准要求值提高了45%，满足II类胶合板工业化生产需要。
【关键词】大豆蛋白胶粘剂；豆粕粉；涂布挂胶性；胶合性能
张锋锋1，侯莹莹1，王凤玲1，徐世杰1，邓来宏2，张春梅1
（1.山东中烟工业有限责任公司青岛卷烟厂，山东 青岛 266101；2.山东中烟工业有限责任公司生产制造中心，山东 济南 250100）
【摘 要】分别以4,4'-二氨基二苯甲烷（DDM）和4,4'-二氨基二苯砜（DDS）为固化剂，采用非等温差示扫描量热法（DSC）研究了E-44和E-51两种双酚A型环氧树脂的固化反应动力学。收集与分析了在25~350 ℃范围内分别以5、10、15、20 ℃/min的升温速率进行固化的反应参数，然后采用Starink法计算得到不同环氧固化体系的表观活化能。同时，借助各固化体系的动态流变性能，分析了双酚A型环氧树脂/芳香胺固化体系的固化反应机理，并选用双参数自催化模型计算了各固化体系的反应速率方程。研究结果表明：当环氧固化体系的固化剂不同时，采用DDM作为固化剂的环氧固化体系（E-44/DDM、E-51/DDM），其表观活化能均低于添加DDS固化剂的环氧体系；选用同种固化剂（DDM或DDS）时，E-51树脂体系的表观活化能均低于E-44树脂固化体系。反应速率方程结果显示，该双参数自催化模型与实际试验结果的吻合性良好，可用于描述双酚A型环氧树脂/芳香胺固化体系的固化历程。
【关键词】环氧树脂；固化动力学；动态流变性；DSC
郭宇婷，宋彩雨，孙明明，张 斌，张绪刚，王 磊，薛 刚，李坚辉
(黑龙江省科学院石油化学研究院，黑龙江哈尔滨 150040)
【摘 要】以聚四氢呋喃二元醇、甲苯-2,4-二异氰酸酯和1,2,4-苯三甲酸酐为原料，合成了端羧基聚氨酯低聚物（PUIC）；利用羧基与部分环氧基团反应，制备了一系列PUIC改性多官能环氧树脂（TGDDM-PUIC）。详细考察了改性树脂的粘接性能、热机械性能、热稳定性等。研究结果表明：成功制备了TGDDM-PUIC改性环氧树脂；引入PUIC改性TGDDM树脂整体的粘接性能和热稳定性能保持良好，并没有像其他增韧改性方法造成环氧树脂自身热性能的大幅度降低，实现了提高粘接性能与保持热稳定性之间的平衡；当PUIC质量分数为40%时，改性树脂的25 ℃剪切强度和剥离强度较纯树脂分别提升了163%和378%，热稳定性保持良好，综合性能优异。
【关键词】端羧基聚氨酯；多官能环氧树脂；粘接性能；热稳定
（中国电子科技集团公司第三十三研究所，山西 太原 030006）
【摘 要】以α-ω二羟基聚硅氧烷为基胶，以镀银铜粉为导电填料，以硅微粉、白炭黑和硬脂酸锌为体质填料，制备了具有良好粘接性能和电磁屏蔽性能的导电胶粘剂。考察了镀银铜粉的粒径、形貌、银含量及填充量对胶粘剂搭接剪切强度、导电性能、电磁屏蔽性能的影响。研究结果表明：镀银铜粉的银含量与填充量的增加明显提升了导电胶粘剂固化后的导电性能，随着银含量与填充量的增加，体积电阻率先降低、后趋于稳定；胶粘剂的剪切强度则是随着导电粉的粒径与填充量的增加而不断降低。试验中采用银含量为20%（质量分数）的45 μm枝状铜导电粉在添加量为70.8%时，制得的导电胶粘剂的综合性能较佳，固化后体积电阻率达到0.007 Ω·cm，剪切强度为1.05 MPa，电磁屏蔽性能≥85 dB（300 MHz～10 GHz）。
王观军1，韩 庆1，谭晓林2，王道阳3，刘海波1，孔德奥3
(1.中国石油化工股份有限公司胜利油田分公司技术检测中心，山东 东营 257000；2.胜利油田检测评价研究有限公司，山东 东营 257000；3.哈尔滨工业大学，黑龙江 哈尔滨 150006)
【摘 要】系统研究了一种水下可固化环氧胶粘剂在不同温度水浸泡条件下的水吸收、热-力学性能演化，并利用Arrhenius方程对在实际服役温度下胶粘剂和胶粘剂-钢界面的长期寿命进行了预测。研究结果表明：该胶粘剂的饱和吸水率为2.05%；长期浸泡后其玻璃化转变温度、拉伸性能均发生退化，但其拉伸强度长期寿命保留率超过60%，胶粘剂-钢界面的粘接强度长期寿命保留率为54.30%，说明该胶粘剂能够在水浸泡环境下长期使用。
【摘 要】设计了一种不同于以往同类型硅烷封端聚氨酯（SPU）预聚体的合成方案。以一种端—NCO硅烷和端—OH聚氨酯预聚体封端反应，得到硅烷封端聚氨酯预聚体。然后以此为基料，并添加催化剂和补强填料，通过配方筛选，制备了一种弹性密封胶产品。研究结果表明：当以MDI-100制备的产品作为调胶基料，以KH-540作为偶联剂，选择使用改性有机锡催化剂，w(纳米碳酸钙)=25%，w(疏水性白炭黑)=2%（相对于总质量而言）时，制备的密封胶综合性能较优。该密封胶克服了聚氨酯和硅酮密封胶的缺点，具有湿气固化特性，胶层不起泡、弹性好、可涂饰，综合性能优异，并且合成过程简单易控，产物稳定，目前已在工程密封领域得到了应用。
(1.广东三和化工科技有限公司，广东 中山 528429；2.广东三和控股有限公司，广东 中山 528429)
【摘 要】考察了不同类型的乙烯基硅油、硅乙烯基与硅氢基的比例和不同气相二氧化硅添加量对双组分加成型室温硫化硅橡胶的力学性能影响。研究结果表明：当使用复配的两种乙烯基硅油进行制备时，其得到的力学性能相对最佳；当m(硅乙烯基)∶m(硅氢基)=100∶3.5时，其剪切强度和硬度最大；当气相二氧化硅添加量为10%时，其综合性能相对最佳。
（中国安能集团第三工程局有限公司，四川成都 611130）
【摘 要】水工工程大量使用粉煤灰取代水泥，使用粉煤灰配制混凝土的性能严重影响施工效果，因此研究引水隧道混凝土衬砌中粉煤灰含量对抗压强度的影响有重要意义。本研究通过调整粉煤灰含量，分别制备了15%、25%与35%等3种粉煤灰含量的混凝土试件，并改变养护温度，调整粉煤灰细度，分别验证这些影响因素下掺合粉煤灰混凝土的抗压强度。考虑到引水隧道衬砌所处的实际环境，还研究了自然环境对于粉煤灰混凝土抗压强度的影响。研究结果表明：含量为25%的粉煤灰具有更加良好的抗压强度，同时将温度控制在22 ℃时，选择45 mm的方孔筛且筛余量为25%的粉煤灰细度，更能提升混凝土的抗压强度；粉煤灰会与酸性物质发生反应，所以粉煤灰掺量过多会降低混凝土的抗压强度。
【关键词】粉煤灰；引水隧道；混凝土衬砌；抗压强度；粉煤灰细度；养护温度
（浙江大学化学工程与生物工程学院，浙江 杭州 310014）
【摘 要】聚硫醇常用作环氧树脂低温或室温固化剂以及不饱和树脂紫外光交联剂。本文综述了国内外聚硫醇固化剂主要生产企业的产品结构、性能、应用领域及生产工艺。从市场需求角度分析了这些产品的特性及其在胶粘剂、涂料和油墨等领域中的应用。
