王淑娜,高玉宝,金欣,宋红玮

• 1:青岛科技大学化工学院
• 2:美瑞新材料股份有限公司

摘要(Abstract)：

湿固化聚氨酯热熔胶(PUR)固化前初始粘接强度弱，粘接过程中易发生滑移或错位，限制了其在高速粘接场景中的应用。针对上述问题，文中以聚己二酸丁二醇酯(PBA)为软段、4,4′-二苯基甲烷二异氰酸酯(MDI)为硬段，引入具有仲胺结构特征的天冬氨酸酯(PAE)作为扩链剂，构建PAE改性湿固化聚氨酯热熔胶体系，研究PAE含量对体系氢键作用、结晶特性、粘接性能及力学性能等的影响。结果表明，PAE分子中的仲胺结构可与异氰酸酯反应生成取代脲基甲酸酯，增强硬段间氢键作用并提高聚集度，同时其柔性链段可调节分子运动并抑制软段结晶，从而在保持低熔体黏度的条件下提升粘接强度和力学性能。当PAE添加量为6%(质量分数)时，PUR体系综合性能最优，其熔体黏度仅为3 325 mPa·s，而初始剥离强度达到3 N/25 mm，较未扩链体系提高150%；最终剥离强度为198 N/25 mm，提高了100%；断裂伸长率为808.25%，提高了170%；拉伸强度为14.97 MPa，提高了56%，耐热性和固化速率均优于未扩链体系，为低黏度、高性能PUR的开发提供了一种有效途径。

关键词(KeyWords)： 聚氨酯;湿固化;热熔胶;天冬氨酸酯;粘接强度

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(21576144)

