Thermally stable polymers from 1,4,5,8-naphthalenetetracarboxylic acid and aromatic tetraamines

Polycondensations of 1,4,5,8-naphthalenetetracarboxylic acid (NTCA) with both 3,3′-diaminobenzidine (DAB) and 1,2,4,5-tetraaminobenzene tetrahydrochloride (TAB) in polyphosphoric acid (PPA) were found to produce soluble polymers which exhibit excellent thermal stabilities. Polymer structures were deduced from infrared, thermal, and elemental analyses of model compounds and polymers. Polymer derived from TAB had a ladder-type structure. Polymers with solution viscosities near 1 or above (determined in H₂SO₄) were obtained from polymerizations near 200°C., and analysis showed these to possess a very high degree of completely cyclized benzimidazobenzophenanthroline structure. Less vigorous reaction conditions gave polymers with lower solution viscosities which appeared to be less highly cyclized. Low-viscosity polymer was also prepared from DAB and NTCA by solid-phase polycondensation. Some advancements in the solution viscosities of polymers synthesized from DAB in PPA were caused by second staging in the solid phase.     

Synthesis and characterization of phenylated pyrazino-benzimidazophenanthroline polymers

Novel phenylated quinoxaline tetraamines have been prepared and polymerized with 1,4,5,8-naphthalenetetracarboxylic acid in polyphosphoric acid solution. The resulting BBB-type polymers with pendant phenyl groups along the polymer backbone are soluble in m-cresol. The polymers, with inherent viscosities ranging from 0.3 to 0.6 dl/g in sulfuric acid, exhibited thermal stabilities near 500°C under nitrogen and near 400°C in air.     

Synthesis and Properties of Pyrrones Containing p-Benzoquinone Units

Novel pyrrones were synthesized by one-stage polycondensation in polyphosphoric acid of 2,3,5,6-tetraamino-l,4-benzoquinone with pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, or 3,4,9,10-perylenetetracarboxylic dianhydride. The prepared polymers showed a considerable percentage of imide linkages, so they were heated at 350°C under high vacuum to increase the ring closure to the pyrrone structure. The polymers were insoluble in all common polar aprotic solvents, even in dimethylacetamide-water mixture, after reduction with sodium dithionite, but were slightly soluble in concentrated sulfuric and methanesulfonic acid. The thermal decomposition of the polymers (weight loss 5%) started above 400°C both under nitrogen and in air.     

Ladder polymers from tetraaminodiquinoxalpyrene

A new fused aromatic heterocyclic tetraamine 2,3,11,12-tetraaminodiquinoxal [2,3-e,2′,3′-1] pyrene has been prepared and polymerized with 1,4,5,8-naphthalenetetracarboxylic acid and pyromellitic dianhydride. The resulting ladder polymers with inherent viscosities ranging from 0.5 to 1.0 dl/g in methanesulfonic acid exhibited thermal stabilities near 600°C in nitrogen and near 450°C in air.     

Rigid-Rod benzobisthiazole polymers with reactive fluorene moieties: Synthesis and characterization

High purity 2,7-fluorenedicarboxylic acid chloride was synthesized in a multistep reaction scheme from 2,7-dibromofluorene. Subsequent polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with terephthaloyl chloride and 2,7-fluorenedicarboxylic acid chloride led to rigid-rod benzobisthiazole polymers with reactive fluorene moieties. The proportion of fluorene in the resultant polymers was controlled through reaction stoichiometry. Soluble polymers with intrinsic viscosities as high as 33.7 dL/g (methanesulfonic acid, 30°C) were obtained if the polymerization temperature was not allowed to exceed 165°C. Insoluble, presumably crosslinked polymers were obtained at higher temperature (190–200°C). Thermal characterization of the polymers by differential thermal analysis and thermal gravimetric analysis/mass spectroscopy did not disclose any thermal transition to 450°C. Onset of weight loss in air did not occur until over 550°C.     

