儿茶酚型水下胶粘剂的研究进展

张承钰^1,2，吴雯晓^1,2，杨智慧^1,2，史浩伯³，

田伟智³，谢雨辰^1,2，秦佳琦^1,2，卢海峰^1,2

（1.山东大学化学与化工学院，山东济南 250100；2.山东省先进有机硅材料与技术重点实验室，山东济南  256401；3.北京星航机电装备有限公司，北京  100074）

【摘  要】海洋工业、生物医疗等应用领域需要与浸没在水中的表面进行粘接的胶粘剂，但水化层通常会阻碍胶粘剂和表面之间的相互作用。受生物启发，儿茶酚官能化聚合物已被广泛研究并用于水下黏附。尽管相较于干胶，其粘接强度和基材多样性还有不少提升空间，但在粘接强度方面获得了很大进步。本综述梳理、概述了含有儿茶酚基团的水下胶粘剂的国内外最新研究进展。从海洋生物贻贝的吸附原理展开，探讨儿茶酚基团的界面吸附，概述基于不同机理的水下胶粘剂的性能。最后对其可能的发展方向进行展望，为解决潮湿环境下的粘接难题提供新的思路与方法。

【关键词】水下；胶粘剂；粘接；儿茶酚

牙齿粘接剂新进展

方  昭，侯丹丹，杜  超，周  同，王春堯，郭  敏

（中国石油化工股份有限公司医用卫生材料研究与应用重点实验室，北京 100013）

【摘  要】近年来，牙齿粘接剂通过引入各种新结构，有效改善粘接性能，提升修复效果，在简便化与通用性方面已经取得了重大进展。为此，本文通过梳理汇总，旨在探讨近年来牙齿粘接领域出现的通用型粘接剂及其所反映的发展趋势：如功能单体增强粘接界面之间的微机械作用力、强化树脂材料与各种底物之间的化学相互作用以提高粘接材料的性能，以及生物活性分子赋予抗菌等其他功能等。最后对行业的未来发展进行展望，认为在保持材料力学性能的基本前提下，牙齿粘接剂正朝着简单、高效、持久的方向快速发展。

【关键词】粘接剂；粘接；甲基丙烯酸酯；树脂

聚氨酯微球及其增韧环氧树脂的制备和性能研究

宋彩雨，薛双乐，孙明明，郭宇婷，袁志刚，张  斌，王红杨，谢天怡

(黑龙江省科学院石油化学研究院，黑龙江哈尔滨  150040)

【摘  要】以二元醇、多元醇和异氰酸酯为原料，采用沉淀聚合法，制备了系列纯净、尺寸均匀且保留部分活性基团的聚氨酯微球，并以三辊研磨混合方式制备了聚氨酯微球改性环氧树脂。详细考察了微球及其改性环氧树脂的红外光谱和微观形态，对改性环氧树脂的应用性能进行了探讨。研究结果表明：⑴成功制备了系列保留—NCO活性基团的聚氨酯微球，二元醇PTMG分子质量的改变，能够有效调控微球的尺寸及粒径分布。⑵制备形成了系列聚氨酯微球增韧改性环氧树脂，微球与环氧树脂进行三辊研磨过程中，同时发生了物理混合和化学反应过程。聚氨酯微球均匀分散于环氧树脂中，并保持稳定的球形形态。⑶聚氨酯微球能够有效提升环氧树脂粘接铝合金试件的剪切强度和剥离强度。调控PM₁₀₀₀P微球引入量至20%，室温剪切强度和90°剥离强度分别达到38.07 MPa和9.05 kN/m，较空白试样分别提高了40%和125%，表明微球改性体系具有优异的粘接性能。

【关键词】聚氨酯；微球；增韧改性；环氧树脂；粘接性能

偏光片用可光扩散黏着层的制备和性能研究

乔立根^1,2，巫  柯¹，白永平²

(1.广州鹿山新材料股份有限公司，广东广州  510530；2.哈尔滨工业大学化工与化学学院，黑龙江哈尔滨  150001)

【摘  要】采用β-丙烯酰氧基丙酸(β-CEA)作为官能单体、异丁烯酸甲酯(MMA)作为硬单体、丙烯酸-2-乙基己酯(2-EHA)作为软单体，使用HDI三聚体为交联剂、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为偶联剂，通过自由基溶剂聚合的方法合成了偏光片用可光扩散黏着层基体树脂，并探究了软硬单体比例、官能单体添加量对性能的影响。与交联剂、偶联剂复配得到了性能优异的黏着层，并在偏光片用黏着层基础上通过与光扩散微粒复配得到了性能优异的光扩散黏着层。分别探究了交联剂、偶联剂添加量对黏着层性能和10 rad/s条件下储能模量、耐候性的影响。研究结果表明：⑴当软硬单体比例为83∶17，官能单体添加量为3%时，偏光片用可光扩散黏着层基体树脂成膜后初粘力可达到6#球，剥离强度为21.7 N/in，持粘时间为9.0 h，10 rad/s条件下的储能模量为85 395 Pa。⑵作为黏着层时，交联剂质量分数在0.45%，偶联剂质量分数在0.45%时为宜。⑶在制备光扩散黏着层时，选择光扩散微粒添加量4%较为合适。⑷结合影响性能和模量、雾度等各项因素，制备了一款性能优异、满足使用条件的偏光片用可光扩散黏着层。其初粘力可达2#球，180°剥离强度为4.1 N/in，85 ℃持粘时间为66 h，10 rad/s条件下的储能模量为140 930 Pa，雾度为35%，60 ℃及90%RH环境下经时500 h无不良。

