聚酰胺酸-聚氨酯嵌段共聚物及其热亚胺化弹性体的制备与性能  

Preparation and properties of polyamic acid-polyurethane block copolymers and thermoimide elastomers

作　　者：万立祥 崔锦峰[1,2] 郭军红 包雪梅[1] 杨保平[1] WAN Lixiang;CUI Jinfeng;GUO Junhong;BAO Xuemei;YANG Baoping(College of Petrochemical Engineering,Lanzhou University of Technology,Lanzhou 730050,Gansu,China;Lanzhou Petrochemical University of Vocational Technology,Lanzhou 730060,Gansu,China)

机构地区：[1]兰州理工大学石油化工学院,甘肃兰州730050 [2]兰州石化职业技术大学,甘肃兰州730060

出　　处：《化工进展》2025年第1期398-406,共9页Chemical Industry and Engineering Progress

基　　金：甘肃省教育厅产业支撑项目(CYZC2023-31)。

摘　　要：以均苯四甲酸酐(PMDA)、4,4′-二氨基二苯醚(ODA)为原料,合成聚酰胺酸齐聚物(PAA),后与异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇(PTMG)和1,4′-丁二醇(BDO)合成的聚氨酯预聚体进行嵌段,合成聚酰胺酸聚氨酯嵌段共聚物(PAA-PU),通过平板硫化仪热亚胺化,制备聚酰亚胺-聚氨酯嵌段共聚物(PI-PU)弹性体。采用红外光谱(FTIR)、核磁共振波谱(NMR)、热重分析(TGA)、X射线光电子能谱(XPS)、力学性能测试、动态热机械分析(DMA)、差示扫描量热分析(DSC)、凝胶渗透色谱(GPC)对齐聚物PAA、嵌段聚合物PAA-PU、PI-PU及PU进行结构表征和性能测试。结果表明,相较于拉伸强度23.8MPa的PU,引入PAA的嵌段聚合物拉伸强度提高到63.7MPa,亚胺化后的聚合物拉伸强度进一步提高到86.4MPa,聚合物最大热分解温度提高到352.6℃,残留质量上升。DMA测试结果表明,随着PI的嵌段引入,嵌段聚合物Tg由37.2℃提升至91.6℃,随着PI含量增加,Tg进一步提升至128.5℃。此外,嵌段聚合物的储能模量增大,损耗模量降低,橡胶平台变宽。The polyamic acid(PAA)was synthesized by pyromellitic dianhydride(PMDA)and 4,4'-diaminodiphenyl ether(ODA),followed by polymerization with a polyurethane prepolymer constructed by isophorone diisocyanate(IPDI),polytetramethylene tetramethylene ether glycol(PTMG)and 1,4'-butanediol(BDO)to prepare a block copolymer poly(amide-urethane)(PAA-PU).Subsequently,the PAA-PU evolved to final poly(imide-urethane)(PI-PU)by thermal imidization by a plate vulcanizer.The chemical structure and performance of aforementioned copolymers were characterized by infrared spectroscopy(FTIR),nuclear magnetic resonance spectroscopy(NMR),thermogravimetric analysis(TGA),X-ray photoelectron spectroscopy(XPS),mechanical property testing,dynamic thermomechanical analysis(DMA),differential scanning calorimetry(DSC)and gel permeation chromatography(GPC).As a result,the tensile strength was enhanced to 63.7MPa for PAA-PU and 86.4MPa for PI-PU,compared to 28.3MPa for polyurethane(PU).Besides,the temperature of maximum degradation rate of copolymer reached to 352.6℃and the residual retention was increased.In addition,the glass transformation temperature of copolymer was improved from 37.2℃to 91.6℃as polyimide segments incorporated and further elevated to 128.5℃due to additional content of polyimide segments.Meanwhile,the increases of storage modulus,reduction of loss modulus and widened rubber platform of PI-PU copolymer were also displayed in respect to PU.

关 键 词：聚氨酯 聚酰亚胺 嵌段共聚 弹性体 力学性能 

分 类 号：TQ334[化学工程—橡胶工业]