Synthesis And Fluorescent Properties Of Functionalized Polystyrene By ATRP With Salicylaldehyde And Its Derivate As Initiator

(1) Atom transfer radical polymerization(ATRP) of styrene(St) proceeded using 5-chloromethyl-2-hydroxy-benzaldehyde(CMOB) as initiator, CuCl as catalyst and N,N,N',N',N'- pentamethyldiethyltriamine(PMDETA) or Bpy as ligand. The effects of solvents, concentration of monomer, reaction temperature and monomer to initiator mole ration on the polymerization displayed living character were discussed. The kinetic plot, the end structure of PSt analyzed by ~1H—NMR and block copolymer(PSt-b-PMMA) initiated by PSt all proved the polymerization accorded with the mechanism of atom transfer radical polymerization. But the inhibition of phenolic hydroxyl is not negligible during the atom transfer radical polymerizaition. Compared with PMDETA, the bulk polymerization of St was under better control using Bpy as ligand.(2) Atom transfer radical polymerization of styrene proceeded using 5-chloromethyl-2-methoxy-benzaldehyde (CMMB) as initiaor at the same conditions of using CMOB as initiator. The effects of different substituting group in initiator on the polymerization displayed living character were discussed. The fluorescent properties of functionalized polystyrene containing salicylaldehyde and o-methoxybenzaldehyde end group were also discussed here in. The results showed that compared with the initiator CMOB, the reaction rate was obviously accelerated, the efficiencies of the initiator were very high and even the polymerization could proceed at low temperature(40℃-70℃). It was concluded that the inhibition of phenolic hydroxyl was really existed. The functionalized polystyrene containing salicylaldehyde end group emitted obviously fluorescence at 500nm in the alkaline condition with λex=330nm, while the functionalized polystyrene containing 2-methoxy -benzaldehyde end group could not emit fluorescence at the same condition.(3) Fuctionalized polystyrene ligand containing schiff base end group (N-Salicyliden-(4-methoxy-Anilin)) was obtained by condensation of p-methoxyanilin with polystyrene containing salicylaldehyde end group. The polystyrene ligand was applied to prepare Zn(Ⅱ) complex. The polystyrene ligand and its complex werecharacterized through 'H-NMR, IR, UV-Vis and fluorescent spectra. We also imitated the reaction of using N-Salicyliden-(4-Methoxy-anilin), which is the end group of the polymer, to coordinate with Zn(II) in order to study the structure of polystyrene Zn(II) complex(PSt-CH2-SMOA-Zn). The effects of different molecular weights, amount of solvent in coordination, reaction methods including conventional heating and microwave irradiation and substituting group in aniline on Zn contents and fluorescent intensity were also discussed. The results showed that PSt-CH2-SMOA-Zn emitted intense fluorescence at 515 nm with A ex=330nm. Compared with analogous Zn(II) complexs with low molecular weight, the polystyrene Zn(II) complex was soluble in common solvents, easy to form film and showed intensive fluorescence. Choosing the suitable amount of solvent and small molecular weight of PSt could augment the fluorescent intensity. Microwave irradiation could accelerate the reaction rate. The fluorescent intensity was influenced by variation of the substituents.