【摘 要】航空灯具结构紧凑，密封性要求高，所以散热一直是产品中的突出问题。本文介绍了航空灯具类产品中主要使用的导热胶粘剂种类，包括导热胶、导热凝胶、导热垫片以及导热硅脂。概述了每种导热胶粘剂的导热特性及导热原理，并总结了影响导热性能的因素。最后对导热胶粘剂的使用提出建议，并对其发展进行了展望。
【关键词】导热胶粘剂；导热特性；导热原理；导热性能
[1.虹石（江苏）新材料科技有限公司，上海 200235；2.南京邮电大学材料科学与工程学院，江苏南京 210003；3.东方雨虹民用建材有限责任公司，北京 100176]
【摘 要】综述了醋酸乙烯-乙烯共聚乳液（VAE乳液）的特性，从共聚、共混、互穿网络、加助剂等方法介绍了VAE乳液的改性技术。同时，概括VAE乳液在胶粘剂、可再分散性乳胶粉、防水涂料、复膜胶以及建筑建材等方面的应用进展。最后对VAE乳液未来发展提出建议。
【关键词】VAE乳液；胶粘剂；共混改性；共聚改性；乳液应用
Scientific Research Report
Study on preparation of soybean meal-based adhesive for type II plywood
He Wencheng1, Kan Yufei1, Kan Haofeng1, Liu Zeshun1, Shu Huanran2, Gao Zhenhua1,3
(1.College of Materials Science and Engineering, Northeast Forestry University, Harbin 150040, Heilongjiang, China; 2.Zhejiang Quzhou Bolan Decoration Materials Co., Ltd., Quzhou 324000, Zhejiang, China; 3. Heilongjiang Province Key Laboratory of Wood Science and Technology, Harbin 150040, Heilongjiang, China)
【Abstract】In order to reduce the cost of soybean protein adhesive and improve its water resistance and coating performance, the soybean protein adhesive was prepared in this study, by using high-temperature defatted soybean meal powder as main raw material, polyamide polyamine-epichlorohydrine (PAE) as crosslinker, and adding sodium dodecyl sulfate (SDS). The effects of the amount of high-temperature defatted soybean meal powder and SDS content on the coating properties, bonding strength and water resistance of soybean protein adhesive as well as their mechanism were emphatically discussed. The research results showed that the addition of appropriate amount of SDS could stretch soybean protein through its emulsification, thus enhancing the wettability and crosslinking activity of soybean protein adhesive, which in turn improved the bonding performance and coating properties. When the amount of high-temperature defatted soybean meal powder was 70% and SDS content was 0.30%, the prepared soybean protein adhesive achieved the best bonding performance and coating properties, and its wet strength of 63 ℃soaking was increased to 1.45 MPa, which was 45% higher than the national standard requirements, meeting the needs of industrial production of type II plywood.
【Keywords】soybean protein adhesive; soybean meal powder; coating property; bonding performance
Study on curing kinetics of bisphenol A epoxy resin/aromatic amine curing system
Zhang Fengfeng1, Hou Yingying1,Wang Fengling1, Xu Shijie1, Deng Laihong2, Zhang Chunmei1
（1.Qingdao Tobacco Factory of China Tobacco Shandong Industrial Co., Ltd., Qingdao 266101, Shandong, China; 2.Production and Manufacturing Center of China Tobacco Shandong Industrial Co., Ltd., Ji'nan 250100, Shandong, China）
