一步法合成P4HB基热塑性聚氨酯弹性体及其性质  

One-Step Synthesis and Properties of P4HB Based Thermoplastic Polyurethane Elastomers

作　　者：谭智宇 宋红玮 沈勇 李志波 TAN Zhiyu;SONG Hongwei;SHEN Yong;LI Zhibo(College of Chemical Engineering,Shandong Provincial Education Department,College of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042,Shandong,China;Key Laboratory of Biobased Polymer Materials,Shandong Provincial Education Department,College of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042,Shandong,China)

机构地区：[1]青岛科技大学化工学院 [2]青岛科技大学高分子科学与工程学院,山东省教育厅生物基高分子材料重点实验室

出　　处：《功能高分子学报》2024年第3期187-195,共9页Journal of Functional Polymers

基　　金：国家自然科学基金重点项目(22031005)。

摘　　要：以聚(4-羟基丁酸酯)(P4HB)为软段、不同异氰酸酯和1,4-丁二醇(BDO)为硬段,通过一步法合成了一系列可解聚回收的P4HB基聚氨酯(P4HB-TPU)。研究了投料比、P4HB的数均分子量、扩链剂BDO含量以及异氰酸酯种类对聚氨酯性能的影响,以及P4HB-TPU的可控解聚与单体回收。采用傅里叶变换红外光谱、热重分析、差示扫描量热、单轴机械拉伸等对P4HBTPU的热性能、力学性能以及热解聚回收性进行了研究。结果表明,当投料配方设计中n(—NCO)/n(—OH)为1.1、异氰酸酯为二环己基甲烷-4,4’-二异氰酸酯(HMDI)、P4HB的数均分子量为1.9×103时,P4HB-TPU的拉伸强度可达到37.8 MPa,性能与商用聚己内酯基热塑性聚氨酯(PCL-TPU)相近。随着P4HB分子量的增大,其结晶性使得聚氨酯由弹性体开始向塑料转变。BDO含量的增加在一定程度上有助于提高TPU的力学性能。使用环状对称的异氰酸酯可以有效提升材料的拉伸强度。在170℃、200 Pa的条件下,通过对P4HB-TPU热解聚,可以将P4HB解聚为γ-丁内酯(γ-BL)单体,并达到约98%的单体回收率。A series of depolymerizable and recyclable thermoplastic polyurethanes(TPU)were synthesized through a one-step method using poly(4-hydroxybutyrate)(P4HB)as the soft segment and different diisocyanates and 1,4-butanediol(BDO)as the hard segment.The effects of feed ratio,P4HB molecular weight,chain extender content,and isocyanates on the properties of P4HB based TPU(P4HB-TPU)were studied,and the controllable depolymerization and monomer recovery of P4HB-TPU were also investigated.The thermal properties,mechanical properties,and thermal decomposition recovery of P4HB-TPU were studied using Fourier transform infrared spectroscopy,thermogravimetric analysis,differential scanning calorimetry,uniaxial mechanical stretching,and other testing methods to illustrate the relationship between polyurethane structure and properties.Results show that when n(-NCO)/n(-OH)is 1.1,tensile strength of P4HB-TPU can reach 37.8 MPa with comparable mechanical performance to commercial TPU.With the increase of molecular weight,the P4HB segment starts to crystallize and thus causes a transition of P4HB-TPU from elastic to plastic polyurethane.The increase of BDO content can improve the mechanical properties of P4HB-TPU to a certain extent,and use of cyclic symmetric isocyanates can effectively improve the tensile strength of materials.Notably,P4HB-TPU can use Sn(Oct)2 at 170℃,200 Pa that be depolymerized intoγ-BL monomer,and achieves a monomer recovery rate of approximately 98%.

关 键 词：聚酯聚氨酯 聚(4-羟基丁酸酯) 闭合循环 聚氨酯解聚 热塑性聚氨酯 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]