光固化含能粘合剂的设计与合成

doi:10.12382/bgxb.2022.0315

摘要/Abstract

摘要：

为满足复杂结构固体推进剂在增材制造成型及能量方面的需求,以环氧氯丙烷为原料,经三氟化硼乙醚引发剂体系阳离子开环聚合,叠氮化钠叠氮化反应,异氰酸酯类化合物及丙烯酸羟乙酯亲核加成反应,合成3种光固化含能预聚物。产物结构通过傅里叶红外光谱、核磁共振氢谱和凝胶渗透色谱进行表征测试。通过高低温差示扫描量热分析对预聚物的热稳定性和玻璃化转变温度进行测试,预聚物的热聚合起始温度均为140℃,热分解起始温度均为220℃,玻璃化转变温度分别为-43.8℃、-52.7℃和-55.8℃。将3种预聚物与稀释剂和光引发剂复配制得液态光敏树脂,并将其固化成膜进行力学性能测试,其中叠氮聚醚聚氨酯丙烯酸酯GAP/IPDI/HEA-PUA固化膜抗拉强度为0.38MPa,断裂延伸率为470%,满足推进剂用粘合剂基本力学性能要求,是一种具有应用前景的新型光固化含能粘合剂。

关键词: 光固化, 含能粘合剂, 光敏树脂, 力学性能, 增材制造

Abstract:

To meet the demand of solid propellants with complex structuresin additive manufacturing and energy, epichlorohydrin was used as the raw material for cationic ring opening polymerization by boron trifluoride ethyl ether initiator system, azide reaction by sodium azide, isocyanate compound, and hydroxyethyl acrylate nucleophilic addition reaction.Three kinds of energetic binderprepolymers with light-curing properties were synthesized.The structures of the products were characterized by Fourier infrared spectroscopy, nuclear magnetic resonance hydrogen spectroscopy, and gel permeation chromatography. The thermal stability and glass transition temperature of the prepolymers were tested by high and low temperature differential scanning calorimetry analysis.The thermal polymerization onset temperature of the prepolymers was 140℃, the thermal decomposition onset temperature was 220℃, and the glass transition temperatures were -43.8℃, -52.7℃ and -55.8℃, respectively. The three prepolymers were compounded with diluent and photoinitiator to obtain a liquid photosensitive resin, and the cured film was further prepared and tested for mechanical properties, in which the tensile strength of GAP/IPDI/HEA-PUA cured film was 0.38MPa and the elongation at break was 470%, meeting the basic mechanical property requirements of adhesives for propellants, which is a new type of UV-curable energetic binders with practical applications.

Key words: light curing, energetic binders, photosensitive resin, mechanical property, additive manufacturing

袁璟, 蔺向阳, 彭洋, 檀成. 光固化含能粘合剂的设计与合成[J]. 兵工学报, 2023, 44(7): 2023-2032.

YUAN Jing, LIN Xiangyang, PENG Yang, TAN Cheng. Design and Synthesis of Light-Curable Energetic Binders[J]. Acta Armamentarii, 2023, 44(7): 2023-2032.

图/表 15

图1 GAP/TDI/HEA-PUA的合成反应路线

Fig.1 Synthetic routes of GAP/TDI/HEA-PUA

图2 PECH的傅里叶变换红外光谱图

Fig.2 IR spectrum of PECH

图3 GAP的傅里叶变换红外光谱图

Fig.3 IR spectrum of GAP

图4 GAP/TDI/HEA-PUA的傅里叶变换红外光谱图

Fig.4 IR spectrums of GAP/TDI/HEA-PUA

图5 GAP/IPDI/HEA-PUA和GAP/HDI/HEA-PUA的FT-IR谱图

Fig.5 IR spectrums of GAP/IPDI/HEA-PUA and GAP/HDI/HEA-PUA

图6 PECH的核磁共振氢谱(DMSO)

Fig.6 1H-NMR spectrum ofPECH(DMSO)

图7 GAP的核磁共振氢谱(DMSO)

Fig.7 1H-NMR spectrum of GAP (CDCl3)

图8 GAP/TDI/HEA-PUA的核磁共振氢谱(CDCl3)

Fig.8 1H-NMR spectrum of GAP/TDI/HEA-PUA (CDCl3)

图9 GAP/IPDI/HEA-PUA的核磁共振氢谱(CDCl3)

Fig.9 1H-NMR spectrum of GAP/IPDI/HEA-PUA(CDCl3)

图10 GAP/HDI/HEA-PUA的核磁共振氢谱(CDCl3)

Fig.10 1H-NMR spectrum ofGAP/HDI/HEA-PUA (CDCl3)

表1 3种目标预聚物的GPC测试结果

Table 1 GPC test results for three target prepolymers

样品	理论M_n	实测M_n	M_w	多分散性
GAP	6561	6561	8962	1.37
GAP/TDI/HEA-PUA	7141	14582	45979	3.15
GAP/IPDI/HEA-PUA	7238	13256	41054	3.10
GAP/HDI/HEA-PUA	7130	9634	16290	1.69

图11 引发剂体系用量对PECH数均相对分子质量的影响

Fig.11 Influence of initiator system amount on average molecular weight of PECH

图12 GAP与3种预聚物的高温DSC曲线

Fig.12 High-temperature DSC curves of GAP and three prepolymers

图13 3种预聚物的低温DSC曲线

Fig.13 Low-temperature DSC curves of three prepolymers

图14 3种目标预聚物的力学性能测试

Fig.14 Mechanical properties testing of three target prepolymers

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