【Abstract】Using 4,4'-diaminodiphenyl methane (DDM) and 4,4'-diaminodiphenyl sulfone (DDS) as curing agent, the curing kinetics of two kinds of bisphenol A epoxy resin, i.e. E-44 and E-51, were studied by non-isothermal differential scanning calorimetry (DSC). The reaction parameters of curing at 5, 10, 15 and 20 ℃/min in the temperature range of 25-350 ℃ were collected and analyzed, and then the apparent activation energies of different epoxy curing systems were calculated by Starink method.At the same time, the curing reaction mechanism of bisphenol A epoxy resin/aromatic amine curing system was analyzed by using the dynamic rheological properties of each curing system, and the reaction rate equation of each curing system was calculated by using the two-parameter autocatalytic model. The research results showed that when the curing agent of epoxy curing system was different, the apparent activation energies of epoxy curing systems with DDM as curing agent (E-44/DDM, E-51/DDM) were lower than those of epoxy systems with DDS curing agent. When the same curing agent (DDM or DDS) was selected, the apparent activation energy of E-51 resin system was lower than that of E-44 resin curing system. The reaction rate equation results showed that the two-parameter autocatalytic model was in good agreement with the actual test results, which could be used to describe the curing process of bisphenol A epoxy resin/aromatic amine curing system.
【Keywords】epoxy resin; curing kinetics; dynamic rheological property; DSC
Study on multi-functional epoxy resin toughened and modified by carboxy-terminated polyurethane
Guo Yuting, Song Caiyu, Sun Mingming, Zhang Bin, Zhang Xugang, Wang Lei, Xue Gang, Li Jianhui
(Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin 150040, Heilongjiang, China)
【Abstract】Carboxy-terminated polyurethane oligomer (PUIC) was synthesized by using polytetrahydrofuran diol, 2,4-toluene diisocyanate and 1,2,4-benzenetricarboxylic anhydride as raw materials. By the reaction of carboxyl group with partial epoxy groups, a series of multi-functional epoxy resin (TGDDM-PUIC) modified by PUIC were prepared. The bonding properties, thermal mechanical properties and thermal stability of modified resin were investigated in details. The research results showed that modified epoxy resin TGDDM-PUIC was prepared successfully. TGDDM resin modified by PUIC remained good bonding properties and thermal stability, unlike other toughening methods leading to a significant reduction of thermal properties of epoxy resin, which achieved the balance between improving bonding properties and maintaining thermal stability. When the mass fraction of PUIC was 40%, the shear strength at 25 ℃ and peel strength of modified resin increased by 163% and 378%, respectively, compared to the pure resin. The thermal stability was good and the comprehensive performance was excellent.
