Fluorescent Supramolecular Materials Based On Multi-amine And Multi-carboxylic Acid

Fluorescent polymers of multiple response in sensing,detection,display and other fields have good application prospect,and the design and synthesis of multiple response fluorescence polymers is a challenging problem,so multiple response fluorescence polymers have attracted extensive attentions.However,the present multiple response fluorescence polymers almost have aromatic conjugated groups and need much organic solvents in the synthesis and application.Moreover,they can only show their responsiveness in solution.Therefore,there is an urgent need to explore the multiple responsive polymers that can produce response in solid state.In this thesis,we obtained a series of fluorescence supramolecular polymers with citric acid and aliphatic amines.Subsequently,we systematically explored multi-response properties of supramolecular polymers.Finally,we explored the factors that affected fluorescence properties of supramolecular polymers.The results obtained were summarized as follows:1.In this work,we prepared a supramolecular polymer with citric acid and aliphatic amines.Infrared analysis showed the proton transfer occured between citric acid and N-aminoethyl piperazine in supramolecular polymer.The fluorescence spectra and optical images showed the supramolecular polymer could emit strong fluorescence.This is because the relaxation of tertiary amine group was greatly restricted owing to the strong electrostatic interaction between carboxyl and amine.The DSC analysis showed the glass transition temperature(-8.7℃)of the supramolecular polymer is lower than the hyperbranched poly(amide amine)s,which shows the supramolecular polymers are more likely to undergo relaxation transition.The WXRD showed the structures of supramolecular polymers and hyperbranched polyamide amine are similar because the shape and location of their diffraction peaks are similar.However,the diffraction peak intensity of supramolecular polymers is smaller than hyperbranched poly(amide amine)s,the result showed the structure of supramolecular polymers is not as compact as hyperbranched poly(amide amine)s,which showed supramolecular polymer have better stimuli-responsive property.Multiple response analysis showed:1)the fluorescence intensity decreased with the extension of supramolecular polymers exposed to moist air,and humidity response of supramolecular polymers also had good reversibility.2)the fluorescence intensity decreased with the extension of supramolecular polymers exposed to triethylamine gas.3)the fluorescence intensity decreased with the extension of supramolecular polymers exposed to acetic acid gas.4)the supramolecular polymer also had good response ability for temperature,and the fluorescence intensity decreased with the increase of temperature.Finally,we also found the supramolecular polymers also had good self-healing performance.2.In this work,we obtained two supramolecular films of difference structure based on proton transfer reaction among citric acid and N,N,N’,N’-teramethylethylenediamine,N,N,N’,N’-tetramethyl-1,3-propanediamine.Thus,in this paper,we mainly investigate the influence of structure on it’s fluorescence property.We discovered supramolecular film from citric acid and N,N,N’,N’-teramethylethylenediamine was crystalline state and emited strong fluorescence,supramolecular film from citric acid and N,N,N’,N’-tetramethyl-1,3-propanediamine was amorphous state and emited weak fluorescence.In addition,we also found that these two supramolecular films could be responsive to humidity and triethylamine gas.But supramolecular film of crystalline state had better response capability than supramolecular film of amorphous state.This because molecules of crystalline supramolecular films are more regular,more compact,and more powerful than amorphous supramolecular film.These showed the structure had a significant effect on the fluorescence property of supramolecular materials containing tertiary amine group.In summary,we have successfully synthesized the fatty fluorescence supramolecular polymers which don’t contain aromatic conjugated group.Theses environmentally friendly fluorescence supramolecular polymers can be used in the fields of sensing,detection and display.