嵌段分布对IPDI型聚氨酯结晶行为及弹性性能的影响  

Effect of Segmented Distribution on Crystallized Behavior and Elastic Property of IPDI-based PU

作　　者：王玉杰 聂慧芳[1] 王国锋 黄淼铭 刘浩 刘文涛[2] Yu-jieWang;Hui-fang Nie;Guo-feng Wang;Miao-ming Huang;Hao Liu;Wen-tao Liu(School of Chemical and Printing-dyeing Engineering,Henan University of Engineering,Zhengzhou 450007;School of Material Science and Engineering,Zhengzhou University,Zhengzhou 450001;Henan Tuoren Medical Equipment Group Co.,Ltd,Xinxiang 453400)

机构地区：[1]河南工程学院化工与印染工程学院,郑州450007 [2]郑州大学材料科学与工程学院,郑州450001 [3]河南驼人医疗器械集团有限公司,新乡453400

出　　处：《高分子学报》2022年第11期1379-1387,共9页Acta Polymerica Sinica

基　　金：国家重点研发计划项目(项目号2018YFD0400702);国家自然科学基金(基金号U1504527,21803060);河南工程学院博士培育基金(基金号D2021004)资助.

摘　　要：嵌段分布是影响聚氨酯(PU)性能的关键因素之一,而探明嵌段分布对具有环形结构硬段PU性能的影响是开发高性能PU的关键.在控制硬段含量相似的条件下,分别以不同分子量的聚己内酯二元醇(PCL-diol)作为软段,以异佛尔酮二异氰酸酯(IPDI)和1,4-丁二醇(BDO)为硬段,合成出一系列具有不同嵌段分布的IPDI型PU.通过傅里叶变换红外光谱仪、超导核磁共振仪和X射线衍射仪表征不同分子量PCLdiol和不同嵌段分布IPDI型PU的化学结构.使用偏光显微镜、3D超景深显微镜和原子力显微镜观察了IPDI型PU的结晶形态,并通过示差扫描量热仪分析其结晶行为.此外,通过力学性能测试及样条拉伸断裂前后的形状回复探究了IPDI型PU的拉伸性能.结果表明:IPDI型PU中仅存在软段的晶体,且随着嵌段分布的集中,即软段分子量的提高,形成的球晶尺寸增加,PU中软段的结晶能力随之提高.不同嵌段分布的IPDI型PU具有相似的应力-应变曲线,拉伸性能相接近,但越分散的硬段其空间位阻效应越强,导致软段的取向结晶越困难,拉伸应变难以被固定,因此表现出更加优异的弹性.Segmented distribution is one of the key factors affecting the properties of polyurethane(PU).Exploring its effect on the properties of PU with cyclic hard segments will be the key to the successful development of highperformance and functional PU.Controlling the similarity of hard segment content,a series of IPDI-based PU with different segment distributions were synthesized using polycaprolactone diol(PCL-diol)with different molecular weights,isophorone diisocyanate(IPDI),and 1,4-butanediol(BDO).Herein,PCL-diol with different molecular weights was used as the soft segment,and IPDI and BDO were used as the hard segment.The chemical structures of PCL-diol with different molecular weights and the IPDI-based PU with different segment distributions were characterized by Fourier transform infrared spectroscopy,superconducting nuclear magnetic resonance and X-ray diffraction.The surface morphology of IPDI-based PU was observed using a polarizing microscope,3D ultra-depth of field microscope and atomic force microscope,and its crystallization behavior was analyzed by differential scanning calorimetry.Furthermore,the tensile properties of IPDI-based PU were explored by an electronic universal testing machine and photos of the shape of stretched splines before and after fracture.The results show that only soft segment crystals exist in IPDI-based PU,and with the aggregation of the soft segment,that is,with the increase of the molecular weight of the soft segment,the size of the formed spherulites increases,and the crystallization ability of the soft segment is also enhanced.Meanwhile,IPDI-based PU with different segment distributions have similar stress-strain curves and similar tensile properties.However,the more dispersed the hard segment,the stronger the steric hindrance effect,which makes the oriented crystallization of the soft segment more difficult,the tensile strain more difficult to be fixed,and therefore,the more excellent elasticity is exhibited.

关 键 词：聚氨酯 嵌段分布 结晶行为 弹性性能 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]