Synthesis and characterization of new aromatic polyesters and polyethers derived from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene

New polyarylates and aromatic polyethers were synthesized from 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene, and aromatic dicarboxylic acid chlorides and aromatic dihalides, respectively. The polyarylates having inherent viscosities of 0.28–1.05 dL/g were synthesized by either the two-phase method or the high-temperature solution method. All the polymers were easily soluble in N-methyl-2-pyrrolidone, N,N-dimethylformamide, pyridine, m-cresol, 1,4-dioxane, and 1,1,2,2-tetrachloroethane. They have glass transition temperatures in the range of 217–250°C and showed no weight loss below 315°C in both air and nitrogen atmospheres. Aromatic polyethers with inherent viscosities of 0.85–1.21 dL/g were obtained by the polycondensation of 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethylene and aromatic difluorides in the presence of potassium carbonate. These polymers having glass transion temperatures of 193–220°C were also soluble in the aforementioned solvents and stable up to around 350deg;C in both atmospheres. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of a novel perfluorononenyloxy group containing polyarylates

A series of novel perfluorononenyloxy group containing polyarylates were synthesized by a high-temperature solution condensation of 5-(perfluorononenyloxy)-isophthaloyl chloride ( II ) with various aromatic diols in o-dichlorobenzene. All the polyarylates were amorphous and readily soluble in many organic solvents such as o-chlorophenol, o-dichlorobenzene, chloroform, and polar aprotic solvents at room temperature or on heating. Transparent, tough, and flexible films of these polymers could be cast from the o-chlorophenol solutions. The polymers having inherent viscosity of 0.61–1.63 dL/g were obtained in quantitative yields. These polymers were thermally quite stable. The glass transition temperatures of these polyarylates were in the range of 219–242°C by DSC and 224–251°C by DMA, and the 10% weight loss temperatures in nitrogen and air were above 415 and 397°C, respectively. Moreover, these polymers maintained good mechanical properties (G′ ∼ 10⁸ Pa) up to 220°C and had lower moisture absorption than common polyarylates. The dielectric constants of these polymers ranged from 3.23 to 3.75. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 645–653, 1998     

Synthesis and characterization of novel polyarylates from 2,5-bis(4-hydroxyphenyl)-3,4-diphenylpyrrole and various aromatic dicarboxylic acids

A new tetraphenylated heterocylic diol, 2,5-bis(4-hydroxyphenyl)-3,4-diphenylpyrrole, was synthesized in three steps starting from 4-methoxydeoxybenzoin. The tetraphenylpyrrole-containing polyarylates having inherent viscosities of 0.28–0.88 dL/g were prepared from the diol and various aromatic dicarboxylic acid chlorides by both phase transfer catalyzed two-phase polycondensation and high temperature solution polymerization methods. All the polyarylates were semi-crystalline, and were readily soluble in a variety of solvents including N-methyl-2-pyrrolidone, m cresol, pyridine, and 1,4-dioxane. These polymers had glass transition temperatures in the range of 223–279°C, with no weight loss below 400°C in both air and nitrogen atmospheres. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of novel polyarylates from 2,5-bis(4-hydroxyphenyl)-3,4-diphenylfuran and aromatic diacid chlorides

New tetraphenylated heterocyclic diol, 2,5-bis(4-hydroxyphenyl)-3,4-diphenylfuran, was synthesized by the oxidative coupling of 4-methoxydeoxybenzoin as a starting material, followed by simultaneous cyclodehydration and demethylation. Tetraphenylfuran-containing polyarylates with inherent viscosities of 0.2–0.7 dL/g were prepared from various diacid chlorides by both solution polycondensation and phase transfer catalyzed two-phase polymerization methods. All the polymers were easily soluble in dichloromethane, o-chlorophenol, 1,4-dioxane, pyridine, and N-methyl-2-pyrrolidone and showed semicrystalline patterns as evidenced by the X-ray diffraction studies. These polyarylates have glass transition temperatures in the range of 222–236°C and 10% weight loss was observed above 430°C in both air and nitrogen.     

