不同脂环族硬段分布的自愈合聚氨酯的制备及性能  

Preparation and properties of self-healing polyurethanes with different alicyclic-type hard segment distributions

作　　者：王玉杰 聂慧芳 刘梓豪 辛再旺 杨远扬 王非[1] WANG Yujie;NIE Huifang;LIU Zihao;XIN Zaiwang;YANG Yuanyang;WANG Fei(School of Chemical and Printing-Dyeing Engineering,Henan University of Engineering,Zhengzhou 450007,Henan,China)

机构地区：[1]河南工程学院化工与印染工程学院,河南郑州450007

出　　处：《精细化工》2024年第12期2652-2659,共8页Fine Chemicals

基　　金：河南省科技攻关项目(242102311245);河南省高等学校重点科研项目(24A430010);河南工程学院博士培育基金项目(D2021004);河南省大学生创新创业训练计划项目(202411517023、202311517020)。

摘　　要：以六亚甲基二异氰酸酯(HDI)和聚碳酸酯二醇-2000(PCDL-2000)为原料,通过控制PCDL-2000和具有线型结构的HDI的配比及加料顺序,制备出2种不同相对分子质量的PCDL,以PCDL-2000及PCDL分别为软段,与异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)进行聚合反应,制备出不同脂环族硬段分布的3种自愈合聚氨酯(PC-PU)及薄膜。采用FTIR、XRD、TGA、AFM、3D超景深显微镜、电子万能试验机对PC-PU和PC-PU薄膜的晶体结构、结晶形态、热稳定性、拉伸性能及自愈合性能进行了表征和测试,探究了其自愈合机理。结果表明,随着软段PCDL的相对分子质量的增加,脂环族硬段分布趋于集中,PC-PU薄膜的结晶度由23.3%增至26.5%,弹性模量由(17.9±1.1) MPa升至(62.7±2.3) MPa,断裂伸长率由1420%±40%降至1060%±50%,拉伸强度则在(18.6±2.5)和(20.5±3.4)MPa之间。基于氢键作用及软段的热运动,PC-PU薄膜的自愈合效率最高可达81.9%±3.3%。Two kinds of polycarbonate diol(PCDL) with different relative molecular masses were synthesized by controlling the ratio and feeding sequence of raw materials polycarbonate diol-2000(PCDL-2000) and hexamethylene diisocyanate(HDI) with linear structure.Three kinds of self-healing polyurethanes(PC-PU) and films with different alicyclic-type hard-segment distributions were then prepared from polymerization of PCDL-2000 and PCDL with isophorone diisocyanate(IPDI) and 1,4-butanediol(BDO),respectively.PC-PU and films were characterized by FTIR,XRD,TGA,AFM,3D ultra-depth-of-field microscope,and electronic universal testing machine for analysis on the crystal structure,crystalline morphology,thermal stability,tensile strength and self-healing properties,with the self-healing mechanism explored.The results showed that the crystallinity of PC-PU increased from 23.3% to 26.5%,the modulus of elasticity increased from(17.9±1.1) to(62.7±2.3) MPa,the elongation at break decreased from 1420%±40% to 1060%±50%,and the tensile strength ranged between(18.6±2.5) and(20.5±3.4) MPa as the distribution of the alicyclic-type hard segments was concentrated.Based on the hydrogen bonding and the thermal movement of the soft segments,the self-healing efficiency of PC-PU could reach as high as 81.9%±3.3%.

关 键 词：聚氨酯 脂环族硬段分布 氢键作用 分子链热运动 自愈合 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]