CHINESE JOURNAL OF ENERGETIC MATERIALS
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PNIMMO的初始热老化行为的等温量气法研究
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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

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国家自然科学基金(22305197)、西南科技大学研究生创新基金(24ycx1070)


Initial Thermal Aging Behavior of PNIMMO Studied by Isothermal Gasometric Method
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1.State Key Laboratory of Environmentall- Friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China;2.Xi′an Modern Chemistry Research Institute, Xi′an 710065, China

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    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Ea=156.42 kJ·mol-1,lgA=16.86 s-1,老化深度达到0.5%时Ea=156.05 kJ·mol-1,lgA=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,Ea=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。

    Abstract:

    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%, Ea 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, Ea=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─NO2 bond undergoes cleavage followed by hydrogenation, subsequently leading to gradual degradation of the main chain into stable polyaromatic compounds.

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龚雪玲,关健,刘红妮,等. PNIMMO的初始热老化行为的等温量气法研究[J]. 含能材料,DOI:10.11943/CJEM2024157.

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  • 收稿日期: 2024-06-17
  • 最后修改日期: 2024-10-23
  • 录用日期: 2024-10-24
  • 在线发布日期: 2024-10-28
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