Synthesis And Characterization Of Poly(Aryl Ether) Microspheres Containing Triazines

Polymeric microspheres were developed from functional macromolecules and have attracted widespread attention in recent years due to their small size,large specific surface area and abundant functional groups.Among them,aromatic s-triazine-based polymers have recently gained a lot of interests contributed to their unique triazine structure features.The symmetric triaryl-s-triazine structure could enhance the thermal stability of the polymers with the decomposition temperature as high as 486 ^oC.The large conjugated structure between aromatic N-heterocycle and s-triazine rings are beneficial to transport and transfer electrons.Beyond that,the triaryl s-triazine polymer also shows excellent thermal stability,chemical resistance,high strength,high modulus and unique photoelectric properties.Firstly,we explored the synthesis route to obtain 2,4,6-tri-?4-fluorophenyl?-1,3,5-triazine?TFPT?with high yield and purity.The TFPT was prepared successfully from4-fluorobenzene nitrile as raw material.The nitrile groups were cyclized by trimerization to form s-triazine structure with CF₃SO₃H existed as catalyst.The product structure was confirmed by means of Fourier transform infrared spectra?FTIR?and Nuclear magnetic resonance spectroscopy?¹H NMR?,and the purity of the monomer was measured by High-performance liquid chromatography?HPLC?.Secondly,two series of cross-linked poly?aryl ether ketone?microspheres containing s-triazines were synthesized by a direct solution-precipitation polymerization of TFPT with6-?4-hydroxyphenyl?-3?2H?-pyridazinone?HPZ?and1,2-dihydro-4-?4-hydroxyphenyl??2H?-phthalazin-1-one?DHPZ?in strong polar aprotic solvents such as 1-methyl-2-pyrrolidinone?NMP?and N-N-Dimethylacetamide?DMAc?,named as TFPT-HPZ and TFPT-DHPZ microspheres,respectively.The optimal preparation conditions of polymeric microspheres were explored by controlling the reaction condition such as solvent selection,post-polymerization treatment,monomer concentration,reaction time and temperature et al.It was confirmed that the TFPT-HPZ polymer microspheres with uniform morphology and good uniformity was obtained in NMP when the monomer concentration was 1.65 g/L,the reaction time was 10 h,and the reaction temperature was160°C.The optimum reaction conditions for TFPT-DHPZ microspheres are 1.50 g/L,10 h under 160°C in NMP to give good morphology,uniform and good dispensability.The product structure was confirmed by means of FTIR.The prepared polymer microspheres were characterized by Scanning electron microscopy?SEM?,Transmission electron microscope?TEM?and X-ray photoelectron spectroscopy?XPS?.The results showed that the microspheres had an average particle size of 2?m.The surface exhibited granular protrusions and were rich in-OH,-NH groups.The TGA and fluorescence spectrophotometers demonstrated that the microspheres had excellent thermal stability,thermal-oxidative stability,and fluorescence properties.