Synthesis And Properties Of Novel Soluble Poly (Arly Ether Nitrile)s And Poly (Aryl Ether Nitrile Sulfone)s Containing Xanthene Structures

In this dissertation, the recent progress on the study of poly(aryl ether nitrile)s and poly(aryl ether nitrile sulfone)s were investigated. This paper was mainly composed of six parts as follow:1.Reaction of xanthone with thionyl chloride afforded intermediate 9,9-dichloroxanthene, which was treated with phenol in refluxing xylene to form 9,9-bis(4-hydroxyphenyl)xanthene (BHPX) in 82% yield in a one-pot, two-step synthetic procedure.2.According to above synthetic procedure, reaction of xanthenone with thionyl chloride afforded the intermediate 9,9-dichloroxanthene, followed by treatment with phenol, o-cresol,2,6-dimethylphenol furnished two kinds of xthanenebiphenols such as 9,9-bis(4-hydroxyphenyl)xanthene, 9,9-bis(4-hydroxy-3-methylphenyl)xanthene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)xanthene in 80.2% and 82.8 yield in one-pot, two-step synthetic procedure, respectively.3.A series of novel poly(aryl ether nitrile) copolymers containing xanthene structures were synthesized from 9,9-bis(4-hydroxyphenyl)xanthene, 2,6-difluorobenzonitrile and hydroquinone in DMAC by solution polycondensation under the protection of the nitrogen. These polymers had the inherent viscosities in the range of 0.4-1.08 dL/g, and exhibited high heat-resistance with the decomposition temperatures at 5% weight loss ranging from 407℃to 447℃, the glass transition temperatures (Tg's) ranging from 216℃to 257℃.These polymers with tensile strengths of 48-60 MPa, tensile moduli of 0.97-1.2 GPa, elongation at breaks of 5.9-13% were soluble in DMF, DMAC, DMSO, NMP, CH2Cl2, CHCl3,THF and pyridine at room temperature.4.According to above polycondensation procedure, a series of novel poly(aryl ether nitrile) copolymers containing xanthene structures with two methyl pendants were synthesized from 9,9-bis(3-methyl-4-hydroxyphenyl)xanthene, 2,6-difluorobenzonitrile and hydroquinone. These polymers had the inherent viscosities in the range of 0.25-1.38 dL/g, and exhibited the glass transition temperatures (Tg's) ranging from 213℃to 222℃.These polymers with tensile strengths of 56-121 MPa, tensile moduli of 1.11-1.44 GPa, elongation at breaks of 5.1-5.4% were soluble in solvents such as DMF, DMAC and DMSO at room temperature.5.According to above polycondensation procedure, a series of novel poly(aryl ether nitrile) copolymers containing xanthene structures with four methyl pendants were synthesized from 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)xanthene, 2,6-difluorobenzonitrile and hydroquinone. These polymers had the inherent viscosities in the range of 0.4-1.08 dL/g, and exhibited high heat-resistance with the decomposition temperatures at 5% weight loss ranging from 358℃to 398℃, the glass transition temperatures (Tg's) ranging from 248℃to 289℃.These polymers with tensile strengths of 53-59 MPa, tensile moduli of 1.1-1.3 GPa, elongation at breaks of 2.2-3.6% were soluble in DMF, DMAC, DMSO, NMP, CH2Cl2, CHCl3,THF and pyridine at room temperature.6.According to above polycondensation procedure, a series of novel poly(aryl ether nitrile sulfone) copolymers containing xanthene structures were synthesized from 9,9-bis(4-hydroxyphenyl)xanthene,4,4'-dichlorodiphenylsulfone and 2,6-difluorobenzonitrile.These polymers had the inherent viscosities in the range of 0.41-0.65 dL/g, and exhibited high heat-resistance with the decomposition temperatures at 5% weight loss ranging from 447℃to 518℃, the glass transition temperatures(Tg's) ranging from 236℃to 277℃. These polymers with tensile strengths of 91-117 MPa, tensile moduli of 2.4-2.8 GPa, elongation at breaks of 8.3-17.3% were soluble in DMF, DMAC, DMSO, NMP, CH2Cl2, CHCl3,THF and pyridine at room temperature.