【关键词】偏光片；可光扩散黏着层；聚丙烯酸酯

电子显示屏防爆膜用丙烯酸酯压敏胶的研制

李铭杰，李健雄

（皇冠新材料科技股份有限公司，广东中山  528478）

【摘  要】以丙烯酸丁酯（BA）、丙烯酸异冰片酯（IBOA）为软单体，甲基丙烯酸甲酯（MMA）、丙烯酸甲酯（MA）为硬单体，丙烯酸（AA）、丙烯酸羟乙酯（HEA）为功能单体，过氧化二苯甲酰（BPO）、偶氮二异丁腈（AIBN）为引发剂，乙酸乙酯为溶剂，添加硅烷偶联剂，制备了电子显示屏防爆膜用溶剂型丙烯酸酯压敏胶。采用单因素试验法探讨了软硬单体配比、功能单体用量、引发剂用量、硅烷偶联剂用量、丙烯酸异冰片酯用量对压敏胶黏度、180°剥离力、透光率、抗反弹性能的影响。研究结果表明：对于电子显示屏防爆膜用溶剂型丙烯酸酯压敏胶，软硬单体配比、功能单体的用量对压敏胶的180°剥离力和抗反弹性能影响较大；适量的硅烷偶联剂可以提升压敏胶对玻璃基板的粘接性能；适量的丙烯酸异冰片酯单体可以明显改善防爆膜胶带产品的透光率。目前所研发的压敏胶胶水及防爆膜胶带产品已开始批量化生产。

【关键词】防爆膜；丙烯酸酯；压敏胶；剥离力；抗反弹；透光率

湿固化聚氨酯热熔胶中试研究

刘  晨^1,2，杨淑怡¹，张梦婷¹，李  翔¹，

曾  赟¹，兰支利²，曾声红¹，郑和根¹

（1.江西永丰工业园区管理委员会，江西吉安  331500；

2.湖南师范大学化学化工学院，湖南长沙 410081）

【摘  要】在前期250 mL烧瓶试验基础上，本研究采用20 L反应釜进行中试试验。从聚酯多元醇原料、催化剂、温湿度以及扩链剂等方面，研究其对湿固化聚氨酯热熔胶性能的影响，并通过黏度、粘接强度和表干时间等方法对合成材料进行表征。研究结果表明：⑴中试试验不同于小试加料可以是固体或液体，中试在加料方式上尽量采用液体，让合成产物分子量均匀，另外中试需要考虑降温和出料问题。⑵结晶性高的原料会使初始剥离强度增大，但最终剥离强度却先升高后降低，当结晶度太高时，最终剥离强度反而要下降。表干时间随着结晶度提高而缩短。⑶催化剂能提高湿固化聚氨酯热熔胶的粘接力，三乙烯二胺的催化效果最佳，但是催化剂用量对热熔胶的黏度有影响，催化剂用量过多会导致热熔胶凝胶。试验结果表明，三乙烯二胺质量分数选择0.5%时，性能相对最佳。⑷温度、湿度对湿固化聚氨酯热熔胶的粘接力有影响，湿度越高，水汽渗透到胶层越容易，加速—NCO反应，生成极性强的氨基甲酸酯键和脲键等化学键。⑸扩链剂可以使得聚合物分子量增大、黏度增大，基材上受力点密度增大，从而提高粘接力；但用量过多或官能度高时，分子链之间交联程度越高，胶粘剂容易凝胶。中试试验选择1,4-丁二醇（BDO），扩链消耗10%的—NCO的方案最佳。⑹中试研究认为，真空度≤-0.09 MPa，减压真空脱水2 h，聚氨酯预聚体合成温度在(80±5) ℃，反应时间2 h，扩链反应30 min～1 h，异氰酸酯液体投料，催化剂（三乙烯二胺）用量为0.5%，扩链剂（1,4-丁二醇）添加量消耗剩余—NCO（物质的量分数）为10%时，制备的聚氨酯热熔胶性能相对最佳。

【关键词】聚氨酯热熔胶；聚酯多元醇；异氰酸酯；扩链剂；粘接强度

UV固化扬声器中心胶的制备及性能研究

曾柳惠，汪尧双，陆信航，王世伟，谢守华

(国光电器股份有限公司，广东省电声电子技术研发与应用企业重点实验室，广东广州  510800)

