以聚醚多元醇、聚苯醚多元醇、丙烯酸树脂、结晶型聚酯多元醇和4,4'-二苯基甲烷二异氰酸酯（MDI）制备了耐高温反应型聚氨酯热熔胶（PUR）。对比了几种多元醇的耐高温性能，探讨了聚苯醚多元醇用量、丙烯酸树脂用量以及结晶型聚酯多元醇种类和用量对PUR耐热性的影响。研究结果表明：（1）用聚苯醚多元醇制备的PUR耐热性最佳，110℃高温下具有2 MPa以上的剪切强度。（2）结晶型聚酯多元醇的熔点越高，黏度越大，高温下剪切强度越大，耐高温性能并未提高。综合来看，7360型是耐热型PUR应用中结晶型聚酯材料的优选方案。（3）聚苯醚多元醇用量越大，PUR黏度越大，开放时间越短，高温下剪切强度越大，耐高温老化性能越好。聚苯醚多元醇的最佳添加量为15%。（4）丙烯酸树脂用量越大，PUR黏度越大，高温下剪切强度越大，高温老化剪切强度保持率并未提高。综合来看，丙烯酸树脂的最佳添加量为15%。（5）采用15%的聚苯醚多元醇、29.5%的聚醚多元醇、15%的丙烯酸树脂、20%的7360型结晶型聚酯多元醇，以及0.5%的DMDEE与20%的MDI进行反应，所制得的电子产品用耐高温PUR的综合性能相对最佳。该配方制得的热熔胶在110℃下的黏度为7 400 mPa·s，剪切强度达到11.51 MPa，高温条件下剪切强度为2.42 MPa，且在120℃高温老化后剪切强度保持率达到85%。
High temperature resistant reactive polyurethane hot melt adhesive(PUR) was prepared by using polyether polyol,polyphenylene ether polyol,acrylic resin,crystalline polyester polyol,and 4,4'-diphenylmethane diisocyanate(MDI). The high temperature resistance of several polyols was compared,and the influence of the dosage of polyphenylene ether polyol,acrylic resin,and crystalline polyester polyol on the heat resistance of PUR was explored.The research results showed that,(1) The PUR prepared with polyphenylene ether polyol had the best heat resistance,with the shear strength of over 2 MPa at the high temperature of 110 ℃.（2） The higher the melting point and viscosity of crystalline polyester polyols,the greater the shear strength at high temperature,but the high temperature resistance was not improved.Overall,the type 7360 was the preferred solution for crystalline polyester materials in heat-resistant PUR application.(3) The larger the amount of polyphenylene ether polyol used,the higher the viscosity of PUR,the shorter the opening time,the greater the shear strength at high temperature,and the better the high-temperature aging resistance.The optimal addition amount of polyphenylene ether polyol was 15%.(4) The larger the amount of acrylic resin used,the higher the viscosity of PUR,and the higher the shear strength at high temperature. However,the retention rate of shear strength during high-temperature aging did not improve.Overall,the optimal addition amount of acrylic resin was 15%.(5) The comprehensive performance of hightemperature resistant PUR for electronic products was relatively optimal when reacting 15% polyphenylene ether polyol,29.5% polyether polyol,15% acrylic resin,20% crystalline polyester polyol type 7360,and 0.5% DMDEE with 20% MDI.The viscosity of hot melt adhesive produced by this formula was 7 400 mPa·s at 110 ℃,with the shear strength of 11.51 MPa. The shear strength under high temperature condition was 2.42 MPa,and the shear strength retention rate reached 85% after high-temperature aging at 120 ℃.
