2025年 05期
国内外无色透明环氧胶粘剂研究进展
Research progress of colorless and transparent epoxy adhesive at home and abroad
朱宸廷;虞鑫海; Zhu Chenting;Yu Xinhai;无色透明环氧胶粘剂因其独特的透明性和优异的机械性能，在众多领域具有广泛的应用前景。随着科技的发展和市场需求的不断增长，无色透明环氧胶粘剂在航空航天、汽车工业、电子电气以及光学仪器等领域得到了越来越多的关注。本文综述了无色透明环氧胶粘剂的研究进展、种类、制备方法、性能指标及其在不同工业领域的应用情况。在无色透明环氧树脂的研究与应用方面，双酚A型、双酚F型、氢化双酚A型环氧树脂及其他新型无色透明环氧树脂均表现出了独特的性能。通过添加各种改性剂、填料或选择不同的固化剂，可以显著提升环氧树脂的机械性能、耐热性、透明度等关键性能指标。随后对其市场现状和应用领域进行介绍，最后对未来发展进行了展望。
Colorless and transparent epoxy adhesive has broad application prospects in many fields due to its unique transparency and excellent mechanical properties.With the development of technology and the continuous growth of market demand,colorless and transparent epoxy adhesive has received increasing attention in fields such as aerospace,automotive industry,electronic and electrical,and optical instruments.The research progress,types,preparation methods,performance indicators,and application in different industrial fields of colorless and transparent epoxy adhesive were reviewed in this paper.In terms of the research and application of colorless and transparent epoxy resin,bisphenol A type,bisphenol F type,hydrogenated bisphenol A type epoxy resins,and other new colorless and transparent epoxy resins all exhibited unique properties.By adding various modifiers,fillers,or selecting different curing agents,the mechanical properties,heat resistance,transparency,and other key performance indicators of epoxy resin could be significantly improved. Subsequently,the market status and application areas were introduced,and finally,the future development prospects were discussed.
骨胶的研究及应用现状
Research and application of bone glue
杨玉娜;侯清娥;高红芳;薛萍;蒋宝;许海媛; Yang Yuna;Hou Qinge;Gao Hongfang;Xue Ping;Jiang Bao;Xu Haiyuan;Weinan Vocational and Technical College;骨胶是一种在木材、包装、农业等行业得到广泛应用、具有广阔推广市场的天然高分子胶粘剂，其生产原料来源广泛，成本较低，环保无污染。本文概述了骨胶的改性方法、应用领域等方面的研究和现状，指出了骨胶作为胶粘剂当前存在的优势和不足，希望能为骨胶的相关研究提供参考，进而扩展骨胶的应用范围。
Bone glue is a natural polymer adhesive widely used in industries such as wood,packaging,and agriculture,with a broad market for promotion. Its production raw materials are widely sourced,the cost is low,and it is environmentally friendly and pollution-free. The research and current status of modification methods and application fields of bone glue were summarized in this article,and the advantages and disadvantages of bone glue as adhesive were pointed out. It was hoped that this could provide reference for related research on bone glue and expand its application scope.
