| Ferrocene-based hyperbranched polymers and coordination polymers have topological structures. Hyperbranched polymers possess cavities and their structure contains large number of functional groups. Coordination polymers have high surface area and their morphology can be controlled. Hyperbranched and coordination polymers are wildly used in catalysis, hydrogen adsorption and magnetic materials.In this thesis, we focused on the preparation and characterization of ferrocene-based hyperbranched polyehter and coordination polymers. Furthermore, their catalytic, hydrogen storage and magnetic performance were investigated.The hyperbranched polyether (HBPE) was synthesized via self-condensing ring-opening polymerization using boron trifluoride diethyl etherate as a catalyst. Three ferrocene-based hyperbranched polyether (HBPE-Fcs) with different substitution degree of ferrocene were synthesized by the condensation reaction of HBPE with ferrocenylformyl chloride.1H NMR, FTIR and UV-Vis were used to characterize the structures of monomer, HBPE and HBPE-Fc. The polymerization mechanism was proposed. Cyclic voltammetry (CV) was used to investigate electrochemical behavior. It was found that HBPE-Fcs showed good redox behavior. All polymers showed high thermal stability. The catalytic performance of the synthesized polymers on thermal decomposition of ammonium perchlorate (AP) was investigated by thermogravimetry (TG) and differential thermogravimetry (DTG) techniques. HBPE-Fcs exhibited good catalytic activity on thermal decomposition of AP and their catalytic activity was increased with the increase in their weight percentage. The anti-migration behavior of the synthesized polymer was investigated by preparing mimic propellant tubes. After 7 weeks of storage, HBPE-Fc showed less migration than ferrocene or catocene, which proved good anti-migration behavior of HBPE-Fc. UV-Vis spectroscopy was used to investigate total migration amount. Possible anti-migration mechanism of HBPE-Fc was proposed. HBPE-Fc has relatively larger molecule volume than linear polymers and all the hydroxyl groups of HBPE-Fc were not completely substituted with ferrocene, which might result in excellent anti-migration behavior of HBPE-Fc. Unreacted hydroxyl groups could react with cross-link agent isophorone diisocyanate. Therefore, anti-migration property was improved by immobilizing of polymers in cross-link network and making them hard to move.Six series of coordination polymers were synthesized through solvothermal method by using chlorine salts of six transition metals (Mn, Fe, Co, Ni, Cu and Zn) and 1,1’-ferrocene dicarboxylic acid. The morphology of the synthesized coordination polymers was investigated by SEM. We found that different salts resulted in different morphology of coordination polymers. Mn-CP were aggregated in the form of disc and some microspheres were also observed. Fe-CP and Cu-CP were spherical in shape covered by dense particles. Co-CP and Zn-CP were spherical aggregation of flack. However, Co-CP had smooth edge on flack, while Zn-CP had jagged edge. Ni-CP were also aggregated in the form of microspheres with small diameter. The particle size distribution of coordination polymers were confirmed by LPA. The coordination polymers were further characterized by FT-IR and XRD. TG results indicated that these ferrocene-based coordination polymers showed good thermal stability. Among all the synthesized coordination polymers, Co-CP were the most stable. Six coordination polymers were used as additives to investigate their catalytic performance on thermal decomposition of AP. It was found that these coordination polymers can significantly lower thermal decomposition temperature of AP. The catalytic activity of the six samples was in the following order:Co-CP> Mn-CP≈ Fe-CP≈Cu-CP> Ni-CP> Zn-CP. The outstanding catalytic performance of these coordination polymers was might be due to high content of ferrocene and transition metals. Both ferrocene and transition metals are good catalysts for lowering thermal decomposition temperature of AP. Mimic propellant tubes were prepared to investigate their anti-migration behavior. The anti-migration behavior was investigated by observing these tubes