Synthesis and characterization of polyiminobenzothiazoles

A series of polyiminobenzothiazoles was synthesized by the polymerization of either 2,6-dichloro- or 2,6-diphenoxybenzobisthiazole with a number of aromatic diamines. A polymer was also obtained from the self-condensation of either 2-chloro- or 2-phenoxy-6-aminobenzothiazole. The polymers were characterized by their elemental analysis and infrared spectra. Thermogravimetric analysis, differential thermal analysis, and softening under load were used to evaluate their thermal properties. The polymers were found to be light tan to brown powders which showed only slight softening below their decomposition temperatures. Onset of breakdown under thermogravimetric analysis in a nitrogen atmosphere generally occurred at 375–400°C. The polymers were sparingly soluble in organic solvents and had inherent viscosities in the range of 0.11–0.55.     

A new method for the synthesis of sulfonated polynaphthylimides

A new method for the synthesis of sulfonated polynaphthylimides has been developed on the basis of the postsulfonation of high-molecular-mass polynaphthylimides with a sulfuric acid-oleum mixture. Sulfonated polymers of this type have been obtained from the polycondensation products of 5-phenylthiophenylene-1,3-diamine with dianhydrides of 1,4,5,8-naphthalenetetracarboxylic acid and 4,4′-(1,4-phenylenedicarbonyl)-bis-naphthalene-1,8-dicarboxylic acid. It has been shown that hydrogen peroxide oxidation of sulfide bridge groups of these polymers in an acidic medium yields high-molecular-mass compounds that contain sulfonic bridge fragments and, therefore, have increased thermal stabilities and enhanced proton conductivities.     

Synthesis and properties of novel sulfonated polyimides containing 1,5‐naphthylene moieties

A series of novel sulfonated polyimides (equivalent weight per sulfonic acid = 310–744 g/equiv) containing 10–70 mol % 1,5‐naphthylene moieties were synthesized as potential electrolyte materials for high‐temperature polymer electrolyte fuel cells. The polycondensation of 1,4,5,8‐naphthalene tetracarboxylic dianhydride, 4,4′‐diamino‐2,2′‐biphenyldisulfonic acid, and 1,5‐diaminonaphthalene gave the title polymer electrolytes. The polyimide electrolytes were high‐molecular‐weight (number‐average molecular weight = 36.0–350.7 × 10³ and weight‐average molecular weight = 70.4–598.5 × 10³) and formed flexible and tough films. The thermal properties (decomposition temperature > 260 °C, no glass‐transition temperature), stability to oxidation, and water absorption were analyzed and compared with those of perfluorosulfonic acid polymers. The polyimide containing 20 mol % 1,5‐naphthylene moieties showed higher proton conductivity (0.3 S cm^?1) at 120 °C and 100% relative humidity than perfluorosulfonic acid polymers. The temperature and humidity dependence of the proton conductivity was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3901–3907, 2003     

Processing studies and thermal stability of addition polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and Bis-dienes

1,4,5,8-Tetrahydro-1,4;5,8-diepoxyanthracene reacts with various anthracene end-capped polymide oligomers to form Diels-Alder cycloaddition copolymers. The polymers are soluble in common organic solvents, and dehydrate thermally at temperatures of 300–350°C to give thermal oxidatively stable pentiptycene units along the polymer backbone. Because of their high softening points and good thermal oxidative stability, the polymers are candidates for matrix resins for high temperature composite applications. To assess their usefulness for such applications, several parameters have been studied affecting the properties of the final polymer. These parameters include varying the formulated molecular weight of the end-capped prepolymers, and use of meta-substituted aromatic diamine in place of some of the para-substituted diamine. Processability of the resins was studied using rheometric spectrometry, and a processing scheme was devised. Finally, several formulations of neat resins were compression molded into coupons, and evaluated for longterm stability in air at 315 and 371°C. The best combination of good processability and thermal oxidative stability was obtained from polymers synthesized with small amounts of meta-diamine substitution and higher formulated molecular weight prepolymers.     