Preparation and properties of polyarylates both from 2,2′-bibenzoyl chloride and bisphenols and from biphenyl-2,2′-diol and aromatic dicarboxylic acid chlorides

Polyarylates having inherent viscosities up to 1.02 dL/g were synthesized both by the phase-transfer catalyzed two-phase polycondensation of 2,2′-bibenzoyl chloride with various bisphenols and by the high-temperature solution polycondensation of biphenyl-2,2′-diol with aromatic dicarboxylic acid chlorides. All the polyarylates were amorphous and soluble in a variety of organic solvents including N,N-dimethylformamide, N-methyl–2-pyrrolidone, chloroform, m-cresol, and pyridine. Transparent and flexible films of these polymers could be cast from the chloroform solutions. These polyarylates had glass transition temperatures in the range of 120–250°C and began to lose weight at around 380°C in air. © 1992 John Wiley & Sons, Inc.     

Synthesis and properties of new polyarylates from 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols

New 1,4‐naphthyl and 2,6‐naphthyl‐containing polyarylates having inherent viscosities up to 1.28 dL/g were synthesized by the high‐temperature solution polycondensation from the acid chloride of 1,4‐bis(4‐carboxyphenoxy)naphthyl or 2,6‐bis(4‐carboxyphenoxy)naphthyl and various bisphenols. Most of the resulting polyarylates showed amorphous characteristics and were readily soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), o‐chlorophenol, and chloroform. Transparent, flexible, and colorless films of these polymers could be cast from the DMAc solutions. Their cast films had tensile strengths ranging from 54.9 to 84.2 MPa, elongations at break from 5.3% to 19.0%, and initial modulus from 2.0 to 2.8 GPa. These polymers had glass transition temperatures in the range of 172–280°C and began to lose weight around 400°C, with 10% weight loss being recorded at about 450°C in air. Dynamic mechanical analysis (DMA) reveals that the polyarylates containing isopropylidene linkages have three transitions on the temperature scale between −100 and 300°C. However, only two transitions were observed in the other polyarylates without isoproylidene linkage. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 645–652, 1999     

Synthesis and characterization of novel polybenzimidazoles containing 4-phenyl phthalazinone moiety

A novel series of homo- and copoly(phthalazinone benzimidazole)s were synthesized from various stoichiometric mixtures of 4-(4-(4-(4-carboxyphenoxy)phenyl)-1-oxophthalazin-2(1H)-yl)benzoic acid (CPPBC) and isophthalic acid (IPA) with 3,3′-diaminobenzidine (DAB) by solution polycondensation in polyphosphoric acid (PPA). The structures of the obtained polymers were characterized by FT-IR and ¹H NMR. The obtained polybenzimidazoles were found to be soluble in aprotic polar solvents such as N-methyl-2-pyrolidinone (NMP), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and m-cresol, without the addition of inorganic salts. The inherent viscosities of the polybenzimidazoles were in the range of 1.10–2.05 dL/g. All of the polymers show amorphous nature as evaluated by WAXD. These polymers have high glass transition temperatures (T_gs) in the range of 398–408 °C. Thermogravimetric analysis exhibit that these polybenzimidazoles containing 4-phenyl phthalazinone moiety have excellent thermal stability with the temperatures for 5% and 10% weight loss of the polymers ranging from 516 to 594 °C and 560 to 672 °C, respectively.     

Preparation and properties of polyarylates and copolyarylates from phenylindanedicarbonyl chloride and bisphenols

A series of polyarylates having inherent viscosities of 0.4–1.1 dL/g was prepared by the two phase polycondensation of 1,1,3-trimethyl-3-(4-chloroformylphenyl)indanecarbonyl chloride with various bisphenols in an organic solvent–aqueous alkaline solution system in the presence of a phase transfer catalyst. Similarly, copolyarylates of high molecular weights were prepared from a mixture of the phenylindanedicarbonyl chloride, terephthaloyl chloride, and 2,2-bis(4-hydroxy-phenyl)propane. All the polyarylates were characterized by their amorphous nature and high solubility in organic solvents. They gave transparent and tough films by the solution casting. The films had tensile strength of 33–46 MPa, elongation at break of 3–16%, and tensile modulus of 1.2–1.6 GPa. These polyarylates had glass transition temperatures in the range of 205–310°C, and began to decompose at ca. 350°C in air.     