after every week. On 7 weeks of storage,6 tubes containing coordination polymers showed little migration.Ferrocene-based coordination polymers containing seven transition metals (Mn, Fe, Co, Ni, Cu, Zn and Cr) were synthesized by the reaction of metal salts with 1,1’-ferrocene dicarboxylic acid. It was found that uniform ferrocenyl coordination polymers containing Cr3+ salts cannot be obtained by this method. Coordination polymers with uniform morphology could be obtained by using MnCl2, FeCl3, Fe(NO3)3, CoCl2, Co(No3)2, NiCl2, NiSO4, CuCl2, (CH3COO)2Zn and ZnSO4. We further investigated the synthetic conditions of as-synthesized coordination polymers, including reaction time and temperature. The obtained products were characterized by SEM. EDS was used to analyze contents of elements. Their structures were confirmed by FT-IR and XRD. Their particle size distribution was investigated by LPA. TG results indicated that these ferrocene-based coordination polymers showed good thermal stability. The BET surface area, micropore size distribution, mesopore size distribution and total pore volume were investigated by N2 adsorption-desorption techniques. The surface area of Sample 4-02, Sample 4-16, Sample 4-33, Sample 4-49, Sample 4-62 and Sample 4-72 was 112.8,26.6,85.8,53.0,189.8 and 16.9 m2/g, respectively, which was calculated by BET method. All coordination polymers possess micropores with diameter of 0.9-1.0 nm and mesopores with diameter of 3.8 nm. Magnetic property was investigated on VSM. All the samples showed paramagnetic behavior. Coercive force Hc=0.014 T (140 Oe) and residual magnet Br= 0.551 emu/g were found in Sample 4-38. Excessive H2 uptake of Sample 4-02, Sample 4-16, Sample 4-33, Sample 4-49, Sample 4-62 and Sample 4-72 at 163K and under pressure range of 0-4.4 MPa was investigated. Their highest excessive H2 uptake was 1.309,1.374,1.326,0.610,1.094 and 0.218 wt% of the material mass, respectively.Three series of ferrocene-based dual-metal coordination polymers (CoMn, CoCu and MnCu) were synthesized by solvothermal method. The influence of synthetic conditions (including ratio of metals to 1.1’-ferrocene dicarboxylic acid, reaction time and temperature) on morphology was investigated by SEM. It was found that CoMn-CP and CoCu-CP were microspheres with flacks, MnCu-CP was fuzzy and hollow microspheres. All coordination polymers showed macro aggregates under high ratio of metals to 1,1’-ferrocene dicarboxylic acid. Their structures were confirmed by FT-IR and XRD. It was found that these coordination polymers showed some degree of crystallinity and similar crystal structures. Their particle size distribution was investigated by LPA. TG results indicated that these coordination polymers showed good thermal stability. BET surface area, mesopore size distribution and total pore volume were investigated by N2 adsorption-desorption techniques. The surface area of Sample 5-01, Sample 5-02, Sample 5-10, Sample 5-11, Sample 5-19 and Sample 5-20 was 174.8,120.0,181.3,226.9,105.7 and 190.2 m2/g, respectively. All coordination polymers possess mesopores with diameter of 3.8 nm. Magnetic property of 9 samples was investigated on VSM. Sample-5-02 of CoMn-CP showed strongest magnetic response. It might be due to the macro aggregates with worse-ordered structure and weak magnetic response of Sample 5-03, which depressed the saturation magnetization. The magnetic response of CoCu-CP and MnCu-CP was increased with the increase in ratio of metal salts/FcDA. It might be due to higher contents of metal in the products or better ordered atomic magnetic moment. H2 storage capacity of Sample 5-01, Sample 5-02, Sample 5-10, Sample 5-11, Sample 5-19 and Sample 5-20 at 163K and under pressure range of 0-4.4 MPa was investigated. Their highest excessive H2 uptake was -0.235,1.532,1.973,0.404,1.441 and 3.118 wt% of the material mass, respectively. The negative results were due to the low uptake and space occupation of material. SEM and TEM of samples after H2 adsorption showed that samples with lower H2 uptake became crack under high pressure. Among all the synthesized coordination polymers, MnCu-CP showed highest H2 storage capacity. |
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