Synthesis and characterization of poly(benzobisthiazole)s derived from halogenated phthalic acid and isophthalic acid

Poly(benzobisthiazole)s containing tetrafluorophenyl and bromophenyl moieties were synthesized via the polycondensation of 2,5‐diamino‐1,4‐benzenedithiol dihydrochloride with tetrafluorophthalic acid and 4‐bromoisophthalic acid under a nitrogen atmosphere. The polymers were characterized by X‐ray diffraction, spectroscopy (infrared and solid‐state ¹³C NMR), and thermal analysis, including differential scanning calorimetry and thermogravimetric analysis. The thermogravimetric analysis showed that the thermal stability of the polymers was 490–515 °C under a nitrogen atmosphere. The synthesized polymers showed good solubility in organic solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3959–3966, 2002     

New polyphenylquinoxalines linked by m-terphenyl flexibilizing groups

Three new monomers with phenylglyoxyloyl groups fixed on the 4,4′-, 4,6′-, and 4,4″-positions of m-terphenyl were synthesized by different pathways. They were used to prepare a series of polyphenylquinoxalines by solution polycondensation with 3,3′-diaminobenzidine and 3,3′,4,4′-tetraaminodiphenyl ether. These polymers exhibited excellent oxidative and thermal stability as shown by thermogravimetric analysis and isothermal aging in circulating air between 300 and 450°C. Clear yellow films, cast from m-cresol solution, were used to measure their softening temperature by thermomechanical analysis (TMA). Numerical data thus obtained, indicated a thermoplastic behavior in the temperature range 300 ± 15°C. Crosslinking of the linear polymers by isothermal heat exposure under argon between 300 and 500°C was investigated by means of TMA. Molded materials were fabricated under constant pressure (996 psi) at 500–525°C with an Instron testing machine. These polymers were also used for preliminary evaluation as matrices for 181-E glass reinforced composites. Flexural values obtained after isothermal aging in air up to 400°C indicated a potential use varying from 150 hr at 350°C to 24 hr at 400°C.     

Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.     

Synthesis and thermal properties of a new class of high-temperature polyamides from hexahydrobenzodipyrrole

A series of polyamides was synthesized by the interfacial polycondensation of 1,2,3,5,6,7-hexahydrobenzo [1,2-c:4,5-c′] dipyrrole with isophthalic, terephthalic, oxydibenzoic, sebacic and adipic acid chlorides. High molecular weight polymers with inherent viscosities ranging from 0.4 to 2.3 dl/g were obtained. Polymerization with isophthaloyl chloride gave the highest molecular weight polymer in this series. These polyamides melt between 350°C and 475°C, depending on structural differences as determined by differential scanning calorimetry (DSC). Rapid weight loss in these polymers was observed in the range of 350–400°C under thermogravimetric analysis in a nitrogen atmosphere. All these polyamides are susceptible to photooxidative degradation. The results were compared with Nomex polymer poly(1,3-phenylene isophthalamide).     

Thermal properties and solubility of poly-1,4,5,8-naphthalenetetracarboxydiimides containing 1,3,5-triazine rings

Aromatic polyimides were synthesized by polymerization of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2-dialkylamino-4,6-dihydrazino-1,3,5-triazines by a solution polymerization method followed by cyclodehydration. The polyimides had number-average molecular weights over 13,000–16,000 or viscosity values of 0.23–0.65 dl/g. The x-ray diffraction diagram of polyimide I showed a crystal pattern, but the pattern became less pronounced with increasing length of the polymer side chain, and thus polyimide V showed a typical amorphous pattern. Study of the thermal stability of the polyimides by thermogravimetric analysis showed that a steep weight loss occurred in the range 380–410°C. Among the polyimides, I had only poor solubility in organic solvent, while IV and V were soluble even in general organic solvents such as tetrahydrofuran and dioxane.     

