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羧化聚(3,3-双叠氮甲基氧杂环丁烷)共聚物作为高能粘合剂潜在预聚物的合成与表征

Synthesis and characterization of carboxylated PBAMO copolymers as promising prepolymers for energetic binders.

作者信息

Lim Minkyung, Bu Meilan, Jang Yoorim, Jeong Jongoh, Noh Sitae, Rhee Hakjune

机构信息

Department of Bionanotechnology, Hanyang University 55 Hanyangdaehak-ro, Sangnok-gu Ansan Gyeonggi-do 15588 South Korea

NOROO Paint & Coatings Co., Ltd. 351, Bakdal-ro, Manan-gu Anyang-si Gyeonggido 13977 South Korea.

出版信息

RSC Adv. 2020 Mar 2;10(15):8967-8972. doi: 10.1039/c9ra09881j. eCollection 2020 Feb 27.

Abstract

The carboxylated poly[3,3-bis(3-azidomethyl)oxetane] (PBAMO) copolymers (poly(BAMO-carboxylate)) were synthesized by substitution of poly[3,3-bis(3-chloromethyl)oxetane] (PBCMO) with potassium carboxylate and sodium azide in DMSO. The synthesized compounds were characterized using various analytical techniques, such as Fourier-transform infrared (FT-IR) spectroscopy, inverse-gated decoupling C-nuclear magnetic resonance (C NMR) spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), calorimetry, friction, and impact sensitivity analysis. These poly(BAMO-carboxylate) compounds have better thermal properties, with lower glass transition temperatures (ranging from -43 °C to -51 °C) than PBAMO (-37 °C) and higher thermal decomposition temperatures (233-237 °C) than PBAMO (211 °C). Moreover, poly(BAMO-octanoate) and poly(BAMO-decanoate) have higher heats of combustion (5226 and 5665 kJ mol, respectively) and negative formation enthalpies (-0.17 and -0.55 kJ g, respectively), while PBAMO has lower heat of combustion (3125 kJ mol) and positive formation enthalpy (0.06 kJ g). The poly(BAMO-carboxylate) compounds have higher values (38-50 J) than that of PBAMO (14 J) in the impact sensitivities. This is a valuable study for improving the properties of PBAMO, which is a high energetic polymeric binder but difficult to handle because of its sensitivity. Therefore, poly(BAMO-carboxylate) could be a good candidate as a prepolymer for designing the energetic polymeric binder.

摘要

通过在二甲基亚砜中用羧酸钾和叠氮化钠取代聚3,3-双(3-氯甲基)氧杂环丁烷,合成了羧化聚3,3-双(3-叠氮甲基)氧杂环丁烷共聚物(聚(BAMO-羧酸盐))。使用各种分析技术对合成的化合物进行了表征,如傅里叶变换红外(FT-IR)光谱、反门控去耦碳核磁共振(C NMR)光谱、凝胶渗透色谱(GPC)、热重分析(TGA)、差示扫描量热法(DSC)、量热法、摩擦和冲击敏感性分析。这些聚(BAMO-羧酸盐)化合物具有更好的热性能,其玻璃化转变温度(-43℃至-51℃)低于PBAMO(-37℃),热分解温度(233-237℃)高于PBAMO(211℃)。此外,聚(BAMO-辛酸盐)和聚(BAMO-癸酸盐)具有更高的燃烧热(分别为5226和5665 kJ/mol)和负生成焓(分别为-0.17和-0.55 kJ/g),而PBAMO的燃烧热较低(3125 kJ/mol)且生成焓为正(0.06 kJ/g)。聚(BAMO-羧酸盐)化合物的冲击敏感性值(38-50 J)高于PBAMO(14 J)。这是一项对于改善PBAMO性能很有价值的研究,PBAMO是一种高能聚合物粘合剂,但由于其敏感性而难以处理。因此,聚(BAMO-羧酸盐)可能是设计高能聚合物粘合剂的预聚物的良好候选物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9feb/9050039/2d502d2fa2f3/c9ra09881j-s1.jpg

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