Electroactive aromatic polyamides and polyimides with adamantylphenoxy-substituted triphenylamine units

A new triphenylamine-containing aromatic diamine monomer, 4-[4-(1-adamantyl)phenoxy]-4′,4″-diaminotriphenylamine, was synthesized from cesium fluoride-mediated N,N-diarylation of 4-(1-adamantyl)-4′-aminodiphenyl ether with 4-fluoronitrobenzene and subsequent reduction of the resultant dinitro compound. Novel electroactive aromatic polyamides and polyimides with adamantylphenoxy-substituted triphenylamine moieties were prepared from the newly synthesized diamine monomer with aromatic dicarboxylic acids and tetracarboxylic dianhydrides, respectively. All the resulting polymers were amorphous and most of them were readily soluble in polar solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) and could be solution-cast into transparent and strong films with good mechanical properties. These polymers exhibited glass-transition temperatures between 254 and 310 °C, and they were fairly stable up to a temperature above 450 °C for the polyamides and above 500 °C for the polyimides. These polymers exhibited strong UV-vis absorption maxima at 293-346 nm in solution, and the photoluminescence spectra of polyamides showed maximum bands around 408-452 nm in the blue region. Cyclic voltammograms of the polyamide and polyimide films on an indium-tin oxide (ITO)-coated glass substrate exhibited one pair of reversible redox couples at half-wave oxidation potentials (E_1/2) around 0.83-0.86 V and 1.12-1.13 V, respectively, versus Ag/AgCl in an acetonitrile solution. All the polymer films revealed good electrochemical and electrochromic stability by repeatedly switching electrode voltages between 0.0 V and 1.1-1.4 V, with coloration change from the pale yellowish neutral state to the green or blue oxidized state.     

Synthesis and properties of aramids and polyarylates having perfluoro-substituents on the benzene ring

A new series of 16 aramids and 16 polyarylates having perfluoro-substituents on the benzene ring was prepared by a low temperature solution or an interfacial polycondensation. The effects of fluorine substituents on the structure and properties of polymers were examined. Fluorinated aramids exhibited higher crystallinity, while fluorinated polyarylates show lower crystallinity. The melting point (T_m) of aramids decreased with fluorine substitution, whereas T_m of polyarylates from fluorinated aromatic diols was higher than that of those from unfluorinated ones. The temperature of 10% weight loss and the residue at 900°C decreased with fluorine substitution except for the aramids from fluorinated diamines. Solubility and contact angle also increased with fluorine substitution. Some polyarylates were found to exhibit an optical anisotropy.     

Synthesis and characterization of polyamides derived from (4-(4-(2, 6-diphenylpyridin-4yl)phenoxy)phenyl)-3, 5-diaminobezamide

New types of polyamides containing pendent triaryl pyridine groups were successfully synthesized by direct polycondensation of a symmetry diamine,（4-（4-（2,6-diphenylpyridin-4yl）phenoxy）phenyl）-3,5-diaminobezamide（DPDAB）, and various aromatic and aliphatic dicarboxylic diacids in NMP using triphenyl phosphate（TPP） and pyridine as catalyst. The diamine and all the prepared polyamides were fully characterized by using FT-IR,¹H-NMR,UV-Vis spectroscopy, fluorimetry and elemental analysis.The inherent viscosity of polyamides ranged from 0.45 dL/g to 0.68 dL/g.All the polymers exhibited solubility in common polar aprotic solvents such as NMP,DMAc,DMF,DMSO,pyridine,HMPA,and even in less polar solvents such as THF and m-cresol at room temperature.Thermal properties of polyamides were evaluated by means of DSC,DMTA and TGA.These polymers showed glass transition temperatures（T_g） in the range of 138-210℃. Their initial decomposition temperature（T_i） varied from 265℃to 310℃under N₂.The dilute solution（0.2 g/dL） of polyamides in DMF exhibited fluorescence emission withλ_max in the range of 470-550 nm.     

