工业级卡托辛成分分析及其双核二茂铁制备工艺

doi:10.3969/j.issn.1000-1093.2021.05.008

摘要/Abstract

摘要： 2,2-双(乙基二茂铁)丙烷（卡托辛）因其优异的催化活性和制药工艺性，成为当前复合固体推进剂中主要的燃速催化剂之一。由于卡托辛合成工艺复杂，工业级产品成分也很复杂，使得其相关产品的性能难以得到保证。利用气相色谱-质谱联用技术和高效液相色谱技术，对工业级卡托辛的成分进行了分析；依据各成分结构特性及其极性、溶解度差异，通过柱层析法、溶解-析出法对其进行了分离提纯，得到了含量高且分子结构中含有两个二茂铁单元结构的双核二茂铁。结果发现：工业级卡托辛成分中双核二茂铁的总含量为84.82 %，单核二茂铁的总含量为15.18 %。柱层析法可得到含量大于99.0%的双核二茂铁；溶解-析出法可得到含量大于96.5%的双核二茂铁，且该法具有可宏量制备、操作工艺简便、成本低等特点。

关键词: 双核二茂铁, 卡托辛, 乙基二茂铁, 分离提纯, 柱层析

Abstract: 2,2-bis (ethylferrocenyl) propane (catocene) has become one of the main burning rate catalysts in composite solid propellant because of its excellent catalytic activity and pharmaceutical technology. The composition of industrial grade products is also very complicated due to the complex synthesis process of catocene, which makes the performance of related products difficult to be guaranteed. The composition of industrial grade catocene is analyzed by using gas chromatography-mass spectrometry and high performance liquid chromatography. According to the structural characteristics of the components and the differences in their polarities and solubilities, the components of catocene were separated and purified by using column chromatography and dissolution-precipitation method, and the binuclear ferrocene containing two ferrocene units in the molecular structure with high content was obtained. It is found that the total contents of binuclear ferrocene and mononuclear ferrocene in the industrial grade catocene are 84.82% and 15.18%, respectively. The results show that column chromatography can be used to obtain binuclear ferrocene with a content greater than 99.0%; the dissolution-precipitation method can be used to obtain binuclear ferrocene with a content greater than 96.5%, and the proposed method has the characteristics of large-scale preparation, simple operation and low cost, etc.

Key words: binuclearferrocene, catocene, ethylferrocene, separationandpurification, columnchromatography

中图分类号:

V512⁺.3

冯海涛，索齐，张驰，刘晓菊，马晓燕. 工业级卡托辛成分分析及其双核二茂铁制备工艺[J]. 兵工学报, 2021, 42(5): 961-967.

FENG Haitao， SUO Qi， ZHANG Chi， LIU Xiaoju， MA Xiaoyan. Component Analysis of Industrial Grade Catocene and Preparation of Binuclear Ferrocene[J]. Acta Armamentarii, 2021, 42(5): 961-967.

参考文献

［1］ ZHOU W D, WANG L, YU H J, et al. Progress on the synthesis and catalytic and anti-migration properties of ferrocene-based burning rate catalysts [J]. Applied Organometallic Chemistry, 2016, 30(9): 796-805.
[2］ NATALI M, RAVAGLIA M, SCANDOLA F, et al. Long-range charge separation in a ferrocene-(zinc porphyrin)-naphthalenediimide triad. asymmetric role of 1,2,3-triazole linkers [J]. Journal of Physical Chemistry C, 2013, 117(38): 19334-19345.
[3］ GU X S, XIE S B, CHEN Q, et al. Anti-migration and burning rate catalytic performances of novel ferrocene-based porphyrins and their transition-metal complexes [J]. New Journal of Chemistry, 2018, 42(16): 13319-13328.
[4］黎桂辉, 刘学军, 程红彬. 二茂铁及其衍生物的合成与应用研究进展 [J]. 化学研究, 2010, 21(4): 108-112.
LI G H，LIU X J，CHENG H B.Progress in synthesis and application of ferrocene and its derivatives[J].Chemical Research, 2010, 21(4): 108-112.（in Chinese）
[5］ LI Q H, CHEN X, JING B, et al. Redox switched transition of vesicles self-assembled from AOT and ferrocene derivative molecules [J]. Colloid Surface A, 2010, 355(1/2/3): 146-150.
[6］ LI J Z, JIANG L P, JIA D, et al. Ferrocenyl ionic compounds containing [Fe(CN)6]3-anions: synthesis, characterization, and catalytic effects during combustion [J]. Zeitschrift Für Anorganische Und Allgemeine Chemie, 2019, 645(1): 14-21.
[7］ ZHOU W D, WANG L, YU H J, et al. Progress on the synthesis and catalytic and anti-migration properties of ferrocene-based burning rate catalysts [J]. Applied Organometallic Chemistry, 2016, 30(9): 796-805.
[8］ LIU M M, SHAO E S, ZHAO K, et al. Dinuclear (ferrocenyl- methyl)imidazolium ionic compounds with polycyano anions. characterization, migration, and effects during combustion [J]. Zeitschrift für Anorganische und Allgemeine Chemie, 2017, 643(13): 802-810.
[9］ USMAN M, WANG L, YU H J, et al. Recent progress on ferrocene-based burning rate catalysts for propellant applications [J]. Journal of Organometallic Chemistry, 2018, 872:40-53.
[10］ ZAIN U A, WANG L, YU H J, et al. Ferrocene-based polyethyleneimines for burning rate catalysts [J]. New Journal of Che-mistry, 2016, 40(4): 3155-3163.
[11］ ZHOU W D, WANG L, YU H J, et al. Synthesis of a novel ferrocene-based epoxy compound and its burning rate catalytic pro-perty [J]. RSC Advances, 2016, 6(59): 53679-53687.
[12］唐孝明.双核二茂铁衍生物合成及燃速催化研究进展[J].武汉工程大学学报,2012,34(1):19-25.
TANG X M.Progress in synthesis and burning rate catalysis of binuclear ferrocene derivatives [J]. Journal of Wuhan University of Engineering, 2012,34(1): 19-25.（in Chinese）
[13］张晓勤，夏宇，贾利亚，等. 二茂铁类燃烧性能调节剂研究进展[J].化学推进剂与高分子材料,2012,10(3):58-64.
ZHANG X Q，XIA Y，JIA L Y,et al.Research progress of ferrocene based combustion performance regulators [J]. Chemical Propellants and Polymer Materials, 2012,10(3): 58-64.（in Chinese）
[14］ TONG R B, ZHAO Y L, WANG L, et al. Recent research progress in the synthesis and properties of burning rate catalysts based on ferrocene-containing polymers and derivatives [J]. Journal of Organometallic Chemistry, 2013, 755:16-32.
[15］田丹, 刘强, 陈芳，等. 正辛基二茂铁标准物质的制备及定值 [J]. 应用化学, 2018, 35(7): 849-856.
TIAN D，LIU Q，CHENG F,et al. Preparation and value determination of n-octylferrocene standard materials [J]. Chinese Journal of Applied Chemistry, 2018, 35(7): 849-856.（in Chinese）
[16］田丹, 李永江, 张敏, 等. 辛基二茂铁同分异构体标准物质的制备 [J]. 化学分析计量, 2019, 28(4): 1-6.
TIAN D，LI Y J，ZHANG M,et al.Preparation of octylferrocene isomers certified reference materials [J]. Chemical Analysis and Meterage, 2019, 28(4): 1-6. （in Chinese）

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