Study On Synthesis And Properties Of Spiro [Fluorene-xanthene] Diamine And Poly Amide

In this paper, diphenol spiro[fluorene-xanthene] and dimethyl spiro[fluorene-xanthene]were prepared from the condensation reaction of fluorenone with1,3-diphenol or m-cresol. Anew kind of ether-containing spiro[fluorene-xanthene] diamine was synthesized bycondensation reaction and catalytic hydrogenation reaction with diphenol spiro[fluorene-xanthene]. And four different kinds of polyamide monomers were prepared sequentially bythe method of condensation, oxidation, chloride chlorination and interfacial polymerizationreactions with dimethyl spiro[fluorene-xanthene]. And they were used as E-51epoxy resincuring agent and modifier. The spiro[fluorene-xanthene] diamine and polyamides wereidentified via Fourier transform infrared (FT-IR), proton and carbon nuclear magneticresonances (1H NMR and13C NMR). The curing process，curing reaction kinetics of E-51epoxy resin with spiro[fluorene-xanthene] diamine was measured by differential scanningcalorimeter (DSC). The influence of mechanical property and thermal stability of thepolymerizations were investigated by thermal gravimetric analysis (TGA) and dynamicthermomechanical analysis (DMA).On the one hand,3’,6’-dihydroxy-spiro(fluorene-9,9-xanthene)(BHSFX) was preparedby the dehydration condensation reaction using fluorenone as raw material. The total yieldwas68%.2’,7’-bis(4-nitrobenzoic-4-phenyl ester)-spiro(fluorene-9,9-xanthene)(BNSFX) wassynthesized from the reaction of4-nitro chlorobenzene with BHSFX. The total yield was79%.And then, a new kind of ether-containing spiro[fluorene-xanthene] diamine (BASFX)monomer was obtained by catalytic hydrogenation of dinitro compound using hydrazinehydrate and Pd/C as catalyst in refluxing ethanol. The total yield was75%. The results ofdynamics methods show that the curing behaviors of BASFX/E-51system display thecharacteristic of autocatalyzed reaction. The Eaof the system is52.4kJ/mol. TheBASFX/E-51system exhibits good thermodynamic properties. The storage modulus and TgofBASFX/E-51have increased compared with DDM/E-51. The Tgvalues of DDM/E-51curingsystem increase41°C.On the other hand,3’,6’-diformyl-spiro(fluorene-9,9-xanthene) was prepared through thedehydration condensation reaction using fluorenone and M-cresol as raw material. The totalyield was91%. Spiro(fluorene-9,9-xanthene)-3’,6’-diacyl chloride (BCSFX) was synthesized by the reaction of permanganate oxidation and sulfoxide chloride chlorination with3’,6’-diformyl-spiro(fluorene-9,9-xanthene) respectively. And then, four kinds of newspiro[fluorene-xanthene] polyamides were obtained by synthetic BCSFX with aliphaticdiamine (ethylene diamine, butyl diamine, isophorone diamine and hexamethylene diamine)synthesized by interfacial polymerization, respectively. The effects of FXPA’s structure andthe dosage on performance of E-51epoxy resin were studied. The results indicate that FXPAcan effectively increase the char yield at800℃(Yc) and reduce Tgand storage modulus of theDDM/E-51curing system. This indicates that the toughness and thermal stability of thepolymers were improved slightly by adding FXPA. The toughening effect of order is asfollows, hexamethylene diamine>butyl diamine>isophorone diamine>ethylene diamine. Andthe Ycvalue’s order is as follows: ethylene diamine butyl diamine isophorone diamine hexamethylene diamine...