可重复加工型生物基热固性自修复聚氨酯树脂的合成与性能  

Synthesis and Properties of Repeatable Bio-Based Thermosetting Polyurethane Resins

作　　者：李宁 张昊 王璐瑶 张晓宇 高红梅 张驰 曾芳磊 缪丽锋 薛亚波 张其土[2] Ning Li;Hao Zhang;LuyaoWang;Xiaoyu Zhang;Hongmei Gao;Chi Zhang;Fanglei Zeng;Lifeng Miao;Yabo Xue;Qitu Zhang(School of Materials Science and Engineering,Changzhou University,Changzhou 213164,China;School of Materials Science and Engineering,Nanjing Tech University,Nanjing 211816,China;CRRC QISHUYAN INSTITUTE CO.,LTD.,Changzhou 213011,China;Jiangsu Chenguang Coating Co.,LTD.,Changzhou 213000,China)

机构地区：[1]常州大学材料科学与工程学院,江苏常州213164 [2]南京工业大学材料科学与工程学院,江苏南京211816 [3]中车戚墅堰机车车辆工艺研究所有限公司,江苏常州213011 [4]江苏晨光涂料有限公司,江苏常州213000

出　　处：《高分子材料科学与工程》2024年第5期1-10,共10页Polymer Materials Science & Engineering

基　　金：中国博士后基金(2022M721374);常州市重点研发计划产业前瞻与关键核心技术项目(CE20230005)。

摘　　要：热固性聚氨酯树脂存在不可重复加工等问题,大大降低了材料的使用寿命,同时造成资源浪费。文中以水热法制备了以羟甲基化木质素(Lig-OH)为生物基软段、异佛尔酮二异氰酸酯(IPDI)为硬段、三羟甲基丙烷(TMP)为交联型扩链剂、4,4’-二氨基二苯二硫醚(4-SO)为二次扩链剂、4-甲基伞形酮(4-MU)为生物基封端剂的可重复加工型生物基热固性聚氨酯树脂(LPU)。通过傅里叶变换红外光谱表征其结构,通过光学显微镜、3D轮廓仪等研究其自修复性能,通过拉伸测试、重复加工测试对其力学性能和可重复性进行研究。结果表明,LPU-5(TMP用量为18 mmol)的力学性能最佳,拉伸强度可达18.92 MPa,断裂伸长率可达709.82%,全切修复后分别可达16.90 MPa,630.32%,修复效率为89%,仍具有使用价值。样条全切修复后树脂经粉碎后可以重新加工成完整的聚氨酯膜使用,具备优异的可重复加工性。并且可实现加热及紫外光下的双重修复功能,其中LPU-2在75℃时10 min即可完成划痕修复。Thermosetting polyurethane resin has some problems such as non-repeatable processing,which greatly reduces the service life of material and causes waste of resources.In this paper,using hydroxylmethylated lignin(Lig-OH)prepared by hydrothermal method as bio-based soft segment,isophorone diisocyanate(IPDI)as hard segment,trimethylol propane(TMP)as cross-linked chain extender,4,4'-diaminodiphenyl disulfide(4-SO)as secondary chain extender,and 4-methylumbellione(4-MU)as bio-based end sealing agent,the biodegradable thermosetting polyurethane resin(LPU)was successfully prepared.Its structure was characterized by Fourier infrared spectroscopy,its self-healing properties were studied by optical microscope and 3D profiler,and its mechanical properties and repeatability were studied by tensile and repeated machining test.The results show that LPU-5(TMP 18 mmol)has the best mechanical properties,with the tensile strength up to 18.92 MPa,elongation at break up to 709.82%.After total incision repair,the tensile strength and elongation at break can reach 16.90 MPa,630.32%respectively,and the repair efficiency is up to 89%after full-cut repair.After the spline is completely cut and repaired,the resin can be crushed and reprocessed into a complete polyurethane film,which has excellent repeatability.And it can realize the dual repair function under heating and ultraviolet light,in which LPU-2 can complete the scratch repair at 75℃for 10 min.

关 键 词：羟甲基化木质素 热固性聚氨酯 光热修复 可重复加工 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]