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Study on Synthesis, Characterization and Application of Ferrocene-Based Compounds and Ferrocene-Based Polymers and Their Grafted Carbon Materials

Author: GaoJingMin
Tutor: WangLi
School: Zhejiang University
Course: Polymer Chemistry and Physics
Keywords: Ferrocene burning-rate promoter solid propellant anti-migration ATRP graft
CLC: O627.81
Type: PhD thesis
Year: 2012
Downloads: 119
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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.

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