软段结构对于水性聚氨酯性能的影响
The influence of soft segment structure on the performance of waterborne polyurethane
徐一平;张嘉琦;翟瑞雪;周超; Xu Yiping;Zhang Jiaqi;Zhai Ruixue;Zhou Chao;以异佛尔酮二异氰酸酯（IPDI）为硬段，2,2-双（羟甲基）丙酸（DMPA）、1,4-丁二醇（BDO）为主要原料，分别以聚碳酸酯二醇（PCDL）、聚己内酯二醇（PCL）、聚己二酸-1,4-丁二醇酯二醇（PBA）、聚四氢呋喃二醇（PTMG）和聚丙二醇（PPG）为多元醇，通过预聚体法和丙酮法相结合的方法制备了5种不同软段结构（PCDL、PCL、PBA、PTMG和PPG）的水性聚氨酯（WPU）。揭示了软段结构对材料热性能、力学性能、黏附性能以及耐水性的影响。研究结果表明：PCDL基WPU在热性能、力学性能和耐水性能方面表现优异，但过高的刚性可能限制其在某些柔性应用中的使用；PCL和PBA基WPU在综合性能上表现均衡，适合对热稳定性和力学性能有一定要求的应用场景；而PPG基WPU因其高柔顺性和低玻璃化转变温度，适用于对柔韧性要求较高的领域，但其热稳定性和耐水性能需进一步优化。
Using isophorone diisocyanate(IPDI) as the hard segment,2, 2-bis(hydroxymethyl) propionic acid(DMPA),and 1,4-butanediol(BDO) as the main raw materials,five different soft segment structures(PCDL,PCL,PBA,PTMG,and PPG) of waterborne polyurethane(WPU) were prepared by combining pre-polymerization and acetone methods,with polycarbonate diol(PCDL),polycaprolactone diol(PCL),poly(1,4-butanediol adipate) diol(PBA),poly(tetrahydrofuran) diol(PTMG),and polypropylene glycol(PPG) as polyols.The influence of soft segment structure on the thermal properties,mechanical properties,bonding performance,and water resistance of the materials was revealed. The research results showed that PCDL based WPU exhibited excellent thermal,mechanical,and water resistance properties,but its excessively high rigidity might limit its use in certain flexible applications. PCL and PBA based WPU exhibited balanced overall performance,making them suitable for application scenarios with certain requirements for thermal stability and mechanical properties.PPG based WPU was suitable for fields that required high flexibility due to its high flexibility and low glass transition temperature,but its thermal stability and water resistance needed to be further optimized.
氮化硼对丙烯酸酯导热结构胶的改性研究
Study on the modification of boron nitride to acrylate thermal conductive structural adhesive
刘妹;葛冰洁;戚安杰;于竹青;项尚林; Liu Mei;Ge Bingjie;Qi Anjie;Yu Zhuqing;Xiang Shanglin;为解决氮化硼纳米颗粒与高分子基材难以浸润相容、分散性差、易团聚的难题，本文以改性氮化硼（BN）、环氧丙烯酸酯齐聚物、甲基丙烯酸月桂酯（LMA）、三官能团酸酯（SR9051 NS）、偶氮二异丁腈（AIBN）和对苯二酚等为原料，制备了丙烯酸酯导热结构胶，并对其流变性能、导热性能、粘接性能等进行表征。研究结果表明：导热结构胶的黏度及其固化物的导热系数随改性氮化硼用量的增加而增大，改性氮化硼用量为40%时，导热结构胶的导热系数相比未添加氮化硼的结构胶提升了540%。随着改性氮化硼含量的增加，剪切强度呈现先增加后下降的趋势，其中20%BN/SA导热结构胶的剪切强度最高可达15 MPa。
To solve the problems of difficult infiltration compatibility,poor dispersibility,and easy aggregation between boron nitride nanoparticles and polymer substrates,acrylic thermal conductive structural adhesive was prepared in this paper by using modified boron nitride(BN),epoxy acrylate oligomers,lauryl methacrylate(LMA),trifunctional acid ester(SR9051 NS),azobisisobutyronitrile(AIBN),and hydroquinone as raw materials,and its rheological properties,thermal conductivity,and bonding properties were characterized. The research results showed that the viscosity of thermal conductive structural adhesive and the thermal conductivity of its cured material increased with the increase of modified boron nitride amount.When the amount of modified boron nitride was 40%,the thermal conductivity of thermal conductive structural adhesive was 540% higher than that of the structural adhesive without boron nitride added.With the increase of modified boron nitride amount,the shear strength showed a trend of first increasing and then decreasing,among which the shear strength of 20%BN/SA thermal conductive structural adhesive could reach up to 15 MPa.