【摘  要】采用液化改性4,4'-二苯基甲烷二异氰酸酯（MDI）、聚丙二醇（PPG-2000）和丙烯酸羟乙酯（HEA）等原料制备聚氨酯丙烯酸酯预聚体（P）。再以4-丙烯酰吗啉（ACMO）和三甲基环己基丙烯酸酯（TMCHA）为主要稀释剂单体，搭配光引发剂和助剂，得到UV固化胶粘剂。分别对ACMO和TMCHA的添加量和复配比例进行探讨，使复配所得的单体不但能够增加胶粘剂的硬度，也能使胶粘剂具备较好的粘接力。研究结果表明：⑴红外光谱表明，已经成功制备了预期产物聚氨酯丙烯酸酯。⑵通过研究单体的添加量及复配比例对胶粘剂的硬度和各种基材粘接性能的影响，得出ACMO添加量为15%，TMCHA添加量为30%时为最优配方（UV5）。此时PI/PC的剥离强度为1.95 N/mm，硬度为40D。⑶将最优配方UV5与市售AB胶(5705GB)进行基础粘接性能以及各种音膜材料粘接性能的对比，得出在PC/PET、PC/特多龙、玻片/特多龙的粘接上，UV5更为优异。而且在基础粘接性能的对比上，UV5的PC/PC、PC/Zn以及PC/Al的剪切强度要比市售AB胶(5705GB)的好。⑷通过承重胶水耐温试验的分析，在80~130 ℃的范围下进行粘接样条的挂重，发现UV5和市售5705GB耐温性均比较好，耐温均能够达到130 ℃。⑸根据声学性能曲线，发现配方UV5粘接的喇叭样品符合各项声学性能要求，且比市售5705GB产品性能更好。

【关键词】UV胶粘剂；稀释剂单体；中心胶；音膜

室温固化耐热型金属修补剂的研制

王冠璋，王德鹏，田学深，夏令明，姜  哲，杨  猛

（哥俩好新材料股份有限公司，辽宁抚顺  113004）

【摘  要】以特种环氧树脂作为基料，改性脂环胺为固化剂，配以增韧剂、填料，制备出剪切强度高、耐热性好、储存稳定的耐热型金属修补剂。重点考察了特种环氧树脂、固化剂、增韧剂、填料以及固化条件对金属修补剂性能的影响。研究结果表明：选用E-51与AG-80作为主体树脂时，胶体的交联程度得到了提高，在140℃下仍有较高的剪切强度；选用改性脂环胺SF-2351作为固化剂，其脂环和长链的结构，不仅保证了胶体力学性能，还提高了热变形温度；当增韧剂QS-330C添加量为树脂质量的10%时，不仅保证了胶体的热变形温度，还提高了胶体的力学性能；选用铁粉和硅微粉配合作为填料，当添加量为50%时，胶体黏度适中，无沉降情况，且提升了力学性能；通过不同固化条件下剪切强度的对比，发现胶体在室温固化条件下就可以达到较为完整的固化程度。

【关键词】室温固化；耐热；金属修补剂；剪切强度

单组分聚氨酯热固化胶粘剂用于内嵌式推拉窗的可行性研究

詹  锋，黄加俊，李桂妃，谢志明

（广东普赛达材料科技股份有限公司，广东东莞  523600）

【摘  要】将单组分聚氨酯热固化胶和湿气固化聚氨酯密封胶用于汽车内嵌式推拉窗制造过程中的铝型材粘接。对比了两种胶的固化性能、剪切性能，着重探讨了热固化胶用于内嵌式推拉窗的可行性。研究结果表明：⑴热固化胶用于阳极氧化铝基材与黑边玻璃的粘接组装时，必须配合活化剂和底涂同时使用。⑵不同温度对两种密封胶固化速度表现明显差异。随着温度的升高，湿固化胶结皮速度加快，固化厚度呈现先增加后降低的情况，但变化幅度较小。热固化胶粘剂低温表干时间较慢，随着温度增加，固化厚度快速增加。⑶湿固化胶养护时间为8 h，23、70和90 ℃条件下，剪切力分别为203、243和187 N，均小于装箱要求的600 N，无法满足8 h内快速装箱技术要求。⑷热固化胶在70 ℃、养护4 h时，固化厚度可达3.56 mm，剪切力达到1 466 N，可以实现清胶快速装箱；提高养护温度到90 ℃，清胶装箱的间隔时间可以缩短到20 min，此时固化厚度可达5.24 mm，剪切力达到2 126 N。热固化胶的这两种工艺条件均能有效适用于内嵌式推拉窗短周期装配。

【关键词】单组分；聚氨酯；热固化胶；推拉窗

侧羟基氟碳低聚物的合成及固化性能研究

安靖怡¹，张天福²，张孝阿¹，王成忠¹，江盛玲¹，张军营¹

（1.北京化工大学，碳纤维及功能高分子教育部重点实验室，材料科学与工程学院，北京 100029；2.航天化学动力技术国防科技重点实验室，湖北航天化学技术研究所，湖北襄阳  441003）

