聚氨酯硬段中非平面环含量对其多尺度性能的影响  

Effect of the non-planar ring content in the hard segment of polyurethane on its multi-scale properties

作　　者：徐伟[1] 张若愚[1] 郭洪霞[2] 

机构地区：[1]中国科学院宁波材料技术与工程研究所,浙江宁波315201 [2]中国科学院化学研究所,北京100190

出　　处：《北京化工大学学报（自然科学版）》2016年第4期59-65,共7页Journal of Beijing University of Chemical Technology(Natural Science Edition)

基　　金：浙江省自然科学基金(LY15B040006)

摘　　要：首先以对苯二异氰酸酯(PPDI)和对苯二酚二羟乙基醚(HQEE)为硬段,聚四氢呋喃醚二醇(PTMG)为软段合成基础聚氨酯化合物。在第一种系列中,保持HQEE不变,以异佛尔酮二异氰酸酯(IPDI)逐步替换PPDI,直至完全替换;在第二种系列中,保持PPDI不变,以1,4-环己烷二甲醇(CHDM)或螺环乙二醇(SPG)逐步替换HQEE,直至完全替换。用AFM单分子力谱对这些聚氨酯样品进行单分子链拉伸模量和库恩链长度的测量,结果表明:不同结构取代苯环后,各自的库恩链长受到的影响较小,而各自的单分子链模量受到影响较大;分子链模量的演变规律并不是简单的模量叠加,各种类型的结构对模量的影响规律各不相同。由于受到分子链结构的影响,一系列聚合物的微相分离和宏观性能也发生了显著的变化。通过本文研究结果,可以清楚地看到微观结构的改变对聚氨酯微观和宏观性能的多尺度影响。Polyurethane composed of 1,4-phenylene diisocyanate（ PPDI） and hydroquinone bis（ 2-hydroxyethyl）ether（ HQEE）,as hard segment,and poly（ tetramethylene glycol）（ PTMG）,as soft segment,was synthesized as a reference. For the first type of samples,a series of polyurethanes was prepared by gradually substituting PPDI with isophorone diisocyanate（ IPDI）. For the second and third types of samples,two series of polyurethanes were prepared by gradually substituting HQEE with 1,4-cyclohexanedimethanol（ CHDM） or 3,9-bis（ 1,1-dimethyl-2-hydroxyethyl）-2,4,8,10-tetraoxaspiro[5. 5]undecane（ SPG）. Single molecule force spectroscopy（ SMFS） was performed to measure the molecular chain modulus and Kuhn length of these polyurethane samples. After the benzene ring was substituted,the change of Kuhn length was small. However,its influence on molecular chain modulus was obvious. The evolution of the molecular chain modulus was not a simple superposition of moduli,and the influence of three types of non-planar ring structure on the moduli was different. Owing to the changing structure of the main chain,microphase separation and macroscopic mechanical performance were altered significantly. In this study,the multi-scale effects of micro-scale structure on the nano and macro-scale performances of polyurethane were clearly observed.

关 键 词：聚氨酯 单分子力谱 分子链模量 拉伸模量 

分 类 号：O631.11[理学—高分子化学]