【作者】 高敬民；

【导师】 王立；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2012， 博士

【摘要】 二茂铁基化合物和二茂铁基聚合物以及它们接枝的碳材料由于具有独特的结构和优异的性能使得它们在高氯酸铵基推进剂中有着广泛的应用。本论文围绕二茂铁基化合物和二茂铁基聚合物以及它们接枝碳材料的合成、表征和应用展开研究：(1)制备了六种二茂铁基化合物1,1’-二茂铁二甲酸羟乙酯(FDCHE)、1,3-二-(二茂铁酰氧基)-2-丙醇(DFAPO)、1,2,3-三-(二茂铁酰氧基)-丙三(醇)酯(TFAGOE)、1,2,3,4-四-(二茂铁酰氧基)-季戊四(醇)酯(TFAPOE)、1,1’-二茂铁甲酰氧基环氧丙烷(GEFDC)和聚二茂铁二甲酸双酚A酯缩水甘油醚(GEPFDCBPE),用核磁共振(1H-NMR)和红外光谱(FT-IR)表征了所得产物的结构。用TGA法研究了这些新型二茂铁基化合物对高氯酸铵(AP)热分解性能的影响规律。研究发现,这些二茂铁基化合物的加入都对AP的热分解产生较大的影响。加入二茂铁基化合物的量越大,对AP热分解的促进效果越好；支化程度提高,抗迁移效果改善。将制备的模拟推进剂样品置于真空干燥箱中(50℃)50天未发现有明显的二茂铁基化合物迁移现象发生。提出了二茂铁基化合物迁移的可能机理,同时也提出了相应的抗迁移方法。(2)合成了两种二茂铁基化合物单体丙烯酸二茂铁甲酰氧基乙酯(AFFEE)和甲基丙烯酸二茂铁甲酰氧基乙酯(MAFFEE),采用溶液聚合法分别制备了聚丙烯酸二茂铁甲酰氧基乙酯(PAFFEE)和聚甲基丙烯酸二茂铁甲酰氧基乙酯(PMAFFEE)。用FT-IR、1H-NMR等方法对产物结构进行了表征与分析。以TGA法研究了PAFFEE、PMAFFEE.聚二茂铁二甲基硅烷(PFDMS)和聚二茂铁甲基苯基硅烷(PFMBS)对AP的热分解性能的影响。发现它们均可使AP的分解温度明显降低；聚合物的分子量对AP的热分解性能影响不明显；二茂铁基聚合物用量增加使得AP的高温分解温度降低,当用量增加到一定程度之后,进一步增加其用量对AP的热分解性能影响不明显。将制备的模拟推进剂样品置于真空干燥箱中(50℃)50天,未发现明显的二茂铁基聚合物迁移现象。提出了二茂铁基聚合物促进AP热分解的可能机理。(3)制备了表面羧酸化炭黑(CBs-COOH)和表面羟基化炭黑(CBs-OH);使CBs-OH跟二茂铁单甲酰氯反应,将二茂铁基团接枝到炭黑表面(CBs-g-Fc)。采用FT-IR、1H-NMR等方法表征了产物；用TEM观察了其形貌；通过TGA法对系列产物进行了热失重分析,发现CBs-COOH和CBs-OH的失重明显较纯炭黑增加；以CBs-OH与2-甲基-2-溴丙酰溴反应合成了CBs-Br,然后以CBs-Br为引发剂,以AFFEE为单体制备了聚丙烯酸二茂铁甲酰氧基乙酯接枝炭黑(CBs-g-PAFFEE);采用FT-IR、1H-NMR、TGA法等方法表征与分析了相关产物。用TGA法研究了CBs-g-Fc和CBs-g-PAFFEE对AP的热分解性能的影响。发现CBs用量的增加可使AP的分解温度下降。但进一步增加炭黑的用量,对AP热分解的影响不明显。CBs-g-Fc和CBs-g-PAFFEE的加入都可明显降低AP的分解温度。将制备的含二茂铁基聚合物接枝炭黑的模拟推进剂样品置于真空干燥箱中(50℃)50天,未发现二茂铁基聚合物接枝炭黑有明显迁移现象发生。提出了二茂铁接枝炭黑化合物促进AP热分解的可能机理。CBs-g-Fc和CBs-g-PAFFEE性能优异,有望作为新型燃速促进剂被实际应用。(4)制备了表面羧酸化碳管(MWCNTs-COOH)和表面羟基化碳管(MWC-NTs-OH);将MWCNTs-OH与二茂铁单甲酰氯反应制得二茂铁接枝碳管(MWCN-Ts-g-Fc).将MWCNTs-OH-1与2-甲基-2-溴丙酰溴反应合成了MWCNTs-Br-1,然后以其为引发剂,以AFFEE为单体制备了聚丙烯酸二茂铁甲酰氧基乙酯接枝碳管(MWCNTs-g-PAFFEE),采用FT-IR和TGA法等对产物进行了表征和分析,用TEM观察了其形貌,发现MWCNTs-g-PAFFEE已成功合成。用TGA法研究了MWCNTs、MWCNTs-g-Fc及MWCNTs-g-PAFFEE等对AP的热分解性能的影响,发现MWCNTs、MWCNTs-g-Fc及MWCNTs-g-PAFFEE的加入均可使AP的分解温度下降。将制备的模拟推进剂样品置于真空干燥箱中(50℃)50天,未发现MWCNTs-g-Fc及MWCNTs-g-PAFFEE有明显迁移现象。提出了二茂铁基聚合物接枝碳纳米管促进AP热分解的可能机理。更多还原