Synthesis and photoluminescence properties of novel polyarylates bearing pendent naphthylamine chromophores

A new series of blue photoluminescent aromatic polyesters (polyarylates) were synthesized from 1-[N,N-di(4-carboxyphenyl)amino]naphthalene with various bisphenols by the diphenylchlorophosphate (DPCP) activated direct polycondensation in a medium of pyridine and lithium chloride. The synthesis, basic characterizations, photoluminescence and electrochemical properties of this series of novel polyarylates bearing pendent naphthylamine chromophores were investigated. All polymers not only had good solubility in many polar aprotic solvents and excellent thin-film-forming ability, but also exhibited high T_g values, good thermal stability and lower highest occupied molecular orbital (HOMO) level. Thus, these naphthylamine-containing polyarylates may be widely applied in P-LED as hole-transporting layer and blue light-emitting materials due to their proper HOMO level, excellent thermal stability and fluorescence quantum efficiency.     

Synthesis, photoluminescent and electrochromic properties of new aromatic poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s derived from 4,4′-dicarboxy-4″-methyltriphenylamine

A series of new poly(amine-hydrazide)s I were prepared from the dicarboxylic acid 4,4′-dicarboxy-4″-methyltriphenylamine with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. Polymers I were readily soluble in many common organic solvents, and could be solution cast into transparent, tough, and flexible films with good mechanical properties. Differential scanning calorimetry (DSC) indicated that the hydrazide polymers had T_g’s in the range of 222-223 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300-400 °C. The resulting poly(amine-1,3,4-oxadiazole)s II exhibited T_g’s in the range of 269-283 °C, 10% weight-loss temperatures in excess of 511 °C, and char yield at 800 °C in nitrogen higher than 63%. These poly(amine-hydrazide)s I exhibited strong UV-Vis absorption bands at 351-355 nm in NMP solution. Their photoluminescence spectra in NMP solution and film showed maximum bands around 459-461 nm in the blue region for I series. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the poly(amine-hydrazide)s I prepared by casting polymer solution onto an indium-tin oxide (ITO)-coated glass substrate exhibited one reversible oxidation redox couples at 1.32-1.33 V vs. Ag/AgCl in acetonitrile solution. All obtained poly(amine-hydrazide)s I revealed excellent stability of electrochromic characteristics, changing color from original pale yellowish to blue.     

含4-苯基二氮杂萘酮结构共聚芳酯的合成及性能

以4-[4-(4羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮(DHPZ-DA)、4,4'-二羧基二苯醚(DAPE)和2,2'-二(4-羟基苯基)丙烷(PBA)为原料,采用溶液缩聚法,合成了一系列聚芳酯,其数均分子量在1.2×104～1.7×104之间.通过FTIR和1H-NMR对聚芳酯结构进行了表征.该系列...     

Synthesis, characterization, and thermal properties of new silarylene-siloxane-acetylene polymers

New silarylene-siloxane-acetylene polymers have been synthesized by coupling reactions employing 1,3-bis(p-ethynylphenyl)-1,1,3,3-tetraphenyldisiloxane (3) as the key monomer. Their thermal properties have been evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). All of the new polymers showed good thermal stability, with their temperatures at 5% weight loss (T_d5) being higher than 540 °C under nitrogen and higher than 460 °C in air. Their char yields at 1000 °C under N₂ were above 80%. Broad exothermic peaks, attributable to reaction of the acetylenic units, were observed by DSC analysis in the temperature range 270-450 °C.     