硫酸钙晶须对环氧树脂胶粘剂粘接强度及热性能的影响
Effect of calcium sulfate whiskers on bonding strength and thermal properties of epoxy resin adhesive
赵明;张雪;孙明明;张绪刚;张斌;李坚辉;王磊;李金籽; Zhao Ming;Zhang Xue;Sun Mingming;Zhang Xugang;Zhang Bin;Li Jianhui;Wang Lei;Li Jinzi;按照70∶30∶20的质量比例将WSR618型环氧树脂、AG-80型环氧树脂、增韧剂进行混合，组成主体树脂体系，以双氰胺、有机脲为固化促进剂体系，并添加硅烷偶联剂、硫酸钙晶须填料组成胶粘剂体系。考察了硫酸钙晶须填料对环氧树脂胶粘剂在不同胶层厚度下单搭接剪切强度的影响，并对添加硫酸钙晶须的胶粘剂体系的固化反应热、玻璃化转变温度(Tg)、膨胀系数、热稳定性进行了研究。研究结果表明：(1)在环氧树脂胶粘剂中添加硫酸钙晶须可以降低胶粘剂随胶层增厚而单搭接剪切强度下降的幅度，并在一定程度上增强了胶粘剂在0.5 mm和1.0 mm厚胶层下的剪切强度。(2)添加硫酸钙晶须能降低环氧树脂胶粘剂体系的固化反应热，提高体系固化反应峰值温度。(3)硫酸钙晶须的加入降低了胶粘剂体系的Tg，当其添加量为10份时体系Tg的降低幅度很小，当添加量超过10份时，体系Tg的降低幅度开始变大。(4)添加硫酸钙晶须能降低环氧树脂胶粘剂体系的热膨胀系数(
WSR618 epoxy resin,AG-80 epoxy resin,and toughening agent were mixed in a mass ratio of 70∶30∶20 to form the main resin system.Dicyandiamide and organic urea were used as curing accelerators,and silane coupling agent and calcium sulfate whiskers filler were added to form the adhesive system.The effect of calcium sulfate whisker filler on the single lap shear strength of epoxy resin adhesive at different adhesive layer thicknesses was investigated,and the curing reaction heat,glass transition temperature(Tg),expansion coefficient,and thermal stability of the adhesive system with calcium sulfate whiskers added were studied.The research results showed that,(1) Adding calcium sulfate whiskers to epoxy resin adhesive could reduce the magnitude of the decrease in single lap shear strength of the adhesive as the adhesive layer thickened,and to some extent enhanced the shear strength of the adhesive under 0.5 mm and 1.0 mm thick adhesive layers.(2) Adding calcium sulfate whiskers could reduce the curing reaction heat of epoxy resin adhesive system and increased the peak curing reaction temperature of the system.(3) The addition of calcium sulfate whiskers reduced the Tg of the adhesive system. When the addition amount was 10 phr,the decrease in Tg of the system was very small.When the addition amount exceeded 10 phr,the decrease in Tg of the system began to increase.(4) Adding calcium sulfate whiskers could reduce the thermal expansion coefficient(
具有全温域特性聚氨酯结构胶的制备与性能研究
Preparation and performance study of polyurethane structural adhesive with full temperature range characteristics
龚鸿亮; Gong Hongliang;采用多元醇组分（包括小分子扩链剂1,4-丁二醇、分子量为5 000的三官能度大分子聚醚）、异氰酸酯组分（包括特制的聚氨酯预聚体、碳化二亚胺改性液化MDI、粗MDI等）和其他助剂（填料、分子筛活化粉、消泡剂等），制备了一种双组分聚氨酯结构胶粘剂。测试了其在较宽温度范围内各项性能（拉伸强度、断裂伸长率、剪切强度、储能模量）以及热性能分析。另外，还研究了不同扩链剂或交联剂对全温域体系性能的影响。研究结果表明：（1）QWY-1制备的聚氨酯结构胶表现出很好的低温韧性和全温域特性。在低温下（-30℃）有很高的本体强度，达到29.67 MPa，同时表现为很高的断裂韧性，断裂伸长率高达330%左右。另外，其在-40～80℃范围内各项力学性能稳定，不随着温度有较大的变化幅度，可以规避掉由于玻璃化转变温度引起的材料性能的突变。（2）通过不同的扩链剂或交联剂可以制备出不同模量梯度的全温域特性聚氨酯结构胶（QWY-1、QWY-2和QWY-3胶样），其25℃模量分别为57.52、15.97和663.77 MPa。其中，QWY-3胶样表现为出色的低温韧性和高温强度，其60℃下的拉伸强度达12.23 MPa，断裂伸长率为39.07%，也表现出一定的全温域特性。