【Abstract】 Ferrocene-based compounds, ferrocene-based polymers and their grafted carbon materials can be widely used in ammonium perchlorate (AP)-based propellants due to their unique structure and excellent performance. The synthesis, characterization and application of some ferrocene-based compounds, ferrocene-based polymers and their grafted carbon materials were studied in this thesis.(1) Six different ferrocene-based compounds including ferrocene dicarboxylate hydroxyethyl (FDCHE),1,3-di(ferrocene acyloxy)-2-propanol (DFAPO),1,2,3-triferro-cene acyloxy glycerol ester (TFAGOE),1,2,3,4-tetraferrocene acyloxy pentaerythritol ester (TFAPOE), glycidyl ester of1,1’-ferrocene dicarboxylate (GEFDC) and glycidyl ether of polyferrocene dicarboxylate bisphenol A ester (GEPFDCBPE) were prepared and their structures were characterized by FT-IR and1H-NMR spectroscopy. The influence of these ferrocene-based compounds on the decomposition of AP was studied by TGA method. It was found that the addition of the synthesized ferrocene-based compounds decreased the decomposition temperature of AP. These ferrocene-based compounds had good promotive effect on the decomposition of AP. The results showed that the promotive effects were improved with increasing the content of ferrocene-base compounds. A good anti-migration effect was achieved when the branching degrees of the ferrocene-based compounds were increased. Furthermore, no obviously migration phenomenon of the synthesized ferrocene-based compounds was found after aging at50℃under vacuum. The possible migration mechanism and the corresponding antimigration measures of ferrocene-based compounds were proposed.(2) Methacrylate ferrocenyl formyloxy ethyl ester (MAFFEE) and acrylate ferrocenyl formyloxy ethyl ester (AFFEE) were prepared and then poly(meth)acrylate ferrocenyl formyloxy ethyl esters (P(M)AFFEE) were prepared by solution polymerization. Their structures were characterized by FT-IR and1H-NMR spectroscopy. PMAFFEE, PAFFEE, poly(ferrocenyldimethylsilanes)(PFDMS) and poly(ferrocenylphenylmethylsilanes)(PFMBS) were used as promoters and their promotive effects on the thermal decomposition of AP were studied by TGA method. It was found that all of these ferrocene-based polymers could decrease the decomposition temperature of AP, and the molecular weight of ferrocene-based polymers had no obvious influence on the decomposition of AP. As the amount of the same molecular weight ferrocene-based polymers increased, the decomposition temperature peak of AP decreased. When the amount reached a certain level, the decomposition temperature of AP did not decreased any more. Moreover, no obviously migration phenomenon of the synthesized ferrocene-based polymers was found by accelerated aging at50℃under vacuum after50d storing process. The possible promotive mechanism of ferrocene-based polymer on the thermal decomposition of AP was proposed.(3) CBs-COOH and CBs-OH were synthesized. CBs-g-Fc were synthesized by using ferrocenyl carboxylic chloride and CBs-OH. The relevant products were characterized by using FT-IR and1H-NMR spetroscopy. Their morphologies were investigated using TEM and HRTEM. The thermal properties of CBs-COOH and CBs-OH were investigated by TGA method. The results showed that the weight loss of CBs-COOH and CBs-OH increased significantly as compared to pure CBs. CBs-Br were synthesized via the reaction of CBs-OH with2-bromo-2-methyl-propionyl bromide. Polyacrylate ferrocenyl formyloxy ethyl ester grafted CBs were prepared by using CBs-Br as an initiator and acrylate ferrocenyl formyloxy ethyl ester as a monomer. The relevant products were characterized and analyzed by using FT-IR,1H-NMR spetroscopy and TGA techniques. The influence of CBs, CBs-g-Fc and CBs-g-PAFFEE on the thermal decomposition of AP was investigated by TGA methods. With increasing the amount of CBs, the decomposition temperature of AP decreased. Further increasing the amount of CBs had no obviously affect on the decomposition process of AP. Both of CBs-g-Fc and CBs-g-PAFFEE decreased the decomposition temperature of AP. Moreover, no obviously migration phenomenon of the synthesized ferrocene-based polymers grafted CBs was found when the simulated propellant was stored at50℃under vacuum after50d storing process. The possible promotive mechanisms of CBs-g-Fc and CBs-g-PAFFEE on the thermal decomposition of AP was proposed. CBs-g-Fc and CBs-g-PAFFEE materials have very good properties and they have very good potential application prospect as a new kind of burning rate promoter.(4) MWCNTs-COOH and MWCNTs-OH were synthesized. MWCNTs-g-Fc were prepared by using ferrocene carboxylic chloride and MWCNTs-OH. MWCNTs-Br were synthesized via the reaction of MWCNTs-OH with2-bromo-2-methyl-propionyl bromide. Polyacrylate ferrocenyl formyloxy ethyl ester grafted MWCNTs were prepared by using MWCNTs-Br as an initiator and acrylate ferrocenyl formyloxy ethyl ester as a monomer. The relevant products were characterized and analyzed by using FT-IR and TGA techniques. Their morphologies were investigated by using TEM. The results showed that MWCNTs-g-Fc and MWCNTs-g-PAFFEE were successfully obtained. The influence of MWCNTs, MWCNTs-g-Fc and MWCNTs-g-PAFFEE on the thermal decomposition of AP was studied by TGA method. It was found that the thermal decomposition temperature of AP decreased with the addition of MWCNTs, MWCNTs-g-Fc and MWCNTs-g-PAFFEE. However, no obviously migration phenomenon of the synthesized MWCNTs-g-Fc and MWCNTs-g-PAFFEE was found when the imitated propellant stored at50℃under vacuum after50d storing process. The possible promotive mechanisms of MWCNTs-g-Fc and MWCNTs-g-PAFFEE on the thermal decomposition of AP were proposed.更多还原