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[1]王晓川,舒远杰,卢先明,等.2,4,6-三甲基间苯二腈氧化物的合成及固化性能分析[J].火炸药学报,2018,41(2):143-146,152.[doi:10.14077/j.issn.1007-7812.2018.02.007]
 WANG Xiao-chuan,SHU Yuan-jie,LU Xian-ming,et al.Synthesis of 2,4,6-Trimethylisophthtalodinitrile Oxide and Analysis on Its Curing Properties[J].,2018,41(2):143-146,152.[doi:10.14077/j.issn.1007-7812.2018.02.007]
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2,4,6-三甲基间苯二腈氧化物的合成及固化性能分析()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
41卷
期数:
2018年第2期
页码:
143-146,152
栏目:
出版日期:
2018-04-27

文章信息/Info

Title:
Synthesis of 2,4,6-Trimethylisophthtalodinitrile Oxide and Analysis on Its Curing Properties
作者:
王晓川 舒远杰 卢先明 刘宁 莫洪昌 徐明辉
西安近代化学研究所, 陕西 西安 710065
Author(s):
WANG Xiao-chuan SHU Yuan-jie LU Xian-ming LIU Ning MO Hong-chang XU Ming-hui
Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
关键词:
246-三甲基间苯二腈氧化物13-偶极环加成反应固化剂聚丁二烯固化性能
Keywords:
246-trimethylisophthtalodinitrile oxideoxidationcuring agentpolybutadienecuring property
分类号:
TJ55;O62
DOI:
10.14077/j.issn.1007-7812.2018.02.007
文献标志码:
-
摘要:
以均三甲苯为原料,经溴甲基化反应、氧化反应、缩合反应、脱氢氧化反应合成了含能固化剂2,4,6-三甲基间苯二腈氧化物,总收率42%;利用红外光谱、1H NMR、13C NMR及元素分析等方法对目标化合物和中间体的结构进行了表征;利用DSC分析了2,4,6-三甲基间苯二腈氧化物的热分解性能;探讨了溴甲基化和氧化反应的机理,确定了合成2,4,6-三甲基间苯二腈氧化物的最佳工艺条件。结果表明,当氧化反应时间为3 d,缩合反应的催化剂为NaOH,脱氢氧化反应NaClO摩尔量为43 mmol时,合成的2,4,6-三甲基间苯二腈氧化物产率最高,为73%;2,4,6-三甲基间苯二腈氧化物的腈氧基团相对比较稳定,100℃才开始分解,在室温下即可固化液体聚丁二烯橡胶。
Abstract:
An energetic curing agent 2,4,6-trimethylisophthtalodinitrile oxide was synthesized using mesitylene as raw material by bromomethylation, oxidation, condensation and dehydrogenation oxidation etc.reactions with a total yield of 42%. The structures of target compound and intermediates were characterized by IR, 1H NMR, 13C NMR and elemental analyses etc. methods and the thermal decomposition property of 2,4,6-trimethylisophthtalodinitrile oxide was analyzed by DSC. The synthetic mechanism for bromomethylation and oxidation was discussed and the optimum synthesis technology conditions of 2,4,6-trimethylisophthtalodinitrile oxide were determined. The results show that when the oxidation reaction time is 3 days, molar amount of NaClO of the dehydrogenation oxidation is 43 mmol, the highest yield of synthesizing 2,4,6-trimethylisophthtalodinitrile oxide is 73%. The nitrile oxide group of 2,4,6-trimethylisophthtalodinitrile oxide is relatively stable, which is decomposed under 100℃. 2,4,6-Trimethylisophthtalodinitrile oxide can cure liquid polybutadiene rubber at room temperature.