Two-component polyurethane structural adhesive was prepared by using polyol components(including small molecule chain extender 1,4-butanediol,trifunctional macromolecule polyether with a molecular weight of 5 000),isocyanate components(including specially formulated polyurethane prepolymers,carbodiimide modified liquefied MDI,crude MDI,etc.),and other additives(fillers,molecular sieve activation powder,defoamers,etc.).Its various properties(tensile strength,elongation at break,shear strength,storage modulus) and thermal performance analysis over a wide temperature range were tested.In addition,the influence of different chain extenders or crosslinkers on the performance of the full temperature range system was also studied.The research results showed that,(1) The polyurethane structural adhesive prepared by QWY-1 exhibited excellent lowtemperature toughness and full temperature range characteristics.At low temperatures（-30 ℃）,it had high intrinsic strength,reaching 29.67 MPa,and exhibited high fracture toughness,with elongation at break of about 330%.In addition,its mechanical properties were stable within the range of-40～80 ℃,without significant changes with temperature,which could avoid sudden changes in material properties caused by glass transition temperature.(2) By using different chain extenders or crosslinkers,polyurethane structural adhesive with different modulus gradients could be prepared in the full temperature range(QWY-1,QWY-2,and QWY-3 samples),with modulus of 57.52,15.97,and 663.77 MPa at 25 ℃,respectively.Among them,QWY-3 adhesive sample exhibited excellent low-temperature toughness and high-temperature strength,with tensile strength of 12.23 MPa at 60 ℃ and elongation at break of 39.07%,demonstrating certain full temperature range characteristics.
各向同性导电胶膜的固化行为及固化工艺性研究
Research on curing behavior and curing processability of isotropic conductive adhesive film
魏运召;赵濛;何影翠;吴健伟;王雪松;付刚;赵玉宇; Wei Yunzhao;Zhao Meng;He Yingcui;Wu Jianwei;Wang Xuesong;Fu Gang;Zhao Yuyu;采用流变仪测定了导电胶膜的化学流变特性，以差示扫描量热法测试了不同升温速率下的放热曲线，并进行了动力学计算。系统研究了固化温度、固化压力对导电胶膜的导电性和粘接性能的影响。研究结果表明：（1）导电胶膜可加压定位，在升温过程中实现对被粘材料良好的浸润和粘接。（2）固化温度在125～160℃，活化能约109 kJ/mol，在此区间内导电胶膜可实现良好的固化和较低的体积电阻率。（3）提高固化温度有利于提高导电胶膜的导电性能。（4）增加固化压力有利于导电胶膜对被粘表面的浸润，提高剪切强度。
The chemical rheological properties of conductive adhesive film were measured by using rheometer,and the heat release curves at different heating rates were tested by using differential scanning calorimetry,followed by kinetic calculations. The effects of curing temperature and curing pressure on the conductivity and bonding properties of conductive adhesive film were systematically studied.The research results showed that,(1) The conductive adhesive film could be pressurized and positioned to achieve good wetting and bonding of the adhered material during the heating process.(2) The curing temperature was between 125-160 ℃,and the activation energy was about 109 kJ/mol.Within this range,the conductive adhesive film could achieve good curing and low volume resistivity.(3) Raising the curing temperature was beneficial for improving the conductivity of conductive adhesive film.(4) Increasing the curing pressure was beneficial for the infiltration of conductive adhesive film on the adhered surface and improved the shear strength.
