Study On Synthesis And Properties Of Novel Poly(aryl Ether Ketone)s Containing Biphenyl And Naphthalene Moieties In Main Chain

The synthesis, modification and applications of PAEK are reviewed in thisdissertation. In order to modify the properties of PAEK, we have prepared fivearomatic ether monomers, which were copolymerized with terephthaloyl chloride(TPC) or isophthaloyl chloride(IPC) by electrophilic substitution polycondensation inthe presence of anhydrous AlCl3and NMP in1,2-dichloroethane. A series of novelpoly(anyl ether ketone)s containing diphenyl and naphthalene moieties in main chainwere obtained.1. The synthesis and characterization of PEKKEKK containing diphenyl and1,4-naphthylene units in main chain.A series of poly(ether ketone ketone ether ketone ketone)s containing diphenyland1,4-naphthylene units in main chain were synthesized by electrophilic Friedel-Crafts solution copolycondensation of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP)and1,4-bis(4-phenoxybenzoyl)naphthalene(1,4-BPOBN) with isophthaloyl chloride(IPC), in the presence of anhydrous AlCl3and NMP in1,2-dichloroethane. Therandom copolymers were characterized by Fourier Transform Infrared Spectrometer(FT-IR), Differential Scanning Calorimetry(DSC), Thermogravimetric Analysis(TGA), X-Ray Powder Diffraction(XRD) etc. The results show that PEKKEKKcopolymers with high molecular weight can be synthesized by electrophiliccopolycondensation. The copolymers possess the Tgvalues of173.3~181.9℃, and Tmvalues of333.5~359.4℃. The decrease in concentration of BPOBDP resulted in thedecrease in the regularity and crystallinity of the polymer. The temperatures at5%weight loss Td(5%) are all above540℃. The resultant copolymers process high Tgsalong with exceptional thermooxidative stability, while maintaining insolubility in allcommon organic solvents at room temperature, except for strong protonating acidssuch as concentrated H2SO4.2. The synthesis and characterization of PEKKEKK containing diphenyl and2,6-naphthylene units in main chain.A series of poly(ether ketone ketone ether ketone ketone)s containing diphenyland2,6-naphthylene units in main chain were synthesized by electrophilic Friedel-Crafts solution copolycondensation of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP) and2,6-bis(4-phenoxybenzoyl)naphthalene(2,6-BPOBN) with isophthaloyl chloride(IPC), in the presence of anhydrous AlCl3and NMP in1,2-dichloroethane. Therandom copolymers were characterized by Fourier Transform Infrared Spectrometer(FT-IR), Differential Scanning Calorimetry(DSC), Thermogravimetric Analysis(TGA), X-Ray Powder Diffraction(XRD) etc. The results show that PEKKEKKcopolymers with high molecular weight can be synthesized by electrophiliccopolycondensation. The copolymers possess the Tgvalues of172.8~178.6℃, and Tmvalues of327.3~359.4℃. The decrease in concentration of BPOBDP resulted in thedecrease in the regularity and crystallinity of the polymer. The temperatures at5%weight loss Td(5%) are all above550℃. The resultant copolymers have high Tgsalong with exceptional thermooxidative stability, while maintaining insolubility in allcommon organic solvents at room temperature, except for strong protonating acidssuch as concentrated H2SO4.3. Copolymerization of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP) and1,3-bis(4-phenoxy benzoyl)benzene(m-EKKE) with isophthaloyl chloride(IPC).A series of poly(ether ketone ketone ether ketone ketone)s containing diphenylunits in main chain were synthesized by electrophilic Friedel-Crafts solutioncopolycondensation of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP) and1,3-bis(4-phenoxybenzoyl)benzene(m-EKKE) with isophthaloyl chloride(IPC), in the presenceof anhydrous AlCl3and NMP in1,2-dichloroethane. The random copolymers werecharacterized by Fourier Transform Infrared Spectrometer(FT-IR), DifferentialScanning Calorimetry(DSC), Thermogravimetric Analysis(TGA), X-Ray PowderDiffraction(XRD) etc. The results show that a series of PEKKEKK copolymers withhigh molecular weight can be synthesized by electrophilic copolycondensation. Thecopolymers possess the Tgvalues of152.2~178.6℃, which increase gradually withthe increase in concentration of diphenyl unit and Tmvalues range from327.5~359.4℃. The temperatures at5%weight loss Td(5%) are all above540℃. Theresultant copolymers possess high Tgalong with exceptional thermooxidative stability,while maintaining insolubility in all common organic solvents at room temperature,except for strong protonating acids such as concentrated H2SO4.4. Copolymerization of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP) and1,4-bis(4-phenoxy benzoyl)benzene(p-EKKE) with isophthaloyl chloride(IPC).A series of poly(ether ketone ketone ether ketone ketone)s containing diphenylunits in main chain were synthesized by electrophilic Friedel-Crafts solutioncopolycondensation of4,4’-bis(4-phenoxybenzoyl)diphenyl(BPOBDP) and1,4-bis(4- phenoxybenzoyl)benzene(p-EKKE) with isophthaloyl chloride(IPC), in the presenceof anhydrous AlCl3and NMP in1,2-dichloroethane. The random copolymers werecharacterized by Fourier Transform Infrared Spectrometer(FT-IR), DifferentialScanning Calorimetry(DSC), Thermogravimetric Analysis(TGA), X-Ray PowderDiffraction(XRD) etc. The results show that a series of PEKKEKK copolymers withhigh molecular weight can be synthesized by electrophilic copolycondensation. Thecopolymers possess the Tgvalues of161.5~178.6℃, which increase gradually withthe increase in concentration of diphenyl units and Tmvalues range from328.6to359.4℃. The temperatures at5%weight loss Td(5%) are all above540℃. Theresultant copolymers possess high Tgs along with exceptional thermooxidativestability, while maintaining insolubility in all common organic solvents at roomtemperature, except for strong protonating acids such as concentrated H2SO4.5. The synthesis and characterization of PEKKEKK/PEKK containing1,4-naphthylene units in main chainA series of poly(ether ketone ketone ether ketone ketone)s containing1,4-naphthylene units in main chain were synthesized by electrophilic Friedel-Craftssolution copolycondensation of diphenyl ether(DPE),1,4-bis(4-phenoxybenzoyl)naphthalene(1,4-BPOBN), terephthaloyl chloride(TPC) and isophthaloyl chloride(IPC), in the presence of anhydrous AlCl3and NMP in1,2-dichloroethane. Meanwhile,the same component of the copolymers were obtained by using1,4-bis(4-phenoxybenzoyl)benzene(p-EKKE) in place of the DPE. The random copolymers werecharacterized by Fourier Transform Infrared Spectrometer(FT-IR), DifferentialScanning Calorimetry(DSC), Thermogravimetric Analysis(TGA), X-Ray PowderDiffraction(XRD) etc. The results show that a series of PEKKEKK/PEKKcopolymers with high molecular weight can be synthesized by electrophiliccopolycondensation. The copolymers possess the Tgvalues of164.6~171.2℃, whichincrease gradually with the increase in concentration of1,4-naphthylene units and Tmvalues range from about314.1to328.7℃. The temperatures at5%weight loss Td(5%)are all above540℃. The resultant copolymers possess high Tgs along withexceptional thermooxidative stability, while maintaining insolubility in all commonorganic solvents at room temperature, except for strong protonating acids such asconcentrated H2SO4.