PNIMMO的初始热老化行为的等温量气法研究  

Initial Thermal Aging Behavior of PNIMMO Studied by Isothermal Gasometric Method

作　　者：龚雪玲 关健 刘红妮[2] 莫洪昌[2] 张庆元 彭汝芳 金波 GONG Xue-ling;GUAN Jian;LIU Hong-ni;MO Hong-chang;ZHANG Qing-yuan;PENG Ru-fang;JIN Bo(State Key Laboratory of Environmentall‑Friendly Energy Materials,Southwest University of Science and Technology,Mianyang 621010,China;Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

机构地区：[1]西南科技大学环境友好能源材料国家重点实验室,四川绵阳621010 [2]西安近代化学研究所,陕西西安710065

出　　处：《含能材料》2025年第3期277-283,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22305197);西南科技大学研究生创新基金(24ycx1070)。

摘　　要：为了研究聚3-硝酸酯甲基-3-甲基氧杂环丁烷(PNIMMO)的初始等温热老化行为,采用等温量气装置,对PNIMMO在100~120℃等温条件下的老化动力学参数和热老化机理进行了探究,采用Berthelot方程外推了PNIMMO在不同温度下的贮存寿命。结果表明,由Arrhenius方程得到PNIMMO老化深度达到0.1%时E_(a)=156.42 kJ·mol^(-1),lgA=16.86 s^(-1),老化深度达到0.5%时E_(a)=156.05 kJ·mol^(-1),IgA=16.03 s^(-1);由模式配合法得出,在100~120℃时,PNIMMO热老化均符合28号机理函数,即反应级数n=1/4,E_(a)=154.33 kJ·mol^(-1);以老化深度0.1%作为评判标准,PNIMMO在室温下可贮存51.6年;PNIMMO在热分解初期主要为侧链—O—NO2键断裂加氢,随后主链缓慢分解,生成稳定的多聚芳香类化合物。The initial isothermal aging behavior of poly(3-nitratomethyl-3-methyloxetane)(PNIMMO)was studied.The aging kinetic parameters and thermal aging mechanism of PNIMMO at 100-120℃were investigated using an isothermal gas measuring device.The storage life of PNIMMO was determined by the Berthelot equation.The results indicate that the activation energy(Ea)is 156.42 kJ·mol^(-1)and the logarithm of the pre-exponential factor(lgA)is 16.86 s^(-1)when the aging depth of PNIMMO reaches 0.1%.Conversely,at an aging depth of 0.5%,E_(a)is measured at 156.05 kJ·mol^(-1)and lgA at 16.03 s^(-1),as derived from the Arrhenius equation.According to the mode matching method,the thermal aging of PNIMMO at 100-120℃conforms to the mechanism function No.28,that is,the reaction order n=1/4,E_(a)=154.33 kJ·mol^(-1).Using an aging depth of 0.1%as the evaluation criterion,PNIMMO can be stored at room temperature for 51.6 years.During the initial phase of thermal decomposition,the side chain─O─NO_(2)bond undergoes cleavage followed by hydrogenation,subsequently leading to gradual degradation of the main chain into stable polyaromatic compounds.

关 键 词：聚3-硝酸酯甲基-3-甲基氧杂环丁烷 等温热老化 动力学 贮存寿命 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O631.33[理学—高分子化学]