一种聚氨酯/环氧改性PVC高温固化焊缝密封胶的制备
Preparation of a polyurethane/epoxy modified PVC high-temperature curing weld sealant
郭盟;招兆林;边峰;江虹; Guo Meng;Zhao Zhaolin;Bian Feng;Jiang Hong;以聚氯乙烯（PVC）树脂为主要原料，加入聚氨酯树脂、环氧树脂等，制备了一种高温固化不黄变、力学性能优异的焊缝密封胶。讨论了PVC树脂、热稳定剂、环氧树脂/固化剂的用量比例、聚氨酯树脂对密封胶高温固化后力学性能、外观黄变、粘接性能的影响。研究结果表明：高温固化的焊缝胶优先选用高聚合度的PVC树脂；热稳定剂可明显改善密封胶高温固化的性能，最佳添加量控制在2.5%左右（质量分数）适宜；引入环氧树脂能提升密封胶的拉伸强度、粘接性，环氧树脂添加量在6%左右适宜，环氧树脂与固化剂比例在10∶1左右较为适宜；加入聚氨酯树脂能明显改善密封胶的力学性能和黄变性，添加量在2%～4%较为适宜。
A high-temperature curing weld sealant with excellent mechanical properties and no yellowing was prepared by using polyvinyl chloride(PVC) resin as the main raw material,and adding polyurethane resin,epoxy resin,etc. The effects of PVC resin,heat stabilizer,epoxy resin/curing agent amount proportion,and polyurethane resin on the mechanical properties,appearance yellowing,and bonding properties of sealant after high-temperature curing were discussed.The research results showed that high degree of polymerization PVC resin was preferred for high-temperature curing weld adhesive. Heat stabilizer could significantly improve the hightemperature curing performance of sealant,and the optimal addition amount should be controlled at around 2.5%(mass fraction).Introducing epoxy resin could improve the tensile strength and adhesion of sealant.The appropriate amount of epoxy resin added was around 6%,and the proportion of epoxy resin to curing agent was around 10∶1.Adding polyurethane resin could significantly improve the mechanical properties and yellowing of sealant,and the appropriate addition amount was 2% to 4%.
瓷器类文物补配材料耐老化性能研究
Research on aging resistance of patching materials for porcelain cultural relics
周璐;王晓燕; Zhou Lu;Wang Xiaoyan;补配是瓷器类文物修复工艺中十分重要的环节，其中所用的补配材料，不仅影响到后期上色、绘纹和仿釉等工艺的开展，也关系到文物完整结构的恢复和长期的展陈效果。本文选用3种环氧胶粘剂（红星509、WD3620和合众AAA）作基料、高岭土作填料来制备补配材料，通过力学性能测试，筛选出基料/填料的相对最优比。按照瓷器类文物本体强度的不同需求，制备不同粘接强度的腻子用于补配，避免对文物本体产生损伤。此后，对最优比腻子进行人工加速老化试验，表征其老化前后的拉伸剪切强度、抗拉强度、色度及接触角等，并通过傅里叶变换红外光谱分析其老化机理。研究结果表明：（1）高岭土作填料不仅能够有效填充环氧胶粘剂的组织缺陷，起到一定的支撑作用，还能够提高环氧胶粘剂的粘接力。当环氧胶粘剂与高岭土的质量比为100∶55时，所制备的腻子粘接力和抗变形能力最好。（2）3种环氧胶粘剂制备的腻子中，腻子A的抗拉强度虽总体低于腻子B、腻子C，但基于整体稳定性的考量，其综合耐老化性能最好，适用于多种环境下的补配工作。（3）腻子B的耐紫外、耐湿性能次之，但经人工加速老化试验后，其粘接力和抗变形能力衰减幅度较大，适用于临时性的粘接补配。（4）温度是环氧型补配材料老化的主要影响因素，其次是紫外光和湿度。因此，经环氧胶粘剂修复后的瓷器类文物在展陈或保藏时，首要条件是控温，同时也应尽量做好避免紫外光和控湿工作。
Patching is a crucial step in the restoration process of porcelain cultural relics.The materials used for patching not only affect the subsequent coloring,pattern drawing,and glaze imitation techniques,but also affect the restoration of the complete structure of cultural relics and their long-term display effect.In this paper,three types of epoxy adhesive(Red Star 509,WD3620,and Hezhong AAA) was selected as base materials and kaolin as fillers to prepare patching materials. Through mechanical property testing,the relative optimal ratio of base materials/fillers was obtained.According to the different strength requirements of porcelain cultural relics,putty with different bonding strength was prepared for patching to avoid damage to the cultural relics. Afterwards,artificial accelerated aging tests were conducted