针对直升机的多层薄壁橡胶-金属结构的有效粘接，研发了一款新型胶粘剂（H-A&B）。该胶粘剂包含对金属和橡胶都有较好粘接性能的底胶（H-A）和面胶（H-B）。通过红外光谱仪对胶粘剂的官能团进行了分析，通过剥离强度试验、扫描电镜等对胶粘剂H-A&B的综合性能进行分析。研究结果表明：（1）H-A和H-B内部有类似的分子结构，二者更容易相互溶解，相互作用能量更低，使粘接效果更佳。（2）不锈钢或镍金属表面经底胶H-A刷涂后形成均匀、多孔、粗糙的粘接层，再经面胶H-B覆盖后形成完整胶层，显著改善表面形貌。能谱分析显示，刷涂胶层后金属表面元素转变为以C、O为主，表明形成有机胶层，与橡胶相容性良好，有助于提升界面粘接性能。（3）新型胶粘剂H-A&B的粘接力学性能表现优异，均高于指标要求，对金属和橡胶材料具有良好的粘接性能。（4）通过无损检测可以看出，采用新型胶粘剂H-A&B制作的典型样件比传统胶粘剂制作的样件脱粘缺陷数量更少、尺寸更小，所有缺陷尺寸均在工程允许范围之内。证明了新型胶粘剂H-A&B在粘接性能和工艺性能上要优于传统胶粘剂。
A new adhesive(H-A&B) was used for effective bonding of multilayer thin-walled rubber metal structures for helicopters.This adhesive contained a bottom adhesive(H-A) and a surface adhesive(H-B) that had good bonding properties to both metal and rubber.The functional groups of the adhesive were analyzed using an infrared spectrometer,and the comprehensive properties of the adhesive H-A&B were analyzed through peel strength tests,scanning electron microscopy,and other methods.The research results indicated that:(1)H-A and H-B had similar molecular structures inside,which made them more easily soluble and had lower interaction energy,resulting in better bonding effect.(2)A uniform,porous,and rough adhesive layer was formed on the surface of stainless steel or nickel metal after brushing with bottom adhesive H-A,and then covered with surface adhesive H-B to form a complete adhesive layer,significantly improving the surface morphology.Energy spectrum analysis showed that after brushing the adhesive layer,the surface elements of the metal changed to mainly C and O,indicating the formation of an organic adhesive layer with good compatibility with rubber,which helped to improve the interfacial bonding performance.(3)The bonding mechanical properties of the new adhesive H-A&B were excellent,both exceeding the required indicators,and had good bonding performance for metal and rubber materials.(4)Through nondestructive testing,it could be seen that the typical samples made with the new adhesive H-A&B had fewer debonding defects and smaller sizes than those made with traditional adhesive,and all defect sizes were within the engineering allowable range.It had been proven that the new adhesive H-A&B outperformed traditional adhesive in terms of bonding performance and processability.
本文系统阐述了汽车内饰领域聚氨酯（PU）胶粘剂及水性聚氨酯（WPU）胶粘剂的基本概况与制备方法，重点围绕WPU胶粘剂的主流改性研究展开综述。通过详细分析环氧树脂、有机硅、有机氟及纳米材料等多元改性方法对WPU胶粘剂的作用机制，深入探讨了改性产物的结构特征与性能演变规律。在此基础上对WPU胶粘剂的未来发展趋势进行了展望。
The basic overview and preparation methods of polyurethane(PU) adhesive and waterborne polyurethane(WPU) adhesive in the automotive interior field were elaborated systematically in this article,with a focus on the mainstream modification research of WPU adhesive.By analyzing in details the action mechanism of various modification methods such as epoxy resin,silicone,organic fluorine,and nanomaterials on WPU adhesive,the structural characteristics and performance evolution of the modified products were deeply explored.On this basis,the future development trend of WPU adhesive was discussed.