作者(Author): 王淑娜,高玉宝,金欣,宋红玮

参考文献(References)：

• [1]黄磊，汪雷.反应型聚氨酯热熔胶的研究进展概述[J].中国胶粘剂，2023,32(12):61-66.HUANG L, WANG L. Overview of research progress of reactive polyurethane hot melt adhesive[J]. China Adhesives, 2023,32(12):61-66.
• [2]邱光南，许剑鸣.反应型聚氨酯热熔胶改性研究进展[J].当代化工研究，2022(22):74-76.QIU G N, XU J M. Research progress on modification of reactive polyurethane hot-melt adhesives[J]. Modern Chemical Research,2022(22):74-76.
• [3]MCCREATH S, BOINARD P, BOINARD E, et al. High clarity poly(caprolactone diol)-based polyurethane adhesives for polycarbonate lamination:Effect of isocyanate and chain-extender[J]. International Journal of Adhesion and Adhesives,2018,86:84-97.
• [4]ZHANG Z P,LIU X S,BAN X Y,et al. The influence of filler types and content on the curing behavior and properties of a bio-based polyurethane engineered sealant[J]. International Journal of Adhesion and Adhesives,2025,136:103866.
• [5]张于弛.增粘树脂对湿固化聚氨酯热熔胶性能的影响[J].广州化学，2015,40(4):43-46.ZHANG Y C. Effect of tackifying resin on the properties of moisture curing polyurethane hot melt adhesive[J]. Guangzhou Chemistry,2015,40(4):43-46.
• [6]刘晨，杨淑怡，张梦婷，等.湿固化聚氨酯热熔胶中试研究[J].中国胶粘剂，2025,34(2):36-42.LIU C,YANG S Y,ZHANG M T,et al. Pilot study on moisture-cured polyurethane hot melt adhesive[J]. China Adhesives,2025,34(2):36-42.
• [7]MOYANO-VALLEJO A, CARBONELL-BLASCO M P, HERN??NDEZ-FERN??NDEZ C, et al. Enhanced green strength in a polycarbonate polyol-based reactive polyurethane hot-melt adhesive[J]. Polymers,2024,16(23):3356.
• [8]吕平，陈国华，黄微波.新型聚天冬氨酸酯聚脲的合成、结构与性能研究[J].高校化学工程学报，2008,22(1):106-112.LYU P,CHEN G H,HUANG W B. Study on synthesis,morphology and properties of novel polyureas based on polyaspartic esters[J].Journal of Chemical Engineering of Chinese Universities,2008,22(1):106-112.
• [9]刘亦曾，佘静丽，徐微，等.铝/聚氯乙烯贴合用反应型聚氨酯热熔胶的制备与性能[J].高分子材料科学与工程，2025,41(5):1-9.LIU Y Z, SHE J L, XU W, et al. Preparation and properties of reactive polyurethane hot melt adhesive for aluminum/polyvinyl chloride bonding[J]. Polymer Materials Science&Engineering,2025,41(5):1-9.
• [10]陈精华，张健臻，邱伟俊，等.湿固化反应型聚氨酯热熔胶的研制[J].广州化工，2024,52(20):57-60.CHEN J H, ZHANG J Z, QIU W J, et al. Preparation of moisture curing reactive polyurethane hot-melt adhesive[J]. Guangzhou Chemical Industry,2024,52(20):57-60.
• [11]RISTI??I, CAKI??S, VUKI??N, et al. The influence of soft segment structure on the properties of polyurethanes[J]. Polymers,2023,15(18):3755.
• [12]陈旭欣.耐热反应型聚氨酯热熔胶的制备及性能研究[D].广州：华南理工大学，2024.CHEN X X. Study on preparation and properties of heat-resistant polyurethane reactive hot melt adhesive[D]. Guangzhou:South China University of Technology,2024.
• [13]MOR??VKOV??Z, PODE??VA J, SHABIKOVA V, et al. Hydrogen bonding of trialkyl-substituted urea in organic environment[J].Molecules,2025,30(7):1410.
• [14]YANG D L,BRETT J K,CELINA M C. Hydrolysis of poly(ester urethane):In-depth mechanistic pathways through FTIR 2D-COS spectroscopy[J]. Polymer Degradation and Stability,2025,231:111094.
• [15]QIN Y L, ZHU P, OUYANG C X, et al. Chain extender-induced hydrogen bonding organization determines the morphology and properties of thermoplastic polycarbonate polyurethane[J]. Chinese Journal of Polymer Science,2024,42(1):87-96.
• [16]WANG H R, CAO L, WANG X L, et al. Effects of isocyanate structure on the properties of polyurethane:Synthesis,performance,and self-healing characteristics[J]. Polymers,2024,16(21):3045.
• [17]LIU Z H, HUANG J Q, SUN L J, et al. PPC-based reactive hot melt polyurethane adhesive(RHMPA)—Efficient glues for multiple types of substrates[J]. Chinese Journal of Polymer Science,2018,36(1):58-64.
• [18]WANG M Q,LIANG S F,GAO W,et al. The effect of promoting hydrogen bond aggregation based on PEMTC on the mechanical properties and shape memory function of polyurethane elastomers[J]. Royal Society Open Science,2022,9(3):211393.
• [19]WONGSAMUT C, SUWANPREEDEE R, MANUSPIYA H. Thermoplastic polyurethane-based polycarbonate diol hot melt adhesives:The effect of hard-soft segment ratio on adhesion properties[J]. International Journal of Adhesion and Adhesives,2020,102:102677.
• [20]JIN X, GUO N S, YOU Z P, et al. Design and performance of polyurethane elastomers composed with different soft segments[J].Materials,2020,13(21):4991.
• [21]SHEN Z Y, ZHENG L C, SONG D Q, et al. A non-isocyanate route to poly(ether urethane):Synthesis and effect of chemical structures of hard segment[J]. Polymers,2022,14(10):2039.
• [22]BUKOWCZAN A,RAFTOPOULOS K N,PIELICHOWSKI K. Crystallinity and liquid crystallinity of polyurethanes:How tailoring of order contributes to customized properties and applications[J]. Polymers,2025,17(6):784.
• [23]MOON H, PARK J E, CHO W, et al. Curing kinetics and structure-property relationship of moisture-cured one-component polyurethane adhesives[J]. European Polymer Journal,2023,201:112579.
• [24]YAN Z X,YANG P Q,YANG H T,et al. Influence of hard segment content on microphase separation and dielectric performance of polyurethane elastomers[J]. Colloid and Polymer Science,2025,303(11):2331-2342.
• [25]NATOUR S, GAJDO??OV??V, MOR??VKOV??Z, et al. Aspartate-based polyurea coatings:Ambient cure process and inevitable transformation of urea groups into hydantoin cycles in polyurea networks and their impact on film properties[J]. Progress in Organic Coatings,2024,192:108449.
• [26]QIN J L, CHEN Y F, GUO X W, et al. Regulation of hard segment cluster structures for high-performance poly(urethane-urea)elastomers[J]. Advanced Science,2024,11(22):2400255.
• [27]郑梦凯，张聪聪，李伯耿.含芳杂环热塑性聚氨酯弹性体的合成与表征[J].高校化学工程学报，2019,33(4):933-941.ZHENG M K, ZHANG C C, LI B G. Synthesis and characterization of thermoplastic polyurethane elastomers containing aromatic heterocycte[J]. Journal of Chemical Engineering of Chinese Universities,2019,33(4):933-941.
• [28]YI S J, CHO S, LEE C K, et al. Thermal resistance of polyurethane adhesives containing aluminum hydroxide and dealkaline or alkaline lignin[J]. Journal of Applied Polymer Science,2024,141(12):e55120.
• [29]SUN L, ZONG Z G, XUE W L, et al. Mechanism and kinetics of moisture-curing process of reactive hot melt polyurethane adhesive[J]. Chemical Engineering Journal Advances,2020,4:100051.
• [30]TENORIO-ALFONSO A, S??NCHEZ M C, FRANCO J M. Impact of moisture curing conditions on the chemical structure and rheological and ultimate adhesion properties of polyurethane adhesives based on castor oil and cellulose acetate[J]. Progress in Organic Coatings,2021,161:106547.