Polymerization Of Polar Αlpha-olefin Containing Ferrocene Groups

In this thesis,five ferrocenyl polarα-olefin monomers were designed and synthesized.The（C₅H₅）Sc（CH₂C₆H₄NMe₂-o）₂（Sc-Cp）/[Ph₃C][B（C₆F₅）₄]catalyst system catalyzed the homopolymerization and copolymerization of the five monomers to access a series of unreported polymers containing ferrocenyl polar groups.The structures of these polymers were characterized by ¹H NMR,¹³C NMR,GPC,SEM and DSC.The electrochemical properties of the polymers were studied by CV and the thermal stability of the polymers was tested by TGA.1.（C₅H₅）Sc（CH₂C₆H₄NMe₂-o）₂（Sc-Cp）/[Ph₃C][B（C₆F₅）₄]catalyzed copolymerization of monomer[4-（butenoxyl）benzene]-4-benzylferrocene B with styrene,isoprene,and ethylene,respectively.The results indicated that when the monomer B was copolymerized with styrene in different feed ratio,copolymers with monomer insertion rate of 3-50mol%and molecular weight range of 12.7-59.7 x10³were obtained.The glass transition temperature（T_g）of these copolymers ranges from59℃to 94℃determined by differential calorimetry（DSC）.It was noteworthy that the lower of monomer insertion rate,the higher of T_g.The decomposition temperature of these copolymers ranges from 255℃to 270℃tested by thermogravimetric（TGA）.The copolymers were observed as irregular spheroids characterized by scanning electron microscopy（SEM）.Electrochemistry（CV）tests displayed that the polymers possess reversible REDOX feature.When monomer B copolymerized with isoprene,the diblock copolymers were generated with monomer insertion rate of 11-61 mol%via varying the feed ratio.The NMR analysis showed that the cis-1,4-selectivity of polyisoprene can reached as high as 92%.One of the two T_g came from polyisoprene block,which was slightly different with that of isoprene homopolymer,the other T_gcame from polymonomer B block.As the increase of monomer insertion rate,the latter T_g went higher as well.The copolymers were observed as the linkage of spheroids and gel.Electrochemistry（CV）tests displayed that these polymers possess reversible REDOX feature too.For the copolymerization of monomer B with ethylene,the structures of the copolymers were characterized by NMR,GPC and DSC.GPC displayed bimodal result of the copolymers.DSC showed Tg of polymonomer B and Tm of polyethylene.The resultant products were blends rather than copolymers combining the GPC and DSC results.2.（C₅H₅）Sc（CH₂C₆H₄NMe₂-o）₂（Sc-Cp）/[Ph₃C][B（C₆F₅）₄]catalyzed homopolymerization of monomer（3-propensulfenylbenzene）-4-benzylferrocene C,monomer（3-propenoxy）benzene]-4-benzylferrocene D,monomer 1,1’-bis（4-butenoxybenzene）-4-benzylferrocene E.It was fouund that monomer C and monomer D could not homopolymerize.For the homopolymerization of monomer E,the prepared polymers were not soluble in common organic solvents such as THF,DCM,DMSO etc after adjusting feed ratio,polymerization time,temperature,solvent amount.The T_g of the homopolymer ranges from 160℃to 180℃.The decomposition temperature was 340℃,indicating that the homopolymer was thermally stable.The homopolymer was observed as a tubular cluster with a profile of regular network structure.Powder X-ray diffraction showed that the polymer was amorphous structure.3.The ADMET polymerization of 1,1’-bis（4-butenoxybenzene）-4-benzyl ferrocene catalyzed by GrubbsⅡcatalyst and our newly synthesized Grubbs-like sub-catalyst（Cat.3）.Under the condition of high catalyst loading（5 mol%）,toluene as solvent,80℃,12 h,the highest molecular weight（Mn=7802）polymer was obtained.The T_g increased with the increase of molecular weight ranging from 8-20℃.The decomposition temperature of the polymer was 360℃.Scanning electron microscopy（SEM）showed that the polymer had a spherical particle shape.