以环氧树脂为基体，采用复配胺类化合物为固化剂，添加经表面改性和组合优化的空心玻璃微球，成功制备了一种具有快速固化、低放热特性的低密度环氧填充料。详细考察了填充料的固化行为、凝胶时间、固化放热温度、剪切强度和压缩性能。研究结果表明：（1）固化剂C2活性高，替代三乙烯四胺可降低起始固化温度，促进快速固化；其引入显著降低放热焓变，减少放热量，避免爆聚。通过调控三乙烯四胺、C1与C2的活性梯度，可优化固化动力学，在快速凝胶的同时有效抑制放热峰。（2）固化剂配方优化显著影响体系的凝胶特性与放热行为。三乙烯四胺/C1组合易引发爆聚，引入C2可实现快速固化与均匀性的平衡，满足施工要求。（3）空心玻璃微球添加量的增加使体系密度显著降低，35%添加量时密度小于0.70 g/cm3，满足特定应用需求。该添加量下复合材料的力学性能良好，剪切强度达15.3 MPa，压缩强度超过55 MPa，压缩模量高于2 000 MPa，综合性能符合使用要求。（4）填充料流动性优异，能完整填充蜂窝目标部位，致密无气泡缺陷，与蜂窝材料粘接牢固无开裂。通过单侧注胶另一侧流出的工艺，实现嵌件周围空间填充及固化加固。该填充料可广泛应用于航空、交通等领域，尤其适用于飞机蜂窝结构的封边和填充。
A low-density epoxy filler with fast curing and low heat release characteristics was successfully prepared by using epoxy resin as matrix,compound amine compounds as curing agent,and adding hollow glass microspheres with surface modification and combination optimization. The curing behavior,gel time,curing exothermic temperature,shear strength and compression properties of the filler were investigated in details. The research results showed that,(1) Curing agent C2 had high activity and could replace triethylenetetramine to lower the initial curing temperature and promote rapid curing.Its introduction significantly reduced the enthalpy change of heat release,reduced the amount of heat released,and avoided explosive aggregation. By adjusting the activity gradient of triethylenetetramine,C1 and C2,the curing kinetics could be optimized,and the exothermic peak could be effectively suppressed while the gel was fast.(2) The optimization of curing agent formulation significantly affected the gel properties and exothermic behavior of the system.The combination of triethylenetetramine/C1 was prone to explosive polymerization,and the introduction of C2 could achieve a balance between fast curing and uniformity,meeting construction requirements.(3) The increase in the amount of hollow glass microspheres added significantly reduced the system density,with a density of less than 0.70 g/cm3 at 35% addition,meeting specific application requirements.The mechanical properties of the composite material were good at this addition amount,with the shear strength reaching 15.3 MPa,the compressive strength exceeding 55 MPa,and the compressive modulus higher than 2 000 MPa. The comprehensive performance met the use requirements.(4) The filler had excellent fluidity and could completely fill the target area of the honeycomb.It was dense without bubble defects and firmly adhered to the honeycomb material without cracking.By using the process of injecting adhesive on one side and flowing out on the other side,the space around the inserts was filled and solidified for reinforcement.This filler could be widely used in aviation,transportation and other fields,especially for edge sealing and filling of aircraft honeycomb structures.
<正>《中国胶粘剂》主要报道有关胶粘剂和密封剂领域的科研、生产、应用、发展、市场、产品性能与分析鉴定、粘接技术、管理等文稿，包括专题与综述、论文、成果报告、信息交流和资料介绍等。与作者关于投稿方面的约定（1）来稿必须具有创新性、实用性、科学性、准确性、规范性和可读性。（2）论文必须附不涉及泄密项目、无一稿多投和基金项目（包括基金编号）的单位公章证明。（3）首稿投递需缴纳50元审稿费（银行转账至“账号02000037 0920 0066 059，工行北京广渠路支行，中国胶粘剂和胶粘带工业协会”），录用后与相关费用一同缴纳，未录用不收取。
以2-羟乙基丙烯酸酯磷酸酯（HEMAP）与丙烯酸酯单体为原料，通过共聚反应制备丙烯酸酯磷酸酯压敏胶。重点研究了不同含量HEMAP对压敏胶粘接性能的影响及黏弹性行为。研究结果表明：（1）随着HEMAP含量的增加，1 220 cm~(-1)的P=O双键伸缩振动峰越明显，压敏胶的玻璃化转变温度（T_g）也略微增加。（2）随着HEMAP含量的增加，压敏胶的初粘性呈现逐渐下降趋势，持粘时间及剥离强度增加，而且压敏胶的耐高温性能提升。（3）同一温度下压敏胶的储能模量（G'）及损耗模量（G″）均随HEMAP含量增加而升高；在25～160℃的不同温度下，HEMAP含量增加，压敏胶的温度依赖性减弱，耐温性提升；HEMAP含量影响压敏胶的流变与粘接性能。（4）随着HEMAP含量的增加，压敏胶最大形变减小，恢复率升高，抗蠕变性增强。（5）扫描频率升高使压敏胶的G'和G″增加，而随着HEMAP含量的增加，聚合物链的缠结及交联密度进一步增加，链段松弛时间变短，导致压敏胶的G'及G″在不同频率范围内越来越高。PSA-P0.75具有较高的剥离强度，但其初粘性较差。