【摘  要】以低分子量偏氟乙烯（VDF）-六氟丙烯（HFP）共聚物和氨基醇为主要原料，通过迈克尔加成反应，设计合成了三种侧羟基氟碳低聚物，并进一步与固化剂HDI三聚体、扩链剂1,4-丁二醇反应，得到固化产物。然后采用傅里叶变换红外光谱仪（FT-IR）和核磁共振波谱仪（¹H-NMR），研究了氨基醇种类及用量、氧化镁用量、反应温度、反应时间对侧羟基氟碳低聚物合成的影响，进一步研究了固化物的力学性能、热性能和耐溶剂性能。研究结果表明：⑴成功合成了侧羟基氟碳低聚物，且采用4-氨基-1-丁醇作为亲核试剂时，制备的侧羟基氟碳低聚物具有较高的接枝率。当投料比为20∶10，接枝率为17.39%，反应时间在6.5~9.0 h时为相对最佳制备条件。⑵侧羟基氟碳低聚物固化产物拉伸强度在3.41~9.21 MPa之间。随着氟碳低聚物接枝率的提高，交联反应位点增多，形成了稳定的三维网状结构，使拉伸强度提升。⑶固化后形成交联结构，阻止了聚合物链段的移动，提高了热稳定性。⑷所制备的固化产物具有良好的耐强酸、强碱以及极性溶剂特性。

【关键词】侧羟基氟碳低聚物；氨基醇；迈克尔加成；活性基团

空气净化器塑料面板螺柱滑牙问题改善研究

沈凌峰¹，沈科挺¹，袁世权¹，郭国良²，郑军妹²，魏  俊²

（1.宁波方太厨具有限公司，浙江宁波  315336；2.健康智慧厨房浙江省工程研究中心，浙江宁波  315336）

【摘  要】为解决空气净化器中外观塑料面板频繁出现的ABS塑料螺柱滑牙问题，本研究通过不同种类单组分胶水（如瞬间胶、EVA热熔胶、厌氧胶、溶剂胶等）之间的测试对比，以确定相对最优的螺柱螺纹修复工艺方案。研究结果表明：⑴由于瞬间胶固化后具有相对更高的硬度和粘接强度，这证明其具备更大的内聚力，这使其相比其他单组分胶水在塑料螺柱螺纹修复的工艺过程中具备明显更突出的性能优势。⑵测试对比发现，3种瞬间胶均能满足塑料螺柱螺纹修复的要求，其中瞬间胶-A鉴于其更突出的材料成本优势，被优先考虑用于最终的螺纹修复工艺。⑶通过对比试验，确认了瞬间胶-A在不同温湿度条件下的完全固化时间t₀以及胶水对塑料面板材料韧性的影响。在相同水汽压下，瞬间胶-A的完全固化时间随着温度的升高而减少，即瞬间胶-A的固化速度与空气温度呈现正相关关系。⑷瞬间胶-A会导致塑料螺柱韧性略有下降，但下降幅度不影响后续螺钉的二次固定。⑸本研究一整套塑料螺柱螺纹修复工艺的探究和应用，能够最终实现塑料面板的零报废和降低零件成本，并且能够对行业内频繁出现的塑料螺柱滑牙问题的解决起到很大的经验总结和启示意义。

【关键词】ABS塑料；螺柱滑牙；螺纹修复；瞬间胶

Research progress of catechol-based underwater adhesive

Zhang Chengyu^1,2,Wu Wenxiao^1,2,Yang Zhihui^1,2,Shi Haobo³,

Tian Weizhi³,Xie Yuchen^1,2,Qin Jiaqi^1,2,Lu Haifeng^1,2

(1.School of Chemistry and Chemical Engineering,Shandong University, Ji'nan250100, Shandong, China; 2.Shandong Key Laboratory of Advanced Organo Silicon Materials and Technologies, Ji'nan 256401, Shandong, China; 3.Beijing Xinghang Mechanical-Electric Equipment Co., Ltd., Beijing  100074, China)

【Abstract】The application fields such as marine industry and biomedicine require adhesive capable of bonding to surfaces submerged in water, however, the hydration layer often hinders the interaction between the adhesive and the surface. Inspired by biology, catechol-functionalized polymers have been extensively studied and used for underwater adhesion. Significant progress has been made in enhancing its bonding strength, although there is still room for improvement in terms of bonding strength and substrate diversity compared to dry adhesive. The latest research progress, both domestically and internationally, on underwater adhesive containing catechol groups was systematically summarized in this review. Starting from the adsorption principle of marine mussels, the interfacial adsorption of catechol groups was explored and the performance of underwater adhesive based on different mechanisms was summarized. Finally, the potential development directions were discussed, offering new ideas and methods to solve the bonding problems in humid environments.

