端羟基聚丁二烯(HTPB)接枝含硅双核二茂铁衍生物的合成及其应用性能研究

doi:10.6023/A25040108

化学学报 ›› 2025, Vol. 83 ›› Issue (9): 1018-1024.DOI: 10.6023/A25040108 上一篇下一篇

研究论文

端羟基聚丁二烯(HTPB)接枝含硅双核二茂铁衍生物的合成及其应用性能研究

喻尧^a^,^b^,^†, 李晓强^a^,^†, 刘佳鑫^a, 顾军^a^,^c, 涂涛^c^,^*(), 杨军^a^,^*()

^a 中国科学院上海有机化学研究所先进氟氮材料全国重点实验室中国科学院大学上海 200032
^b 湖北航天江河化工有限公司宜昌 444200
^c 复旦大学化学系上海市分子催化和功能材料重点实验室上海 200438

投稿日期:2025-04-03 发布日期:2025-06-03
作者简介:
† 共同第一作者
基金资助:
中国科学院稳定支持青年团队计划(YSBR-052); 中国科学院战略先导计划(XDB0590200); 国家自然科学基金青年项目(C类)(22305261)

Synthesis and Application of Silicon-containing Biferrocene Derivatives Grafted Hydroxyl-terminated Polybutadiene (HTPB)

Yao Yu^a^,^b,†, Xiaoqiang Li^a,†, Jiaxin Liu^a, Jun Gu^a^,^c, Tao Tu^c^,^*(), Jun Yang^a^,^*()

^a State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China
^b Hubei Aerospace Jianghe Chemical Co., Ltd, Yichang 444200, China
^c Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200438, China

Received:2025-04-03 Published:2025-06-03
Contact: * E-mail: taotu@fudan.edu.cn,yangj@sioc.ac.cn
About author:
† These authors contributed equally to this work
Supported by:
CAS Project for Young Scientists in Basic Research(YSBR-052); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590200); National Natural Science Foundation of China(22305261)

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摘要/Abstract

针对二茂铁类燃速催化剂在推进剂中易挥发和易迁移、含有二茂铁的高分子聚合物铁含量偏低催化效果不佳等问题, 本工作开展了端羟基聚丁二烯(HTPB)接枝含硅双核二茂铁衍生物的合成和应用研究. 首先合成系列含有硅烷的双核二茂铁衍生物, 然后通过硅氢化反应将其接枝在HTPB聚合物上, 获得了三种不同的HTPB接枝含硅双核二茂铁的燃速催化剂, 其铁含量(质量分数)分别为10.7%、11.9%和14.1%, 高于Butacene的铁含量(8%). 同时, 对其热稳定性和催化分解高氯酸铵(AP)的性能进行了测试, 结果表明其热分解温度及其催化AP分解的温度均有所降低, 具有较好的催化分解AP的效果, 未来在HTPB固体推进剂配方中具有应用潜力.

关键词: 双核二茂铁, 端羟基聚丁二烯, 硅氢化反应, 固体推进剂, 燃速催化剂

This work focuses on the synthesis and application research of silicon-containing biferrocene derivatives grafted onto hydroxyl-terminated polybutadiene (HTPB), to address the issues of volatility and migration tendency of ferrocene combustion catalysts in solid rocket propellants, as well as the insufficient catalytic performance caused by low iron content in ferrocene-containing polymeric materials. Firstly, a template reaction was employed to optimize the hydrosilylation reaction conditions. In this part, 4-vinyl-1-cyclohexene was employed as substrate, and the ratio of substrate, solvent, reaction time, reaction temperature was optimized. Based on the optimized condition, ferrocene silane derivatives and HTPB were utilized as substrates to obtain HTPB grafted silicon-containing biferrocene compounds. Subsequently, the relationship of biferrocene silane loading and the iron contents as well as the grafting rate were investigated. As the result, three different HTPB grafted silicon-containing biferrocene combustion catalysts were obtained by grafting biferrocene silane derivatives on HTPB polymers through hydrosilylation reactions. The iron contents of above combustion catalysts were 10.7%, 11.9% and 14.1% respectively, which were higher than that of Butacene (8%). At the same time, its thermal stability and catalytic decomposition performance of ammonium perchlorate (AP) were tested. The combustion catalysts were mixed with ultrafine AP at a mass ratio of 5∶95, then carefully ground it to uniformity. The solvent was evaporated during the grinding process. After grinding, a mixture of combustion catalyst and AP was obtained, and then differential scanning calorimetry (DSC) and thermogravimetric (TG) study were employed. The results demonstrated that the decomposition temperature of AP under catalytic conditions were reduced. The initial and final decomposition temperatures of AP were reduced after adding 5% biferrocene-containing HTPB, with the final decomposition temperature reduced by about 57~77 ℃, and the high decomposition temperature reduced by 87.4~103.7 ℃, which could catalyze the decomposition of AP efficiently. These above combustion catalysts might be utilized in HTPB solid rocket propellant in the future.

Key words: biferrocene, hydroxyl-terminated polybutadiene (HTPB), hydrosilylation reaction, solid rocket propellant, combustion catalyst

引用此文

喻尧, 李晓强, 刘佳鑫, 顾军, 涂涛, 杨军. 端羟基聚丁二烯(HTPB)接枝含硅双核二茂铁衍生物的合成及其应用性能研究[J]. 化学学报, 2025, 83(9): 1018-1024.