Using 2-hydroxyethyl acrylate phosphate(HEMAP) and acrylic monomer as raw materials,acrylate phosphate pressure sensitive adhesive was prepared by copolymerization reaction.The effects of different contents of HEMAP on the bonding performance and viscoelastic behavior of pressure sensitive adhesive were studied emphatically. The research results showed that,(1) As the content of HEMAP increased,the stretching vibration peak of the P=O double bond at 1 220 cm~(-1) became more pronounced,and the glass transition temperature(T_g) of pressure sensitive adhesive also slightly increased.(2) With the increase of HEMAP content,the initial tack of pressure sensitive adhesive gradually decreased,the holding time and peel strength increased,and the high temperature resistance of pressure sensitive adhesive improved.(3) The storage modulus(G') and loss modulus(G″) of pressure sensitive adhesive increased with the increase of HEMAP content at the same temperature.At different temperatures ranging from 25 to 160 ℃,with the increase of HEMAP content,the temperature dependence of pressure sensitive adhesive decreased,and the temperature resistance improved. The HEMAP content affected the rheological and bonding properties of pressure sensitive adhesive.(4) With the increase of HEMAP content,the maximum deformation of pressure sensitive adhesive decreased,the recovery rate increased,and the creep resistance was enhanced.(5) As the scanning frequency increased,the G' and G″ of pressure sensitive adhesive increased.However,with the increase of HEMAP content,the entanglement and cross-linking density of polymer chains further increased,and the relaxation time of chain segments became shorter,resulting in higher G' and G″ of pressure sensitive adhesive in different frequency ranges.PSA-P0.75 had high peel strength,but its initial tack was poor.
基于最新的行业统计数据和产业政策，从行业市场概况、经济运行特点、行业面临的问题与挑战，以及行业发展前景展望四个维度，系统分析并全面阐述中国胶粘剂和胶粘带行业的现状与发展动向。
Based on the updated industry statistics and policies,the current situation and development trends of China's adhesive and tape industry were analyzed systematically and elaborated comprehensively in this article from four aspects of industry market overview,economic operation characteristics,problems and challenges faced by the industry,and industry development prospects.
为突破传统四官能团环氧树脂四缩水甘油基二氨基二苯甲烷（TGDDM）黏度高、韧性差的技术瓶颈，本文以间氨基苯酚环氧树脂（mAP-E）为基体，通过调控其与TGDDM的共混比例，构建了JmAP系列环氧胶粘剂体系。系统研究了该胶粘剂体系的工艺性能、耐热特性和力学性能等关键指标。研究结果表明：（1）mAP-E体系能够显著降低TGDDM的黏度，所制备的JmAP胶粘剂具有较低的黏度，从而表现出良好的工艺性能。（2）通过分析胶粘剂的玻璃化转变温度（T_g），在JmAP系列胶粘剂中，TGDDM含量增加使T_g值向高温区移动，JmAP-5的玻璃化转变温度（T_g=164.7℃）较JmAP-0提高了16.3%，证明TGDDM的引入显著改善了环氧胶粘剂体系的耐热性能。（3）通过分析力学性能，JmAP系列胶粘剂随着TGDDM比例的增加，在不同温度下的各项力学性能都有不同程度的提升。其中，JmAP-5在高温下的综合力学性能相对较为突出，各温度下的拉伸剪切性能优良。在宽温域拉伸剪切性能测试中，JmAP-5也表现出最佳综合性能。（4）吸水性能分析表明，在JmAP系列胶粘剂体系中，各配方胶粘剂的吸水率均未超过0.5%，展现出优异的耐久性和使用寿命。（5）电学性能分析表明，JmAP系列胶粘剂的电容稳定性良好，波动范围在0.15 pF以内，相对介电常数相差不超过0.15，介电损耗在2%以下。其中JmAP-5的电学性能最好，1 000 Hz下的电容为5.37～5.53 pF，介电损耗低于1.72%，相对介电常数在4.14～4.22之间。这说明JmAP-5配方有着优异的电学性能，可以适用于电子绝缘领域。
To overcome the technical bottleneck of high viscosity and poor toughness of traditional tetra functional group epoxy resin of tetraglycidyl diaminodiphenylmethane(TGDDM),a series of JmAP epoxy adhesive systems were established in this article by using m-aminophenol epoxy resin(mAP-E) as the matrix and adjusting its blending ratio with TGDDM.The key performance indicators such as the processability,thermal resistance,and mechanical properties of adhesive systems were investigated systematically.The research results showed that,(1) The mAP-E system could significantly reduce the viscosity of TGDDM,and the prepared JmAP adhesive had a lower viscosity,thus exhibiting good processability.