GAP/PBAMO基含能热塑性弹性体的可控合成和性能研究

Study on controlled synthesis and performance of GAP/PBAMO-based energetic thermoplastic elastomers

为了改善传统聚叠氮缩水甘油醚(GAP)基含能热塑性弹性体(ETPE)的性能,以GAP、聚3,3'-双(叠氮甲基)氧杂环丁烷(PBAMO)为预聚物,采用官能团预聚法合成了不同结构组成的GAP/PBAMO基含能热塑性弹性体(GBETPE)。通过傅里叶变换红外光谱(FTIR)、核磁共振氢谱(^(1)H-NMR)、凝胶渗透色谱(GPC)以及元素分析等测试手段对共聚物的结构进行表征,证实了共聚物结构与组成的可控性。GBETPE的数均相对分子质量(Mn)为30243~33480,分子量分布(PD)保持在1.22~1.60,氮质量分数为37.47%~39.22%。通过热重(TG)、差示扫描量热仪(DSC)以及拉伸测试对共聚物的热性能和力学性能进行了研究,建立了共聚物结构与性能之间的关系。GBETPE的初始热分解温度(T5%)为219.66~234.88℃,玻璃化转变温度(T_(g))为-37.0~-29.7℃,熔点(T_(m))为60.0~75.5℃,具有较佳的热性能。以HMDI(4,4'-二环己基甲烷二异氰酸酯)和1,4-丁二醇(BDO)作硬段,GAP的质量分数为50.98%,硬段质量分数为25.5%时,GBETPE的最大拉伸强度(σ_(m))为4.70MPa,断裂伸长率(ε_(b))为487.2%,具有较好的力学性能。

In order to improve the performance of traditional glycidyl azide polymer(GAP)-based energetic thermoplastic elastomers(ETPE),GAP/PBAMO-based energetic thermoplastic elastomers(GBETPE)with different structural compositions were synthesized using GAP,poly(3,3′-bis-azidomethyloxetane)(PBAMO)as prepolymers by functional group prepolymerization method.The structure of the copolymers was characterized by Fourier transform infrared(FTIR)spectroscopy,nuclear magnetic resonance hydrogen spectroscopy(^(1)H-NMR),gel permeation chromatograph(GPC)and elemental analysis,etc.,which confirmed the controllability of the structure and composition of the copolymer.The number average relative molecular mass(Mn)of GBETPE was 30243~33480,the molecular weight distribution(PD)remained at 1.22~1.60,and the nitrogen mass fraction was 37.47%~39.22%.The thermal and mechanical performance of the copolymers were investigated by thermogravimetry(TG),differential scanning calorimeter(DSC)and tensile test,and the relationship between the structure and performance of the copolymers was established.The initial thermal decomposition temperature(T5%)of GBETPE was 219.66~234.88℃,the glass transition temperature(T_(g))was-37.0℃to-29.7℃,and the melting point(T_(m))was 60.0~75.5℃,showing that it had excellent thermal performance.With HMDI(4,4′-dicyclohexylmethane diisocyanate)and 1,4-butanediol(BDO)as rigid segments,the mass fraction of GAP was 50.98%,and the mass fraction of the rigid segment was 25.5%,the maximum tensile strength(σ_(m))of GBETPE was 4.70MPa,and the elongation at break(ε_(b))was 487.2%,showing that it had good mechanical performance.