【Keywords】underwater; adhesive; bonding; catechol

New progress in dental adhesives

Fang Zhao, Hou Dandan, Du Chao, Zhou Tong, Wang Chunyao, Guo Min

(Sinopec Key Laboratory of Research and Application of Medical and Hygienic Materials, Beijing 100013, China)

【Abstract】In recent years, dental adhesives have made significant progress in simplification and universality by introducing various new structures to effectively improve bonding performance and enhance repair effectiveness. Therefore, the universal adhesives that have emerged in the field of dental bonding in recent years and the development trends they reflect, such as functional monomers enhancing the micro mechanical forces between bonding interfaces, strengthening the chemical interactions between resin materials and various substrates to improve the performance of bonding materials, and biologically active molecules endowing antibacterial and other functions were explored in this article. Finally, the future development of the industry was discussed, believing that while maintaining the basic mechanical properties of materials, dental adhesives were rapidly advancing towards simplicity, efficiency, and durability.

【Keywords】adhesive; bonding; methacrylate; resin

Preparation and properties of polyurethane microspheres and their toughened epoxy resins

Song Caiyu, Xue Shuangle, Sun Mingming, Guo Yuting,

Yuan Zhigang, Zhang Bin, Wang Hongyang, Xie Tianyi

(Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin 150040, Heilongjiang, China)

【Abstract】A series of pure polyurethane microspheres with uniform size and partially retained active groups were prepared by precipitation polymerization method using diols, polyols and isocyanates as raw materials, and then polyurethane microspheres modified epoxy resins were prepared by three-roll grinding mixing. The infrared spectra and microscopic morphology of the microspheres and their modified epoxy resins were investigated in details, and the application properties of modified epoxy resins were discussed. The research results showed that, ⑴ A series of polyurethane microspheres retaining —NCO active groups were successfully prepared. The particle size and distribution of the microspheres could be effectively regulated by the change of molecular weight of diol PTMG. ⑵A series of polyurethane microspheres toughening modified epoxy resins were prepared. During the three-roll grinding process of the microspheres and epoxy resins, physical mixing and chemical reaction occurred at the same time. The polyurethane microspheres were uniformly dispersed in the epoxy resins and maintained the stable spherical shape. ⑶ Polyurethane microspheres could effectively improve the shear strength and peel strength of epoxy resin bonded aluminum alloy specimens. When the amount of PM₁₀₀₀P microspheres was adjusted to 20%, the shear strength at room temperature and 90° peel strength reached 38.07 MPa and 9.05 kN/m, respectively, which increased by 40% and 125% compared with the blank sample, indicating that the microsphere modified system had excellent bonding properties.

【Keywords】polyurethane; microsphere; toughening modification; epoxy resin; bonding property

Preparation and performance of photo-diffusible adhesive layer for polarizer

Qiao Ligen^1,2, Wu Ke¹,Bai Yongping²

(1.Guangzhou Lushan New Materials Co., Ltd., Guangzhou 510530, Guangdong, China;2.School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin  150001, Heilongjiang, China)

【Abstract】Using β-acryloyloxypropionic acid (β-CEA) as the functional monomer, methyl methacrylate (MMA) as the hard monomer, 2-ethylhexyl acrylate (2-EHA) as the soft monomer, HDI trimer as the crosslinking agent, and γ-methacryloyloxypropyltrimethoxysilane (KH-570) as the coupling agent, the photo-diffusible adhesive matrix resin for polarizer was synthesized by free-radical solvent polymerization. The effects of the ratio of soft and hard monomers and the amount of functional monomer added on the performance were investigated.The high-performance adhesive layer was obtained by compounding with crosslinking agents and coupling agents, and the high-performance photo-diffusible adhesive layer was obtained by compounding with photo-diffusible particles on the basis of the adhesive layer for polarizer.The effects of crosslinking agent and coupling agent addition on the performance of adhesive layer, as well as the storage modulus under 10 rad/s condition and weather resistance were investigated, respectively. The research results showed that, ⑴ When the ratio of soft and hard monomers was 83:17 and the amount of functional monomer added was 3%, after the photo-diffusible adhesive layer substrate resin was formed into film, the initial tack could reach 6# ball, the peel strength was 21.7 N/in, the holding time was 9.0 h, and the storage modulus under 10 rad/s condition was 85 395 Pa.⑵ When used as the adhesive layer, it was advisable to have the crosslinking agent mass fraction of 0.45% and the coupling agent mass fraction of 0.45%. ⑶ When preparing the photo-diffusible adhesive layer, it was advisable to choose the photo-diffusible particle addition amount of 4%. ⑷ A photo-diffusible adhesive layer for polarizer with excellent performance and meeting usage conditions was prepared by combining various factors that affected performance, modulus, and haze. Its initial tack could reach 2# ball, 180° peel strength was 4.1 N/in, the holding time at 85 ℃ was 66 h, the storage modulus under 10 rad/s condition was 140 930 Pa, the haze was 35%, and there were no defects after 500 h in 60 ℃&90% RH environment.

