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含氟聚合物/缩水甘油叠氮聚合物(GAP)嵌段共聚氨酯作为新型含能粘合剂:合成、力学性能及热性能

Fluoropolymer/Glycidyl Azide Polymer (GAP) Block Copolyurethane as New Energetic Binders: Synthesis, Mechanical Properties, and Thermal Performance.

作者信息

Xu Minghui, Lu Xianming, Liu Ning, Zhang Qian, Mo Hongchang, Ge Zhongxue

机构信息

State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.

Department of Energetic Materials Science and Technology, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.

出版信息

Polymers (Basel). 2021 Aug 13;13(16):2706. doi: 10.3390/polym13162706.

Abstract

In order to enhance the application performance of glycidyl azide polymer (GAP) in solid propellant, an energetic copolyurethane binder, (poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol--glycidylazide polymer (PBFMO--GAP) was synthesized using poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol (PBFMO), which was prepared from cationic polymerization with GAP as the raw material and toluene diisocyanate (TDI) as the coupling agent via a prepolymer process. The molecular structure of copolyurethanes was confirmed by attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance spectrometry (NMR), and gel permeation chromatography (GPC). The impact sensitivity, mechanical performance, and thermal behavior of PBFMO--GAP were studied by drop weight test, X-ray photoelectron spectroscopic (XPS), tensile test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA), respectively. The results demonstrated that the introduction of fluoropolymers could evidently reduce the sensitivity of GAP-based polyurethane and enhance its mechanical behavior (the tensile strength up to 5.75 MPa with a breaking elongation of 1660%). Besides, PBFMO--GAP exhibited excellent resistance to thermal decomposition up to 200 °C and good compatibility with Al and cyclotetramethylene tetranitramine (HMX). The thermal performance of the PBFMO--GAP/Al complex was investigated by a cook-off test, and the results indicated that the complex has specific reaction energy. Therefore, PBFMO--GAP may serve as a promising energetic binder for future propellant formulations.

摘要

为提高缩水甘油叠氮聚合物(GAP)在固体推进剂中的应用性能,采用阳离子聚合法以GAP为原料制备的聚[3,3-双(2,2,2-三氟乙氧基甲基)氧杂环丁烷]二醇(PBFMO),与甲苯二异氰酸酯(TDI)作为偶联剂,通过预聚物工艺合成了一种含能共聚聚氨酯粘合剂(聚[3,3-双(2,2,2-三氟乙氧基甲基)氧杂环丁烷]二醇-缩水甘油叠氮聚合物(PBFMO-GAP))。通过衰减全反射-傅里叶变换红外光谱(ATR-FTIR)、核磁共振光谱(NMR)和凝胶渗透色谱(GPC)对共聚聚氨酯的分子结构进行了确认。分别通过落锤试验、X射线光电子能谱(XPS)、拉伸试验、扫描电子显微镜(SEM)、差示扫描量热法(DSC)和热重分析(TGA)研究了PBFMO-GAP的冲击敏感性、力学性能和热行为。结果表明,含氟聚合物的引入可明显降低GAP基聚氨酯的敏感性并增强其力学性能(拉伸强度高达5.75 MPa,断裂伸长率为1660%)。此外,PBFMO-GAP在高达200℃时表现出优异的热分解抗性,并且与铝和环四亚甲基四硝胺(HMX)具有良好的相容性。通过烤燃试验研究了PBFMO-GAP/Al复合物的热性能,结果表明该复合物具有特定的反应能量。因此,PBFMO-GAP有望成为未来推进剂配方中一种有前景的含能粘合剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8812/8399772/1e01f6df190f/polymers-13-02706-g001.jpg

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