【Keywords】carboxy-terminated polyurethane; multi-functional epoxy resin; bonding property; thermal stability
Study on the influence of silver-plated copper powder on the properties of electromagnetic shielding conductive adhesive
Li Bingzhang, Fan Jinfeng, Li Jing, Yue Qiaoping, Zhang Xiaogang, Zhang Guien
(China Electronics Technology Group Corporation No.33 Research Institute , Taiyuan 030006, Shanxi, China)
【Abstract】Conductive adhesive with good bonding properties and electromagnetic shielding performance was prepared with α-ω dihydroxy polysiloxane as the substrate adhesive, silver-plated copper powder as conductive filler, silicon micro powder, silica and zinc stearate as bulk filler. The effects of particle size, morphology, silver content and filling amount of silver-plated copper powder on lap shear strength, electrical conductivity and electromagnetic shielding performance of adhesive were investigated. The research results showed that the increase of silver content and filling amount of silver-plated copper powder significantly improved the conductivity of the cured conductive adhesive. With the increase of silver content and filling amount, the volume resistance first decreased and then stabilized. The shear strength of adhesive decreased with the increase of particle size and filling amount of conductive powder. In the experiment, when 45 μm dendritic conductive powder with 20% silver content (mass fraction) was used and the adding amount was 70.8%, the comprehensive performance of the conductive adhesive prepared was relatively good, the volume resistivity after curing reached 0.007 Ω·cm, the shear strength was 1.05 MPa, and the electromagnetic shielding performance was more than 85 dB (300 MHz-10 GHz).
【Keywords】silver-plated copper powder; adhesive; shear strength; electromagnetic shielding
Development and Application
Study on hygrothermal durability of underwater curable epoxy adhesive
Wang Guanjun1, Han Qing1, Tan Xiaolin2,Wang Daoyang3, Liu Haibo1, Kong Deao3
(1.Technology Testing Center, Shengli Oilfield Branch Company, Sinopec, Dongying257000, Shandong, China; 2.Shengli Oilfield Testing and Evaluation Research Co., Ltd., Dongying 257000, Shandong, China;3.Harbin Institute of Technology, Harbin 150006, Heilongjiang, China)
【Abstract】The evolution of water absorption, thermal-mechanical properties of an underwater curable epoxy adhesive immersed in water at different temperatures was systematically studied, and the long-term life of the adhesive and adhesive-steel interface at actual service temperature was predicted using Arrhenius equation. The research results showed that the adhesive had had the saturated absorption rate of 2.05%. After long-term immersion, the glass transition temperature and tensile properties of the adhesive deteriorated, but the long-term life retention rate of its tensile strength exceeded 60%, and the long-term life retention rate of bonding strength of the adhesive-steel interface was 54.30%, indicating that the adhesive could be used in water immersion environment for a long time.
【Keywords】underwater curable; epoxy adhesive; water absorption; durability
Synthesis of a silane-terminated polyurethane and its application in sealant preparation
（National Institute of Clean and Low-Carbon Energy, Beijing 102211）
【Abstract】A synthesis scheme different from previous silane-terminated polyurethane (SPU) prepolymer was designed. A silane-terminated polyurethane prepolymer was obtained by the capping reaction of —NCO silane and —OH terminated polyurethane prepolymer. Then, using it as the base material, adding catalyst and reinforcing filler, an elastic sealant product was prepared through formula selection. The research results showed that when the product prepared by MDI-100 was used as the base material for adhesive conditioning, KH-540 was used as the coupling agent, modified organotin catalyst was selected, w(nano calcium carbonate)=25%,w(hydrophobic silica)=2% (relative to the total mass), the comprehensive performance of the sealant prepared was relatively excellent. The sealant overcame the shortcomings of polyurethane and silicone sealant, had moisture-curing properties, the adhesive layer was non-foaming, elastic and paintable, and had excellent overall performance. Moreover, the synthesis process was simple and easy to control, the product was stable, and had been applied in the field of engineering sealing.