【Keywords】polarizer; photo-diffusible adhesive layer; polyacrylate

Development of acrylate pressure sensitive adhesive for explosion-proof film of electronic display screen

Li Mingjie, Li Jianxiong

（Crown New Materials Technology Co., Ltd., Zhongshan  528478, Guangdong, China）

【Abstract】Solvent-based acrylate pressure sensitive adhesive for explosion-proof film of electronic display screen was prepared by using butyl acrylate (BA) and isobornyl acrylate (IBOA) as soft monomers, methyl methacrylate (MMA) and methyl acrylate (MA) as hard monomers, acrylic acid (AA) and hydroxyethyl acrylate (HEA) as functional monomers, benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) as initiators, ethyl acetate as solvent, and adding silane coupling agent. The single factor experimental method was used to investigate the effects of soft and hard monomer ratio, functional monomer dosage, initiator dosage, silane coupling agent dosage, and isobornyl acrylate dosage on the viscosity, 180° peeling force, transmittance, and rebound resistance of pressure sensitive adhesive. The research results showed that, for solvent-based acrylate pressure sensitive adhesive used in explosion-proof film for electronic display screen, the ratio of soft and hard monomers and the amount of functional monomers had the significant impact on the 180° peeling force and rebound resistance of pressure sensitive adhesive. An appropriate amount of silane coupling agent could enhance the bonding performance of pressure sensitive adhesive to glass substrates. An appropriate amount of isobornyl acrylate monomer could significantly improve the light transmittance of explosion-proof film tape products. At present, the developed pressure sensitive adhesive and explosion-proof film tape products had entered mass production.

【Keywords】explosion-proof film; acrylate; pressure sensitive adhesive; peeling force; rebound resistance; light transmittance

Pilot study on moisture-cured polyurethane hot melt adhesive

Liu Chen^1,2, Yang Shuyi¹, Zhang Mengting¹, Li Xiang¹,

Zeng Yun¹, Lan Zhili², Zeng Shenghong¹, Zheng Hegen¹

(1.Jiangxi Yongfeng Industrial Zone Management Committee, Ji'an 331500, Jiangxi, China;2.College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, Hunan, China)

【Abstract】On the basis of the preliminary 250 mL flask experiment, the pilot-scale experiment was conducted by using a 20 L reactor in this study. The effects of polyester polyol raw materials, catalysts, temperature, humidity, and chain extenders on the properties of moisture-cured polyurethane hot melt adhesive were investigated, and the synthesized materials were characterized by using methods such as viscosity, bonding strength, and surface drying time. The research results showed that, ⑴ The pilot experiment was different from the small-scale experiment in that the feeding of the small-scale experiment could be solid or liquid. In the pilot experiment, liquid was used as much as possible in the feeding method to make the molecular weight of synthesized product uniform. In addition, in the pilot experiment, cooling and discharge issues needed to be considered. ⑵ Raw materials with high crystallinity could increase the initial peel strength, but the final peel strength first increased and then decreased. When the crystallinity was too high, the final peel strength actually decreased. The surface drying time decreased with increasing crystallinity. ⑶ The catalyst could improve the adhesion of moisture-cured polyurethane hot melt adhesive, and the catalytic effect of triethylenediamine was the best, but the amount of catalyst had an impact on the viscosity of hot melt adhesive, and excessive amount of catalyst could cause hot melt adhesive to gel. The test results indicated that the performance was relatively optimal when the mass fraction of triethylenediamine was selected as 0.5%. ⑷ Temperature and humidity had an impact on the bonding strength of moisture-cured polyurethane hot melt adhesive. The higher the humidity, the easier it was for water vapor to penetrate into the adhesive layer, accelerating the —NCO reaction and generating highly polar chemical bonds such as urethane and urea bonds. ⑸ Chain extender could increase the molecular weight and viscosity of polymer, increase the density of stress points on the substrate, and thus improve the bonding strength. However, when the dosage was excessive or the functionality was high, the higher the degree of crosslinking between the molecular chains, the easier the adhesive was to gel. In the pilot experiment, 1,4-butanediol (BDO) was selected and the optimal solution was to expand the chain by consuming 10% —NCO. ⑹In the pilot study, it concluded that the performance of polyurethane hot melt adhesive prepared was optimal when vacuum degree ≤ -0.09 MPa, vacuum dehydration under reduced pressure was for 2 hours, synthesis temperature of polyurethane prepolymer was at (80±5) ℃, reaction time was 2 hours, chain extension reaction was for 30 minutes to 1 hour, liquid isocyanate was added, catalyst (triethylenediamine) dosage was 0.5%, and the addition of chain extender (1,4-butanediol) was 10% of residual —NCO (mass fraction) consumption.