(2) By analyzing the glass transition temperature(T_g) of the adhesive,it was found that in the JmAP series adhesive,the increase in TGDDM content caused the T_g value to shift towards higher temperatures.The glass transition temperature(T_g=164.7 ℃) of JmAP-5 increased by 16.3% compared to JmAP-0,demonstrating that the introduction of TGDDM significantly improved the heat resistance of the epoxy adhesive system.(3) By analyzing the mechanical properties,the JmAP series adhesive showed varying degrees of improvement in various mechanical properties at different temperatures with the increase of TGDDM ratio.Among them,JmAP-5 had relatively outstanding comprehensive mechanical properties at high temperature and excellent tensile shear properties at various temperatures. In the wide temperature range tensile shear performance test,JmAP-5 also showed the best comprehensive performance.(4) The analysis of water absorption performance showed that in the JmAP series adhesive system,the water absorption rate of each formula adhesive did not exceed 0.5%,demonstrating excellent durability and service life.(5) Electrical performance analysis showed that the JmAP series adhesive had good capacitance stability,with the fluctuation range within 0.15 pF,the relative dielectric constant difference of no more than 0.15,and the dielectric loss of less than 2%.Among them,JmAP-5 had the best electrical performance,with the capacitance of 5.37-5.53 pF at 1 000 Hz,the dielectric loss of less than 1.72%,and the relative dielectric constant between 4.14-4.22. This indicated that the JmAP-5 formulation had excellent electrical properties and could be applied in the field of electronic insulation.
针对目前光产碱剂吸收波长短，难以与LED光源匹配的问题，本文以还原态脒（PL-DBN）为光产碱剂，分别与异丙基硫杂蒽酮（ITX）、2-乙基蒽醌（2-EAQ）和9,10-二丁氧基蒽（DBA）三种光敏剂复配，制备了一类LED响应的光产碱体系，并系统研究了其在巯基-环氧胶粘剂中的应用。研究结果表明：（1）PL-DBN/2-EAQ体系具有最小的电子转移吉布斯自由能（-3.227 eV），光敏化效率最高；（2）在365 nm LED辐照下，PL-DBN/2-EAQ体系的pH可从7.65快速升至11.08，表明其具有优异的产碱效率；（3）随光照时间延长（0～15 min），巯基-环氧聚合起始温度可从80.3℃降至56.2℃，表明光产碱体系有效降低了反应能垒。（4）巯基和环氧官能团转化率最终可达95%和100%；光照15 min的样品在60℃放置1 h可完全固化，粘接强度达3.5 MPa，显示出其在精密粘接领域（如柔性电子封装、光学器件组装等）的良好应用前景。
In response to the problem of short absorption wavelength and difficulty in matching with LED light sources,reduced amidine(PL-DBN) was used as a photo alkali generator in this paper,and combined it with three photosensitizers,namely isopropylthioanthraquinone(ITX),2-ethylanthraquinone(2-EAQ),and 9,10-dibutoxyanthracene(DBA),a type of LED-responsive photo alkali system was prepared,and its application in thiol-epoxy adhesive was studied systematically. The research results showed that,(1) The PL-DBN/2-EAQ system had the smallest electron transfer Gibbs free energy（-3.227 eV） and the highest photosensitization efficiency.(2) Under 365 nm LED irradiation,the pH of PL-DBN/2-EAQ system could rapidly increase from 7.65 to 11.08,indicating its excellent alkali production efficiency.(3) With the extension of light exposure time(0-15 min),the starting temperature of thiol-epoxy polymerization could be reduced from 80.3 ℃ to 56.2 ℃,indicating that the photo alkali production system effectively reduced the reaction energy barrier.(4) The conversion rates of thiol and epoxy functional groups could ultimately reach 95% and 100%,respectively. The sample exposed to light for 15 minutes could be completely cured after being placed at 60 ℃ for 1 hour,with a bonding strength of 3.5 MPa,demonstrating its promising application prospects in precision bonding fields such as flexible electronic packaging and optical device assembly.
