文献类型：期刊文献

中文题名：3D打印用紫外光固化衣康酸基不饱和聚酯树脂的制备与性能

英文题名：Preparation and properties of UV-curable itaconic acid-based unsaturated polyester resin for 3D printing

作者：仇宇昊[1,2] 朱国强[2] 赵平[1] 刘承果[2] 周永红[2]

第一作者：仇宇昊

机构：[1]西南林业大学西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明650224;[2]中国林业科学研究院林产化学工业研究所,江苏省生物质能源与材料重点实验室,南京210042

年份：2023

卷号：8

期号：3

起止页码：182-189

中文期刊名：林业工程学报

外文期刊名：Journal of Forestry Engineering

收录：CSTPCD;;Scopus;北大核心:【北大核心2020】；CSCD:【CSCD_E2023_2024】；

基金：云南省“兴滇英才支持计划”;中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2020QA005)。

语种：中文

中文关键词：不饱和聚酯树脂;衣康酸;高生物基含量;动态双硫键;3D打印

外文关键词：unsaturated polyester resin;itaconic acid;high bio-based content;dynamic disulfide bond;3D printing

分类号：TQ321

摘要：受传统化石资源的枯竭和环境污染的影响,利用生物质资源开发新型高分子材料具有十分重要的意义。首先利用衣康酸(IA)和乙二醇(EG)与3,3′-二硫代二丙酸(DTPA)在高温下发生缩聚酯化反应,得到生物基不饱和聚酯光敏预体(IED)。然后,将IED和生物基活性稀释剂甲基丙烯酸四氢糠基酯(THFMA)、光引发剂2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)复配得到光固化不饱和聚酯树脂(IEDT)。通过RT-IR监测IEDT的双键转化率和最大转化速率等光固化动力学参数,并测试了光固化材料的力学、热力学等性能。所得光固化材料具有较高的生物基含量(质量分数45.0%~61.1%)和优异的力学性能(拉伸强度最高可达35.3 MPa)。此外,树脂材料中含有动态双硫键,高温下可以发生动态交换,实现了IEDT材料的热压回收和重复利用。将最优树脂进一步应用于数字光处理(DLP)-3D打印,并测量其工作曲线,成功地打印了不同结构的模型。总体来说,该生物基不饱和聚酯树脂(IEDT)在光固化3D打印等领域有良好的应用潜力。
Due to the depletion of fossil resources and environmental pollution,the utilization of biomass resources to develop new polymer materials is of great significance.As a biomass product,itaconic acid can be prepared by fermentation of agricultural and forestry waste resources.It is widely available,inexpensive and chemically active because it contains conjugated double bonds and carboxyl groups.Moreover,traditional unsaturated polyester resins require to be prepared by fossil materials,and cannot be recycled after curing,causing serious waste pollution,which does not conform to the strategic concept of“green development”around the world.Therefore,the use of biomass resources to prepare recyclable unsaturated polyester resin is of extremely important significance.In this study,itaconic acid(IA)was used to the polycondensation with 3,3′-dithiodipropionic acid(DTPA)and ethylene glycol(EG)at high temperatures to obtain a bio-based unsaturated polyester prepolymer(IED).A set of UV-curable unsaturated polyester resins(IEDT)was prepared by blending IEDs with the bio-based tetrahydrofurfuryl methacrylate(THFMA)diluent and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide(TPO)photoinitiator.The structure of the prepolymer(IED)was analyzed by the Fourier transform infrared spectrometer(FT-IR)and Raman spectra.The UV curing kinetics of IEDT were investigated by RT-IR and the IEDT material gel,physics properties such as viscosity,solvent resistance,and coating were examined.The gel contents of the materials were between 90.8%and 94.7%,and the viscosities were between 323 and 359 mPa·s.The materials had excellent coating properties and solvent resistance,and the mechanical and thermal properties of the UV-cured materials were also studied.The resulting UV-curable materials showed a high bio-based contents(mass ratio of 45.0%-61.1%)and excellent mechanical properties(maximum tensile strength up to 35.3 MPa).The T g of the material was 44.5-87.6℃,and the material had good thermal stability(the initial decomposition temperatures of 251.2-258.3℃and the maximum decomposition temperatures of 351.4-377.3℃).In addition,the resin material contained dynamic disulfide bonds,which could be dynamically exchanged at high temperatures,thus the hot-pressing recovery and reuse of the IEDT materials were achieved.The optimal resin application was for digital optical processing(DLP)-3D printing,and its working curve was measured.Several models with different structures were successfully printed.In general,the bio-based UV-curable unsaturated polyester resins(IEDT)showed good application potential in 3D printing and other fields,it has great application prospect in recyclable photocuring 3D printing.