Design and Synthesis of Light-Curable Energetic Binders

doi:10.12382/bgxb.2022.0315

Abstract

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

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

Figures/Tables 15

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

Fig.2 IR spectrum of PECH

Fig.3 IR spectrum of GAP

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

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

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

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

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

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

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

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

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

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

Fig.13 Low-temperature DSC curves of three prepolymers

Fig.14 Mechanical properties testing of three target prepolymers

References 21

[1]	陆志猛, 曾庆林, 郑丽兵, 等. 固体推进剂混合装备研究现状与发展[J]. 固体火箭技术, 2021, 44(3):372-378.
	LU Z M, ZENG Q L, ZHENG L B, et al. Review on solid propellant mixing equipment[J]. Journal of Solid Rocket Technology, 2021, 44(3): 372-378. (in Chinese)
[2]	郑剑, 侯林法, 杨仲雄. 高能固体推进剂技术回顾与展望[J]. 固体火箭技术, 2001, 24(1):28-34.
	ZHENG J, HOU L F, YANG Z X. Review and prospect of high energy solid propellant technology[J]. Journal of Solid Rocket Technology, 2001, 24(1):28-34. (in Chinese)
[3]	ZHANG W S, ZHANG T, LIU H H. Synthesis and characterization of a novel hydroxytelechelicpolyfluoroether to enhance the properties of HTPB solid propellant binders[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648: 129199. doi: 10.1016/j.colsurfa.2022.129199 URL
[4]	张斌, 毛根旺, 王赫, 等. 高能复合固体推进剂的研究进展[J]. 材料导报, 2009, 23(7):17-20.
	ZHANG B, MAO G W, WANG H, et al. Research advances in high energy composite solid propellant[J]. Materials Reports, 2009, 23(7): 17-20. (in Chinese)
[5]	YADAV A, PANT S C, DAS S. Research advances in bonding agents for composite propellants[J]. Propellants, Explosives, Pyrotechnics, 2020, 45(5):1-11. doi: 10.1002/prep.v45.1 URL
[6]	张伟, 闫石, 郭学永, 等. 端羟基聚叠氮缩水甘油醚与六硝基六氮杂异伍兹烷基四元混合炸药能量释放研究[J]. 兵工学报, 2018, 39(7):1299-1307. doi: 10.3969/j.issn.1000-1093.2018.07.007
	ZHANG W, YAN S, GUO X Y, et al. Study of the energy release of CL-20/GAP-based quaternary explosive[J]. Acta Armamentaii, 2018, 39(7): 1299-1307. (in Chinese)
[7]	HAFNER S, KEICHER T, KLAPOTKEMT. Copolymers based on GAP and 1,2-epoxyhexane as promising prepolymers for energetic binder systems[J]. Propellants, Explosives, Pyrotechnics, 2018, 43(2): 126-135. doi: 10.1002/prep.v43.2 URL
[8]	MATHEW S, MANAU S K, VARGHESE T L. Thermomechanical and morphological characteristics of cross-linked GAP and GAP-HTPB networks with different diisocyanates[J]. Propellants, Explosives, Pyrotechnics, 2008, 33(2): 146-152. doi: 10.1002/(ISSN)1521-4087 URL
[9]	BETZLER F M, HARTDEGEN V A, KLAPOETKE T M, et al. A new energetic binder: glycidylnitraminepolymer[J]. Central European Journal of Energetic Materials, 2016, 13(2): 289-300. doi: 10.22211/cejem/64984 URL
[10]	陈永进. 光固化3D打印异型含能药柱及性能研究[D]. 沈阳: 沈阳理工大学, 2020.
	CHEN Y J. Study on 3D-printed shaped energetic grainand its properties[D]. Shenyang: Shenyang University of Science and Technology, 2020. (in Chinese)
[11]	MCCLAIN M S, AFRIAT A, RHOADS J F, et al. Development and characterization of a photopolymericbinder for additively manufactured composite solid propellant using vibration assisted printing[J]. Propellants, Explosives, Pyrotechnics, 2020, 45(6): 853-863. doi: 10.1002/prep.v45.6 URL
[12]	STRAATHOF M H, DRIEL C A, LINGEN J N J, et al. Development of propellant compositions for vat photopolymerization additive manufacturing[J]. Propellants, Explosives, Pyrotechnics, 2020, 45(1):36-52. doi: 10.1002/prep.v45.1 URL
[13]	YANG W T, HU R, ZHENG L, et al. Fabrication and investigation of 3D-printed gun propellants[J]. Materials and Design, 2020, 192: 108761-18769. doi: 10.1016/j.matdes.2020.108761 URL
[14]	LI MM, YANG W T, XU M H, et al. Study of photocurable energetic resin based propellants fabricated by 3D printing[J]. Materials and Design, 2021(2):109891.
[15]	MAURYA D S, KURMVANSHI K S, MOHANTY S, et al. A review on acrylate-terminated urethane oligomers and polymers: synthesis and applications[J]. Polymer-Plastics Technology and Engineering, 2018, 57(7): 625-656. doi: 10.1080/03602559.2017.1332764 URL
[16]	PARK N H, SUH KD, KIM J Y. Preparation of UV-curable PEG-modified urethane acrylate emulsions and their coating properties. II. effect of chain length of polyoxyethylene[J]. Journal of Applied Polymer Science, 1997, 64(13): 2657-2664. doi: 10.1002/(ISSN)1097-4628 URL
[17]	CHEN J, PASCAULT J P, TAHA M. Synthesis of polyurethane acrylate oligomers based on polybutadiene polyol[J]. Journal of Polymer Science, Part A: Polymer Chemistry, 2015, 34(14): 2889-2907. doi: 10.1002/(ISSN)1099-0518 URL
[18]	YOO H J, LEE Y H, KWON J Y, et al. Comparision of the properties of UV-cured polyurethane acrylates containing different diisocyanates and low molecular weight diols[J]. Fibers & Polymers, 2001, 2(3): 122-128.
[19]	SCHMIDLE C J. Ultraviolet curable flexible coatings[J]. Journal of Coated Fabrics, 1978, 8(1): 10-20. doi: 10.1177/152808377800800102 URL
[20]	PEDROSO L M, SIMOES P, PORTUGAL A. Cyanuric acid/epichlorohydrin energetic prepolymers[J]. Propellants, Explosives, Pyrotechnics, 2005, 30(5):338-343. doi: 10.1002/(ISSN)1521-4087 URL
[21]	RINGUETTE S, DUBOIS C, STOWE R A, et al. Synthesisand characterization of deuterated Glycidyl azide polymer(GAP)[J]. Propellants, Explosives, Pyrotechnics, 2006, 31(2): 131-138. doi: 10.1002/(ISSN)1521-4087 URL