本文采用环氧树脂、界面改性剂、增韧剂和固化剂为原料，采用熔融与机械共混的方法，制备了一种新型环氧胶膜，并对其固化工艺、耐热性能、微观形貌及力学性能进行了研究。研究结果表明：（1）通过DSC法对改性树脂的固化反应动力学进行了研究，通过线性拟合求得反应活化能E_a=68.17 kJ/mol和反应级数n=0.92，说明基体树脂固化反应为一个复杂的固化反应过程。（2）通过tanδ法测试该胶膜的玻璃化转变温度分别为194℃和223℃，胶膜具有良好的热机械性能。TG曲线表明固化后的胶膜质量损失5%的温度约为351℃，说明胶膜具有优异的耐高温特性。（3）23℃下，钛合金与复材及铝合金与铝合金的剪切强度均在40 MPa以上，相差较小；在121℃和177℃下，钛合金与复材的剪切强度明显低于铝合金与铝合金，因此高温条件下（121℃及177℃）钛合金与复材的胶接强度取决于复材的本体强度。（4）常温（23℃）及高温（177℃）测试条件下，两种固化工艺（150℃/3 h及180℃/3 h）下胶膜对钛合金与复材试片的剪切强度都很接近，破坏模式基本一致，表明胶膜在两种固化条件下实现了完全固化，达到同样的粘接效果。（5）该胶膜在航空发动机复合材料叶片领域具有一定的应用前景。
Using epoxy resin,interfacial modifier,toughening agent,and curing agent as raw materials,a new type of epoxy adhesive film was prepared in this paper by a combination of melting and mechanical blending methods. The curing process,heat resistance,micromorphology,and mechanical properties of the film were subsequently investigated.The research results showed that,(1) The curing reaction kinetics of the modified resin were investigated by using the DSC method.Through linear fitting,the reaction activation energy E_a was determined to be 68.17 kJ/mol and the reaction order n was 0.92,indicating that the curing reaction of the matrix resin was a complex curing process.(2) The glass transition temperatures of adhesive film were tested by using the tanδ method and found to be 194 ℃ and 223 ℃,respectively.The adhesive film exhibited excellent thermal and mechanical properties. The TG curve showed that the temperature at which the cured adhesive film lost 5% of its mass was approximately 351 ℃,indicating that the adhesive film had excellent high-temperature resistance.(3) At 23 ℃,the shear strength of titanium alloy and composite material,as well as aluminum alloy and aluminum alloy,were all above 40 MPa,with a small difference.At 121 ℃ and 177 ℃,the shear strength of titanium alloy and composite material was significantly lower than that of aluminum alloy and aluminum alloy.Therefore,the bonding strength of titanium alloy and composite material under high temperature conditions(121 ℃ and 177 ℃) depended on the bulk strength of the composite material.(4) Under the testing conditions of room temperature(23 ℃) and high temperature(177 ℃),the shear strength of adhesive film on titanium alloy and composite specimens was very close under two curing processes(150 ℃/3 h and 180 ℃/3 h),and the failure mode was basically the same,indicating that the adhesive film had achieved complete curing under both curing conditions and achieved the same bonding effect.(5) The adhesive film had certain application prospects in the field of composite blades for aircraft engines.