【Keywords】polyurethane hot melt adhesive; polyester polyol; isocyanate; chain extender; bonding strength

Preparation and performance study of UV curing speaker center adhesive

Zeng Liuhui, Wang Yaoshuang, Lu Xinhang, Wang Shiwei, Xie Shouhua

（GuoGuang Electric Company Limited, Guangdong Provincial Key Laboratory of Electroacoustic Electronic Technology R&D and Application, Guangzhou  510800, Guangdong, China）

【Abstract】Polyurethane acrylate prepolymer (P) was prepared by using liquefied modified 4,4'- diphenylmethane diisocyanate (MDI), polypropylene glycol (PPG-2000), and hydroxyethyl acrylate (HEA) as raw materials. UV curing adhesive was then obtained by using 4-acryloylmethiolane (ACMO) and trimethylcyclohexyl acrylate (TMCHA) as the main diluent monomers, combined with photoinitiators and additives. The addition amount and compounding ratio of ACMO and TMCHA were explored respectively, so that the monomers obtained from compounding could not only increase the hardness of adhesive, but also made the adhesive have good adhesion. The research results showed that, ⑴ The infrared spectrum indicated that the expected product polyurethane acrylate was successfully prepared. ⑵ By studying the effects of monomer addition amount and compounding ratio on the hardness of adhesive and the bonding performance of various substrates, it was found that the optimal formula (UV5) was obtained when the ACMO addition amount was 15% and the TMCHA addition amount was 30%. At this time, the peel strength of PI/PC was 1.95 N/mm and the hardness was 40D. ⑶ Comparing the basic bonding performance of the optimal formula UV5 with commercially available AB adhesive (5705GB) and the bonding performance of various acoustic membrane materials, it was found that UV5 was superior in the bonding of PC/PET, PC/Tedroson, and glass slide/Tedroson. Moreover, in terms of basic adhesive performance comparison, the shear strength of UV5 on PC/PC, PC/Zn, and PC/Al was better than that of commercially available AB adhesive (5705GB). ⑷ Through the analysis of the temperature resistance test of the load-bearing adhesive, the hanging weight of the adhesive strip was carried out in the range of 80-130 ℃. It was found that UV5 and the commercially available 5705GB had good temperature resistance, both of which could reach 130 ℃. ⑸ According to the acoustic performance curve, it was found that the speaker sample bonded with formula UV5 met various acoustic performance requirements and performed better than the commercially available 5705GB product.

【Keywords】UV adhesive; diluent monomer; center adhesive; acoustic membrane

Development of room-temperature curing heat-resistant metal repair agent

Wang Guanzhang, Wang Depeng, Tian Xueshen, Xia Lingming, Jiang Zhe, Yang Meng

(Gleihow New Materials Co., Ltd., Fushun 113004, Liaoning, China)

【Abstract】A heat-resistant metal repair agent with high shear strength, excellent heat resistance, and stable storage was prepared by using special epoxy resins as the base materials, modified alicyclic amine as the curing agent, and incorporating toughening agent and filler. The effects of special epoxy resins, curing agents, toughening agents, fillers, and curing conditions on the properties of metal repair agent were investigated emphatically. The research results showed thatwhen E-51 and AG-80 were selected as the main resins, the crosslinking degree of adhesive was improved, and there was still a high shear strength at 140 ℃. Using modified alicyclic amine SF-2351 as the curing agent, its alicyclic and long-chain structure not only ensured the mechanical properties of adhesive, but also increased the thermal deformation temperature. When the amount of toughening agent QS-330C added was 10% of the resin mass, it not only ensured the thermal deformation temperature of adhesive, but also improved the mechanical properties of adhesive. Using iron powder and silicon micro powder as fillers, when the addition amount was 50%, the adhesive viscosity was moderate, there was no sedimentation, and the mechanical properties were improved. By comparing the shear strength under different curing conditions, it was found that adhesive could achieve a relatively complete curing degree under room-temperature curing conditions.

【Keywords】room-temperature curing; heat-resistant; metal repair agent; shear strength

Feasibility study of one-component polyurethane thermosetting adhesive for embedded sliding window

Zhan Feng, Huang Jiajun, Li Guifei, Xie Zhiming

(Guangdong Pustar Material Technology Co., Ltd., Dongguan 523600, Guangdong, China)

【Abstract】The one-component polyurethane thermosetting adhesive and moisture-curing polyurethane sealant were applied to the bonding of aluminum profiles in the manufacturing process of automotive embedded sliding window. The curing properties and shear performance of two types of adhesive were compared, and the feasibility of using the thermosetting adhesive for embedded sliding window was analyzed. The research results indicated that, ⑴When thermosetting adhesive was used for bonding and assembling anodized aluminum substrate with black edge glass, it must be used together with activator and primer. ⑵There was a significant difference in the curing speed of two sealants at different temperatures. With the increase of temperature, the skinning speed of moisture-curing adhesive accelerated, and the curing thickness showed a trend of first increasing and then decreasing, but the change range was relatively small. The surface drying time of thermosetting adhesive was slow at low temperature, and as the temperature increased, the curing thickness increased rapidly. ⑶The curing time of the moisture-curing adhesive was 8 hours. Under the conditions of 23, 70, and 90 ℃, the shear forces were 203, 243, and 187 N, respectively, all of which were less than the required 600 N for packaging, and could not meet the technical requirements for rapid packaging within 8 hours. ⑷When the thermosetting adhesive was cured at 70 ℃ for 4 hours, the curing thickness could reach 3.56 mm, and the shear force could reach 1 466 N, which could achieve rapid cleaning adhesive and packaging. By increasing the curing temperature to 90 ℃, the interval time between cleaning adhesive and packaging could be shortened to 20 minutes. At this time, the curing thickness could reach 5.24 mm and the shear force could reach 2 126 N. Both of these process conditions for thermosetting adhesive could be effectively applied to the short cycle assembly of embedded sliding window.