Synthesis and characterization of some novel aromatic polyimides

Three new diamines 1,2-di(p-aminophenyloxy)ethylene, 2-(4-aminophenoxy)methyl-5-aminobenzimidazole and 4,4-(aminopheyloxy) phenyl-4-aminobenzamide were synthesized and polymerized with 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BP), 4,4′-(hexafluoroisopropyledene)diphthalic anhydride (HF) and 3,4,9,10-perylene tetracarboxylic acid dianhydride (PD) either by one step solution polymerization reaction or by two step procedure. The later includes ring opening poly-addition to give poly(amic acid), followed by cyclodehydration to polyimides with the inherent viscosities 0.62-0.97 dl/g. Majority of polymers are found to be soluble in most of the organic solvents such as DMSO, DMF, DMAc, m-cresol even at room temperature and few becomes soluble on heating. The degradation temperature of the resultant polymers falls in the ranges from 240 °C to 550 °C in nitrogen (with only 10% weight loss). Specific heat capacity at 300 °C ranges from 1.1899 to 5.2541 J g⁻¹ k⁻¹. The maximum degradation temperature ranges from 250 to 620 °C. T_g values of the polyimides ranged from 168 to 254 °C.     

Preparation and properties of fluorine-containing polyarylates from tetrafluoroisophthaloyl chloride and bisphenols

Fluorine-containing polyarylates having inherent viscosities of 0.2–0.8 dL/g were prepared from tetrafluoroisophthaloyl chloride and various bisphenols by low temperature solution polycondensation in chloroform with triethylamine or by two-phase polycondensation in a dichloromethane-water or nitrobenzene-water system with benzyltriethylammonium chloride as the phase transfer catalyst. These polyarylates were amorphous and were readily soluble in various solvents, including chloroform and N-methyl-2-pyrrolidone. The glass transition temperature of the polymer derived from 2,2-bis(4-hydroxyphenyl) propane was 150°C. These polyarylates started to lose weight around 350°C in an air or nitrogen atmosphere.     

Poly(1,3,4-oxadiazole-ether-imide)s and their polydimethylsiloxane-containing copolymers

Poly(1,3,4-oxadiazole-ether-imide)s were prepared by thermal imidization of poly(amic-acid) intermediates resulting from the solution polycondensation reaction of a bis(ether-anhydride), namely 2,2′-bis-[(3,4-dicarboxyphenoxy)phenyl]-1,4-phenylenediisopropylidene dianhydride, with different aromatic diamines containing 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole. Poly(1,3,4-oxadiazole-ether-imide)-polydimethylsiloxane copolymers were prepared by polycondensation reaction of the same bis(ether-anhydride) with equimolar quantities of an aromatic diamine having 1,3,4-oxadiazole ring and a bis(aminopropyl)polydimethylsiloxane oligomer of controlled molecular weight. A solution imidization procedure was used to convert quantitatively the poly(amic-acid) intermediates to the corresponding polyimides. All the polymers were easily soluble in polar organic solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. The polymers showed good thermal stability with decomposition temperature being above 400 °C. Solutions of some polymers in N-methylpyrrolidone exhibited blue fluorescence, having maximum emission wavelength in the range of 370-412 nm.     

Synthesis and characterization of new aromatic polyesters and a polyether derived from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone

New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71–0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200–240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229–2235, 1998     

Electrochromic properties of novel strictly alternating poly(amine-amide-imide)s with electroactive triphenylamine moieties

A series of novel triphenylamine-containing aromatic poly(amine-amide-imide)s (PAAIs) were prepared by the phosphorylation polyamidation reactions from the diamine, N,N′-bis(4-aminophenyl)-N,N′-diphenyl-1,4-phenylenediamine, and various imide ring-preformed dicarboxylic acids. All the PAAIs were amorphous, had good solubility in many polar aprotic solvents, and exhibited excellent thin film forming capability with good mechanical properties. They displayed relatively high glass-transition temperatures (220-306 °C) and good thermal stability, with 10% weight-loss temperatures in excess of 522 °C in air or nitrogen and char yields at 800 °C in nitrogen higher than 66%. The solutions of polymers in NMP exhibited strong UV-vis absorption bands with a maximum around 315 nm. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the PAAIs prepared by casting polymer solution onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.63 and 1.01 V vs. Ag/AgCl in acetonitrile solution. All the PAAIs revealed very stable electrochromic characteristics, changing color from original pale brownish to green, and then to blue at 0.67 and 1.08 V, respectively.