on the optimal ratio putty to characterize its tensile shear strength,tensile strength,chromaticity,and contact angle before and after aging,and its aging mechanism was analyzed by Fourier transform infrared spectroscopy.The research results showed that,(1) Kaolin as filler could not only effectively fill the structural defects of epoxy adhesive and provide certain support,but also improve the bonding strength of epoxy adhesive. When the mass ratio of epoxy adhesive to kaolin was 100∶55,the bonding strength and deformation resistance of the prepared putty were the best.(2) Among three types of putty prepared with epoxy adhesive,although the tensile strength of putty A was generally lower than that of putty B and putty C,based on the consideration of overall stability,its comprehensive aging resistance was the best and it was suitable for patching work in various environments.(3) The UV resistance and moisture resistance of putty B were the second,but after artificial accelerated aging test,its bonding strength and deformation resistance decreased significantly,making it suitable for temporary adhesive repair.(4) Temperature was the main influencing factor on the aging of epoxy patching materials,followed by ultraviolet light and humidity.Therefore,when displaying or preserving porcelain cultural relics repaired with epoxy adhesive,the primary condition was temperature control,and efforts should also be made to avoid ultraviolet light and humidity control.
新型雷击防护膜90°剥离强度的性能影响研究
Study on performance influence of 90° peel strength of new lightning protection film
孙田培;赵大方;李建恒;刘寒松;李斌太; Sun Tianpei;Zhao Dafang;Li Jianheng;Liu Hansong;Li Bintai;新型雷击防护膜采用功能层和胶膜层制成。本文从防护膜自身组成和结构出发，首先研究了胶膜含量、结构组成对其防雷击性能的影响。在此基础上研究了防护膜自身组成和结构以及90°剥离制样条件和工艺对新型雷击防护膜90°剥离强度的影响。研究结果表明：增加胶膜含量不利于其防雷击性能的提升，但可以提高其90°剥离强度；调整防护膜中功能层和胶膜层的组成顺序不会对防雷击性能造成显著影响，但会影响其90°剥离强度及其破坏模式。此外，制样时防护膜的铺贴方向、铝片尺寸和加工方式等因素会对雷击防护膜的90°剥离强度和破坏形式产生一定的影响。
The new lightning protection film was made of functional layers and adhesive film layers.Starting from the composition and structure of the protective film itself,the influence of the content and structural composition of adhesive film on its lightning protection performance was first studied.On this basis,the influence of the composition and structure of the protective film itself,as well as the conditions and processes for 90° peeling of the sample,on its 90° peel strength of new lightning protection film were studied.The research results showed that increasing the content of adhesive film was not conducive to improving its lightning protection performance,but it could increase its 90 ° peel strength.Adjusting the composition order of the functional layer and adhesive layer in the protective film did not significantly affect its lightning protection performance,but affected its 90 ° peel strength and failure mode.In addition,factors such as the paving direction of the protective film,the size of the aluminum sheet,and the processing method during sample preparation could have a certain impact on the 90 ° peel strength and failure mode of the lightning protection film.