Yao Yu, Xiaoqiang Li, Jiaxin Liu, Jun Gu, Tao Tu, Jun Yang. Synthesis and Application of Silicon-containing Biferrocene Derivatives Grafted Hydroxyl-terminated Polybutadiene (HTPB)[J]. Acta Chimica Sinica, 2025, 83(9): 1018-1024.

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图/表 12

图1. 系列二茂铁燃速催化剂

Figure 1. Ferrocene-based combustion catalysts

Entry^a	催化剂用量	溶剂	反应时间/h	反应温度/℃	收率/%
1	5 μL	甲苯	16	60	22.9
2	50 μL	甲苯	16	60	75.5
3	100 μL	甲苯	16	60	82.4
4	200 μL	甲苯	16	60	73.4
5	100 μL	THF	16	60	78.1
6	100 μL	DCM	16	60	70.6
7	100 μL	甲苯	4	60	81.5
8	100 μL	甲苯	8	60	86.3
9	100 μL	甲苯	24	60	75.8
10	100 μL	甲苯	8	40	82.9
11	100 μL	甲苯	8	80	78.8
12	100 μL	甲苯	8	100	77.4

表1. 烯烃与二茂铁硅烷加成模板反应条件优化

Table 1. Optimization of reaction conditions for ferrocene silane and olefin

Entry^a	产物编号	二茂铁硅烷与HTPB物质的量比	收率/%	接枝率^b/%	铁含量^c/%
1	4a	5∶1	83	13.6	4.2
2	4b	10∶1	97	29.2	8.3
3	4c	15∶1	94	41.6	9.0
4	4d	20∶1	>99	58.3	10.2
5	4e	25∶1	>99	66.7	11.1
6	4f	30∶1	>99	79.2	12.9

表2. 双核二茂铁硅烷与HTPB的硅氢化反应

Table 2. Hydrosilylation reaction of biferrocene silane and HTPB

图2. 系列二茂铁硅烷衍生物

Figure 2. Ferrocene silane derivatives

Entry^a	产物编号	二茂铁硅烷与HTPB物质的量比	收率/%	接枝率^b/%	铁含量^c/%
1	5a	5∶1	93	12.5	3.1
2	5b	10∶1	90	25.0	7.0
3	5c	15∶1	88	33.3	8.7
4	5d	20∶1	79	50.0	11.2
5	5e	30∶1	61	50.0	11.9
6	5f	40∶1	48	45.8	10.4

表3. 双核二茂铁硅烷2b与HTPB的硅氢化反应

Table 3. Hydrosilylation reaction of biferrocene silane 2b and HTPB

Entry^a	产物编号	二茂铁硅烷与HTPB物质的量比	收率/%	接枝率^b/%	铁含量^c/%
1	6a	10∶1	79	25.0	8.8
2	6b	20∶1	55	33.3	9.4
3	6c	30∶1	52	45.8	10.7
4	6d	40∶1	51	41.7	10.6

表4. 双核二茂铁硅烷2c与HTPB的硅氢化反应

Table 4. Hydrosilylation reaction of biferrocene silane 2c and HTPB

Entry^a	产物编号	二茂铁硅烷与HTPB物质的量比	收率/%	接枝率^b/%	铁含量^c/%
1	7a	10∶1	97	20.8	8.3
2	7b	20∶1	80	33.3	11.2
3	7c	30∶1	75	45.8	11.9
4	7d	40∶1	72	58.3	14.1

表5. 双核二茂铁硅烷2d与HTPB的硅氢化反应

Table 5. Hydrosilation reaction of biferrocene silane 2d and HTPB

图3. HTPB接枝二茂铁硅烷与AP的混合物

Figure 3. Mixture of Fc-HTPB and AP

图4. Fc-HTPB与AP二元混合物(质量比5∶95)的TG曲线

Figure 4. TG curves of the mixture of Fc-HTPB and AP (mass ratio of 5∶95) Note: I: AP; II: mixture of 5e and AP; III: mixture of 6c and AP; IV: mixture of 7d and AP; V: mixture of 4f and AP

图5. Fc-HTPB与AP二元混合物(质量比5∶95)的DTG曲线

Figure 5. DTG curves of the mixture of Fc-HTPB and AP (mass ratio of 5∶95) Note: I: AP; II: mixture of 5e and AP; III: mixture of 6c and AP; IV: mixture of 7d and AP; V: mixture of 4f and AP

图6. Fc-HTPB与AP二元混合物(质量比5∶95)的DSC曲线

Figure 6. DSC curves of the mixture of Fc-HTPB and AP (mass ratio of 5∶95) Note: I: AP; II: mixture of 5e and AP; III: mixture of 6c and AP; IV: mixture of 7d and AP; V: mixture of 4f and AP

图7. Fc-HTPB和HTPB的TG曲线

Figure 7. TG curves of Fc-HTPB and HTPB

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端羟基聚丁二烯(HTPB)接枝含硅双核二茂铁衍生物的合成及其应用性能研究

Synthesis and Application of Silicon-containing Biferrocene Derivatives Grafted Hydroxyl-terminated Polybutadiene (HTPB)

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