Synthesis And Properties Of Polyether With Oxazine Moiety At The Chain End

In this thesis, one or two phenolic compounds (bisphenol A, bisphenol AF, bisphenolfluorene,2,7-dihydroxy fluorenone) and4,4’-dichlorodiphenyl sulfone or4,4’-dichlorodiphenyl ketone were used as raw materials to get hydroxyl-ended polyetherprepolymer. Then the hydroxyl-ended polyether prepolymer was reacted with formaldehyde,n-butyl amine to obtain oxazine end-capped polyether prepolymer. The structures of theoxazine end-capped oliogmers were confirmed by nuclear magnetic resonance (1H-NMR),Fourier Transform Infrared Spectroscopy (FT-IR) and gel permeation chromatography (GPC).Thermal properties of the copolymers were investigated by differential scanning calorimeter(DSC) and thermal gravimetric analysis (TGA). Mechanical properties were investigated withdynamic thermomechanical analysis (DMA).The polyether ketone and polyether sulfone with butyl amino benzoxazine at thechain-end were synthesized with bisphenol fluorene as raw material. While the poly (ethersulfone ketone) and poly (ether ketone ketone) oligomers were synthesized with2,7-dihydroxy fluorenone as raw material. The results showed that the yield of the first stepwas about55~65%and the yield of the second step was about67%-75%. The averagemolecular weights of oxazine end-capped homopolymerize oliogmers were1700-2300. TheTgof the products were214-231oC after curing, the char yield at800oC were51.9%-59.3%and the initial thermal decomposition temperature were340-423oC. The thermal propertiesof the ployether ketone (ether ketone ketone) were higher than that of polyether sulfone (ethersulfone ketone). Because the fluorenone molecules increased the rigidity, thus the polymerwith fluorenone in the main chain which were obtained by2,7-hydroxy fluorenone had higherthermal than the polymers with fluorene deribatived overhang the chain which were obtainedwith bisphenol fluorene.The polyether sulfone, polyether ketone, poly (ether sulfone ketone) and poly (etherketone ketone) random copolymer with oxazine rings at chain-end were synthesized withbisphenol fluorene or2,7-dihydroxy fluorenone being mixed respectively with bisphenolA orbisphenol AF as material. The yield of polycondensation reactions were50%-62%, and theyield of Mannich reactions were62%-70%. The random copolybenzoxazines were obtainedby thermal polymerization. The thermal properties of the polymers improved with the bisphenol fluorene or2,7-dihydroxy fluorenone increasing. Compared with thehomopolybenzoxazine, the thermal properties of copolybenzoxazine were under condition.The corresponding membrane materials of oxazine end-capped copolyether could beobtained after casting. It was found that the trorage modulus and Tg, thermal stability andstorage modulus increased when the dosage of2,7-dihydroxy fluoreneone increased, but thefilm transparency reduced.