【Keywords】adhesive; silane-terminated; polyurethane; elastic sealant
Study on mechanical properties of two-component addition type room-temperature vulcanized silicone rubber
Chen Bingyao1, Yang Yongqiang2, Chen Deqi2, Quan Wengao2, Yang Yuqi2
(1. GuangdongSanvo Chemical Industry Technology Limited, Zhongshan 528429, Guangdong, China; 2. Guangdong Sanvo Holding Co., Ltd., Zhongshan 528429, Guangdong, China)
【Abstract】The effects of different types of vinyl silicone oil, the ratio of silicone vinyl to silicone hydrogen, and the adding amount of fumed silica on the mechanical properties of two-component addition type room-temperature vulcanized silicone rubber were investigated. The research results showed that when two types of vinyl silicone oil was compounded for preparation, the mechanical properties obtained were relatively optimal. When m(silicone vinyl)∶m(silicone hydrogen)=100∶3.5, its shear strength and hardness were the largest. When the adding amount of fumed silica was 10%, its comprehensive properties were relatively optimal.
【Keywords】silicone rubber, vinyl silicone oil, fumed silica
Influence of fly ash content on compressive strength of concrete lining of headrace tunnel
(China Anneng Group Third Engineering Bureau Co., Ltd., Chengdu611130, Sichuan, China)
【Abstract】Fly ash is widely used in hydraulic engineering to replace cement, and the performance of concrete prepared with fly ash seriously affects the construction effect. Therefore, it is important to study the influence of fly ash content on compressive strength in concrete lining of headrace tunnel. In this study, by adjusting the fly ash content, concrete specimens with 15%, 25% and 35% fly ash content were prepared, respectively, and the compressive strength of concrete mixed with fly ash under these influencing factors was verified by changing the curing temperature and adjusting the fineness of fly ash.Considering the actual environment of headrace tunnel lining, the influence of natural environment on the compressive strength of fly ash concrete was also studied. The research results showed that the fly ash with a content of 25% had better compressive strength, at the same time, when the temperature was controlled at 22 ℃, 45 mm square hole sieve with 25% fineness of fly ash was selected, it could well improve the compressive strength of concrete. Fly ash could react with acidic substances, therefore excessive amount of fly ash could reduce the compressive strength of concrete.
【Keywords】fly ash; headrace tunnel; concrete lining; compressive strength; fineness of fly ash; curing temperature
Special Topics and Review
Production process and application analysis of polymercaptan curing agent
Qian Dan, Liu Shihe, Fan Hong
(College of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310014, Zhejiang, China)
【Abstract】Polymercaptan is commonly used as low or room temperature curing agent for epoxy resin and UV crosslinking agent for unsaturated resin. In this paper, the product structure, performance, application field and production process of domestic and foreign enterprises producing polymercaptan curing agent were summarized. From the perspective of market demand, the characteristics of these products and their application in the field of adhesive, coating and ink were analyzed.
【Keywords】polymercaptan; polythiol; curing agent; synthetic process
Research status of thermal conductiveadhesive for aviation lighting products
Rao Yonggang, Zhao Xinwei, Chen Liang
(Shanghai Aviation Electric Co., Ltd., Shanghai 201100, China)
【Abstract】Aviation lamps have a compact structure and high sealing requirements, so heat dissipation has always been a prominent problem in the products. In this paper, the main types of thermal conductive adhesive used in aviation lighting products, including thermal conductive adhesive, thermal conductive gel, thermal conductive pad, and thermal conductive silicone grease.The thermal conductive characteristics and principles of each thermal conductive adhesive were outlined, and the factors affecting the thermal conductivity were summarized. Finally, some suggestions on the use of thermal conductive adhesive were put forward and their development was prospected.
【Keywords】thermal conductive adhesive; thermal conductive characteristics; thermal conductive principle; thermal conductivity
Modification and application progress of VAE emulsion
Zheng Jin1, Sun Pengfei2, Cheng Peng3
[1.Hongshi (Jiangsu) New Material Technology Co., Ltd., Shanghai 200235, China; 2.Institute of Materials Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210003, Jiangsu, China;3.Oriental Yuhong Civil Building Materials Co., Ltd., Beijing 100176, China]
【Abstract】The characteristics of vinyl acetate-ethylene copolymer emulsion (VAE emulsion) were reviewed, and the modification technology of VAE emulsion was introduced from copolymerization, blending, interpenetrating network, and addition of additives. Meanwhile, the application progress of VAE emulsion in adhesive, redispersible polymer powder, waterproof coating, laminating adhesive and building material was summarized. Finally suggestions were made for the future development of VAE emulsion.
【Keywords】VAE emulsion; adhesive; blending modification; copolymerization modification; emulsion application
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