【Keywords】one-component; polyurethane; thermosetting adhesive; sliding window

Synthesis and curing properties of side hydroxyl fluorocarbon oligomers

An Jingyi¹,Zhang Tianfu², Zhang Xiaoa¹, Wang Chengzhong¹, Jiang Shengling¹, Zhang Junying¹

(1.Key Laboratory of Carbon Fiber and Functional Polymers of Ministry of Education, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;2. Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechnology, Xiangyang  441003, Hubei, China)

【Abstract】Three types of side hydroxyl fluorocarbon oligomers were designed and synthesized via Michael addition reaction by using low-molecular-weight vinylidene fluoride (VDF)-hexafluoropropylene (HFP) copolymer and amino alcohol as the main raw materials. Subsequently, they were reacted with curing agent HDI trimer and chain extender 1,4-butanediol to obtain the cured products. Then, Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (¹H-NMR) were used to investigate the effects of amino alcohol type and dosage, magnesium oxide dosage, reaction temperature, and reaction time on the synthesis of side hydroxyl fluorocarbon oligomers. Furthermore, the mechanical properties, thermal properties, and solvent resistance of the cured products were studied. The research results showed that, ⑴ The side hydroxyl fluorocarbon oligomers were successfully synthesized. When 4-amino-1-butanol was used as the nucleophilic reagent, the oligomers exhibited a higher grafting rate. When the feeding ratio was 20:10, the grafting rate was 17.39%, and the reaction time was between 6.5 and 9.0 hours, which were the optimal preparation conditions. ⑵The tensile strength of the cured product of side hydroxyl fluorocarbon oligomers was between 3.41 and 9.21 MPa. As the grafting rate of fluorocarbon oligomers increased, the number of crosslinking reaction sites increased, forming a stable three-dimensional network structure that enhanced tensile strength. ⑶After curing, a cross-linked structure was formed, which prevented the movement of polymer segments and improved thermal stability. ⑷ The prepared cured product had good resistance to strong acids, strong bases, and polar solvents.

【Keywords】side hydroxyl fluorocarbon oligomers; amino alcohol; Michael addition; active group

Research on the improvement of screw stripping problems in plastic panel studs of air purifiers

Shen Lingfeng¹, Shen Keting¹, Yuan Shiquan¹, Guo Guoliang², Zheng Junmei², Wei Jun²

(1.Ningbo Fotile Kitchen Ware Co., Ltd., Ningbo 315336, Zhejiang, China; 2.Healthy & Intelligent Kitchen Engineering Research Center of Zhejiang Province, Ningbo  315336, Zhejiang, China)

【Abstract】In order to solve the frequent problems of screw studs stripping in the ABS plastic panel of air purifiers, various types of single-component adhesive (such as cyanoacrylate adhesive, EVA hot melt adhesive, anaerobic adhesive, and solvent-based adhesive) were compared and tested in this study to determine the relatively optimal repair process for screw threads. The research results showed that, ⑴ Cyanoacrylate adhesive exhibited relatively higher hardness and bonding strength after curing, indicating greater cohesive strength compared to other single-component adhesive. This made it significantly more effective in the process of repairing plastic screw threads.⑵ Among the three kinds of cyanoacrylate adhesive tested, all met the requirements for repairing plastic screw threads. However, cyanoacrylate adhesive A was prioritized for its superior cost-effectiveness in the final repair process. ⑶ Through comparative tests, the complete curing time t₀ of cyanoacrylate adhesive A under different temperature and humidity conditions, as well as its impact on the toughness of the plastic panel material were confirmed. Under the same water vapor pressure, the complete curing time of cyanoacrylate adhesive A decreased with increasing temperature, indicating a positive correlation between the curing speed of cyanoacrylate adhesive A and air temperature. ⑷ Cyanoacrylate adhesive A caused a slight decrease in the toughness of the plastic screw studs, but this reduction did not affect the secondary fixation of the screw. ⑸The comprehensive exploration and application of this plastic screw thread repair process in this study could ultimately achieve zero scrap rate for plastic panels and reduced part costs, and provide valuable experience and insights for addressing the frequent problems of screw studs stripping in the industry.

【Keywords】ABS plastic; screw studs stripping; thread repair; cyanoacrylate adhesive