Study On Synthesis,Film Preparation And Film Surface Performance Of Ferrocene-and Azobenzene-based Polymers

Ferrocene is a commonly used redox-responsive group which can reversibly transform between reduced state and oxidized state under(electro)chemical redox stimuli.Different redox states of ferrocene have different properties.Azobenzene is the most common photo-responsive group which can undergo trans/cis isomerization under UV/vis light and change the properties.In this thesis,we devoted our efforts to introduce ferrocene and azobenzene groups into different kind of polymers to get different ferrocene-and azobenzene-based photo-and redox-responsive polymers,studied their photo-and redox-responsive properties.Polymer films were prepared by drop-coating or spin-coating,and their applications in the fields of in information storage and surface morphology regulation were explored.(1)Homopolymer PFcEMA and four ferrocene-and azobenzene-based copolymers(P(FcEMA-co-MAAzo)s)with different ratios(11:1,7:1,4:1 and 3:1)were synthesized using free radical polymerization with AIBN as initiator.1H NMR,FT-IR,GPC and TGA were used to confirm the composition,structure,molecular weight and thermal stability of these five polymers.CV and UV-vis absorption spectra were used to study their redox-and photo-responsive properties.The results showed that the these P(FcEMA-co-MAAzo)s had reversible redox-and photo-responsive properties in solvent.P(FcEMA-co-MAAzo)s films were prepared by coating the polymer solution on glass substrates.Chemical redox stimuli and UV-vis absorption spectra were used to study the redox-and photo-responsive properties of polymer films.It was found that these films were redox-and photo-responsive.The films'color was yellow in reduced state while after oxidation color changed to green.Based on this kind of color change,if we applied selective redox stimuli on selective area of the films,color of this area will be different from remaining area.These polymers have potential applications in information storage devices.(2)Three ferrocene-and azobenzene-based amphiphilic block copolymers(PEO-b-P(FcEMA-co-MAAZOOHEE)s)with different ratios of hydrophilic block and hydrophobic block were synthesized via ATRP using different molecular weight PEO-Br as initiator.1H NMR,FT-IR,GPC and TGA were used to confirm the composition,structure,molecular weight and thermal stability of these three PEO-b-P(FcEMA-co-MAAZOOHEE)s.CV and UV-vis absorption spectra were used to study the redox-and photo-responsive properties.It was found that these polymers have good redox-responsive property and reversible photo-responsive property in solvent.These polymers can be used in honey-comb patterned film fabrication.The influences of temperature,humidity,polymer concentration and polymer structure on the film regularity were studied.The results showed that temperature,humidity,polymer concentration and polymer structure affected the regularity and pore size of honey-comb patterned film.Temperature affected the solvent evaporation rate.Decrease in temperature increased solvent volatilization time and prepared better honey-comb film.Too high or too low humidity and polymer concentration were not beneficial to the preparation of honey-comb patterned film.In appropriate range of humidity and concentration,with the increase of humidity,the pore diameter of honey-comb patterned film gradually increased,while with the increase of polymer concentration,the pore diameter decreased.The ratio of hydrophilic and the hydrophobic chain of amphiphilic block copolymer was important to form the highly ordered honey-comb patterned films.Overlong hydrophilic chain segment induced the coalescence of water droplets and destroyed the regularity of honey-comb patterned film.When using linearly polarized UV light and oxidizing agent to treat honey-comb patterned film,the pore shape and size can be regulated.It was found that after 5 h linearly polarized UV light irradiation,the pore shape of honey-comb patterned film changed from round hexagon into round rhombus.And after oxidation by Ce(NH4)2(NO3)6 aqueous solution,the pore diameter of the honey-comb pattered film slightly decreased and the wall thickness slightly increased.So linearly polarized UV light irradiation and oxidizing agent can be used to regulate pore shape and pore size of honey-comb patterned film.(3)PAZO and PAZO-Fc were synthesized by ring-opening polymerization of bisphenol A diglycidyl ether and disperse orange 3 or aminoazobenyl ferroamide.1H NMR,FT-IR,GPC,TGA and DSC were used to confirm the structure,molecular weight,thermal stability and glass transition temperature of these two polymers.CV and UV-vis absorption spectra were used to study the redox-and photo-responsive properties.It was found that both PAZO and PAZO-Fc had reversible photo-responsive property and PAZO-Fc had redox-responsive property.The THF solutions of these two polymers were spin-coated on PDMS substrates which were pretreated by plasma.The surface wrinkles were induced by heating and cooling.Light irradiation and redox stimulus were used to adjust the mophorlogy of surface wrinkle.The results showed that the surface wrinkles on PAZO/PDMS bilayer system can be regulated by visible light irradiation while surface wrinkles on PAZO-Fc/PDMS bilayer system can be regulated by UV light irradiation and redox stimulus.