参考文献/References:

[1] 王晓川,舒远杰,卢先明,等. 1,3-偶极环加成反应在固化含能黏合剂中的应用[J]. 化学推进剂与高分子材料,2017, 15(4):32-37. WANG Xiao-chuan, SHU Yuan-jie, LU Xian-ming, et al. Application of 1,3-dipolar cycloaddiyion reaction in curing energetic binders[J]. Chemical Propellants and Polymeric Materials, 2017, 15(4):32-37.
[2] Kumar K A, Govindaraju M, Jayaroopa P, et al. Nitrile oxides:a key intermediate in organic synthesis[J]. International Journal of Pharmaceutical Chemical and Biological Sciences, 2012, 3(1):91-101.
[3] Beck W, Evers J, Göbel M, et al. The crystal and molecular structure of mercury fulminate (knallquecksilber)[J]. Zeitschrift Für Anorganische Und Allgemeine Chemie, 2007, 633(9):1417-1422.
[4] 李亚南, 舒远杰, 张志忠. 氧化氰二聚成环:对称氧化呋咱衍生物制备的重要途径[J]. 含能材料, 2009, 17(6):740-744. LI Ya-nan, SHU Yuan-jie, ZHANG Zhi-zhong. Dimerization reaction of cyanide oxide:important route for synthesis of furoxan derivatives[J]. Chinese Journal of Energetic Materials, 2009, 17(6):740-744.
[5] Grundmann C, Dean J M.Nitrile oxides.V.stable aromatic nitrile oxides[J]. Journal of Organic Chemistry, 1965, 30(8):2809-2812.
[6] 吴敏杰,李祥志,毕福强,等. 4,5-二氧代氰基咪唑盐酸盐的合成与表征[J]. 火炸药学报, 2017, 40(3):41-46. WU Min-jie, LI Xiang-zhi, BI Fu-qiang, et al. Synthesis and characterization of 1H-imidazolium-4,5-dinitrile dioxides hydrochloride[J]. Chinese Journal of Explosives & Propellants (Huozhayao Xuebao), 2017, 40(3):41-46.
[7] 薛云娜,杨建明,李春迎,等. 3,4-二苯基氧化呋咱的高效合成[J]. 火炸药学报, 2010, 33(1):34-37. XUE Yun-na, YANG Jian-ming, LI Chun-ying, et al. Synthesis of 3,4-diphenylfuroxan with high efficiency[J]. Chinese Journal of Explosives & Propellants(Huozhayao Xuebao), 2010, 33(1):34-37.
[8] Singh I, Zarafshani Z, Lutz J-F, et al. Metal-free "click"chemistry:efficient polymer modification via 1,3-dipolar cycloaddition of nitrile oxides and alkynes[J]. Macromolecules, 2009, 42(15):5411-5413.
[9] Grundmann C, Dean J. Stable aromatic nitrile oxides[J]. Angewandte Chemie International Edition, 1964, 3(8):585-586.
[10] Tsyganov D V, Yakubov A P, Belenkii L I, et al. Synthesis and properties of stable aromatic bis(nitrile oxides)[J]. Russian Chemical Bulletin, 1991, 40(6):1238-1243.
[11] Huffman B S, Schultz R A, Schlom P J. Novel reagents for heat -activated polymer crosslinking[J]. Polymer Bulletin, 2001, 47:159-160.
[12] 樊亚勤,向尧,雷永林,等. 对苯二腈氧化物的合成及其室温固化性能[J]. 精细化工,2017, 34(9):1063-1069. FAN Ya-qin, XIANG Yao, LEI Yong-lin, et al. Synthesis of terephthalonnitrile oxide and its curing properties at room temperature[J]. Fine Chemicals, 2017, 34(9):1063-1069.
[13] 吴兴宇,崔庆忠,徐军. HTPB/TDI粘结体系的固化反应动力学[J]. 含能材料, 2016, 24(11):1097-1101. WU Xing-yu, CUI Qing-jun, XU Jun. Curing reaction kinetics of HTPB/TDI bonding system[J]. Chinese Journal of Energetic Materials, 2016, 24(11):1097-1101.
[14] Thomas K, Werner K, Siegfried E, et al. Isocyanate-free curing of glycidyl azide polymer (GAP) with bis-propargyl-succinate(Ⅱ)[J]. Propellants, Explosives, Pyrotechnics, 2009, 34:210-217.

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备注/Memo

备注/Memo:
收稿日期:2017-09-11;改回日期:2017-10-22。
基金项目:国家自然科学基金(No.51373159);广州市科技计划项目(No.2016201604030043)
作者简介:王晓川(1985-),男,博士研究生,从事功能材料的合成及应用研究。E-mail:365200401@163.com
通讯作者:舒远杰(1969-),男,研究员,从事含能材料理论设计与实验研究。E-mail:Syj1204172675@163.com
更新日期/Last Update: 1900-01-01