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新型叠氮缩水甘油聚合物水乳液的合成与表征

Synthesis and Characterization of a Novel Aqueous Glycidyl Azide Polymer Emulsion.

作者信息

Song Yufang, Xiao Leqin, Jian Xiaoxia, Zhou Weiliang, He Xu

机构信息

School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.

出版信息

ACS Omega. 2021 Nov 17;6(47):32081-32089. doi: 10.1021/acsomega.1c04865. eCollection 2021 Nov 30.

Abstract

The current domestic and foreign research on azide polymers such as glycidyl azide polymers (GAP) mainly focuses on the design, synthesis, modification, and performance of elastomers; it is difficult to prepare the GAP/NC (nitrocellulose) blends, and they have poor mechanical properties. Here, we developed a green and safe strategy for the blending and compounding of azide binder and NC by blending the emulsion with NC in water and demulsifying. Considering the structural characteristics of GAP, a novel energetic aqueous GAP-E (energetic elastomer) emulsion was prepared by anionic self-emulsion polymerization using 2,2-dimethylol propionic acid as the hydrophilic chain extender, 1,4-butanediol as the chain extender, and triethylamine as a neutralizer. Furthermore, the GAP-E emulsion/triethylene glycol dinitrate/nitrocellulose blends (GAP-E/TEGN/NC) with different proportions were prepared in aqueous phase by the precipitation method. The related properties of the emulsion were studied by gel permeation chromatography, Fourier transform infrared, universal material testing machine, dynamic mechanical analyzer, thermogravimetric analysis, and scanning electron microscopy (SEM). Our results indicated the emulsion exhibited good stability with the number average molecular weight of 76,600. The GAP-E film showed a tensile strength of 17.8 MPa, elongation at break of 415%, glass transition temperature of -28.5 °C, and initial degradation temperature of 242 °C. The GAP-E emulsion and TEGN/NC can be blended in the aqueous phase by the demulsification method to prepare a homogeneous GAP-E/TEGN/NC blend. Fourier transform infrared spectroscopy (FTIR) showed that there was a certain hydrogen bond interaction between GAP-E and TEGN/NC molecules, which was conducive to the improvement of the mechanical properties. The results of SEM indicated that GAP-E could obviously soften the rigid fiber structure of TEGN/GN, and the blends were well mixed with good interfacial compatibility between the GAP-E (5%) and TEGN/NC. When the mass fraction of GAP-E was 5%, the tensile strength and the elongation at break of the blend reached up to 32.1 MPa and 54.4%, which were improved by 33 and 46% compared to those of the TEGN/NC blend system, respectively. The transition temperature remained at -21.6 °C with obvious enhancement on the mechanical properties.

摘要

目前国内外对叠氮聚合物如缩水甘油叠氮聚合物(GAP)的研究主要集中在弹性体的设计、合成、改性及性能方面;制备GAP/NC(硝化纤维素)共混物存在困难,且其机械性能较差。在此,我们开发了一种绿色安全的策略,通过在水中将乳液与NC混合并破乳,实现叠氮粘合剂与NC的共混复合。考虑到GAP的结构特点,以2,2-二甲基丙酸为亲水性扩链剂、1,4-丁二醇为扩链剂、三乙胺为中和剂,通过阴离子自乳化聚合法制备了一种新型含能水性GAP-E(含能弹性体)乳液。此外,采用沉淀法在水相中制备了不同比例的GAP-E乳液/三乙二醇二硝酸酯/硝化纤维素共混物(GAP-E/TEGN/NC)。通过凝胶渗透色谱、傅里叶变换红外光谱、万能材料试验机、动态力学分析仪、热重分析和扫描电子显微镜(SEM)对乳液的相关性能进行了研究。结果表明,该乳液具有良好的稳定性,数均分子量为76,600。GAP-E薄膜的拉伸强度为17.8MPa,断裂伸长率为415%,玻璃化转变温度为-28.5℃,初始降解温度为242℃。GAP-E乳液与TEGN/NC可通过破乳法在水相中混合,制备出均匀的GAP-E/TEGN/NC共混物。傅里叶变换红外光谱(FTIR)表明,GAP-E与TEGN/NC分子之间存在一定的氢键相互作用,有利于机械性能的提高。SEM结果表明,GAP-E能明显软化TEGN/GN的刚性纤维结构,GAP-E(5%)与TEGN/NC之间共混良好,界面相容性好。当GAP-E的质量分数为5%时,共混物的拉伸强度和断裂伸长率分别达到32.1MPa和54.4%,与TEGN/NC共混体系相比分别提高了33%和46%。转变温度保持在-21.6℃,机械性能有明显提高。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8027/8638024/0bca2f01633f/ao1c04865_0002.jpg

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