Synthesis,processing, and third-order nonlinear optical properties of benzobisthiazole polymers containing thiophene moieties

Benzobisthiazole polymers containing mono-, bi-, and terthiophene moieties were synthesized through polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with thiophene-2,5-dicarboxylic acid, 2,2′-bithiophene-5,5′-dicarboxylic acid, and 2,2′:5′,2″-terthlophene-5,5″-dicarboxylic acid, or their corresponding diacid chlorides, respectively. Intrinsic viscosities of up to 8.1 dL/g (methanesulfonic acid, 30°C) were recorded. Polymer structures were verified by elemental analysis and spectroscopic comparison of the polymers with appropriate model compounds. Onset of breakdown under thermogravimetric analysis in air occurred in the 460–590°C range with the benzobisthiazole polymers containing a monothiophene linkage being the most stable. Films suitable for third-order optical susceptibility measurements could be prepared by extrusion techniques from the benzobisthiazole polymer containing a monothiophene linkage. Degenerate four wave mixing measurements on this film yielded a third order optical susceptibility χ⁽³⁾ of approximately 4.5 × 10^?10 esu. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of azo–bisbenzylidene‐based polymers for second order nonlinear optics

Main chain polymers containing azo and bisbenzylidene moiety were synthesized by polycondensation method. The successful polymerization reaction was characterized by UV–vis absorption, FT‐IR and NMR spectroscopy. The resulting polymers were soluble in polar solvents like dimethyl formamide (DMF) and showed good thermal stability up to 250 °C. These polymers were blended with poly methyl methacrylate (PMMA) and corona poled for characterizing second harmonic generation (SHG) property. Temperature stability study of SHG intensity of poled polymer showed that it is stable up to 80 °C. To improve temperature stability further the crosslinking of polymer under UV light is proposed. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4317–4324     

Cryoscopy on sulfuric acid solutions of a heterocyclic polymer (BBB) and related compounds

Cryoscopic measurements have been carried out on solutions in sulfuric acid of a heterocyclic polymer, its monomers, and certain of its oligomers. The polymer, BBB, is prepared by the polycondensation of 1,4,5,8-naphthalenetetracarboxylic acid (NTC) with 3,3′-diaminobenzidine (DAB). The results show that the polymer, its oligomers and one of its monomers, DAB, are all extensively protonated in sulfuric acid, whereas its other monomer is not. The degree of protonation appears to be greater for the polymer than for its low molecular weight oligomers.     

Synthesis and properties of aromatic polyamides based on a benzonorbornane bis(ether carboxylic acid)

A set of new aromatic polyamides containing ether and benzonorbornane units were synthesized by the direct phosphorylation polycondensation of 3,6‐bis(4‐carboxyphenoxy)benzonorbornane with various aromatic diamines. The polymers were produced in high yields and moderate to high inherent viscosities (0.64–1.70 dL/g). The polyamides derived from rigid diamines such as p‐phenylenediamine and benzidine were semicrystalline and insoluble in organic solvents. The other polyamides were amorphous and organosoluble and afforded flexible and tough films via solution casting. These films exhibited good mechanical properties, with tensile strengths of 95–101 MPa, elongations at break of 13–25%, and initial moduli of 1.97–2.33 GPa. The amorphous polyamides showed glass‐transition temperatures between 176 and 212 °C (by differential scanning calorimetry) and softening temperatures between 194 and 213 °C (by thermomechanical analysis). Most of the polymers did not show significant weight loss before 450 °C in nitrogen or in air. Some properties of these polyamides were also compared with those of homologous counterparts without the pendent norbornane groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 947–957, 2002     

Polyamides containing thiadiazole units: Synthesis and optical properties

Highly refractive and transparent polyamides containing thiadiazole units have been developed.These polymers were prepared by a polycondensation reaction of 4,4'-(1,3,4-thiadiazole-2,5-thio) bis(methylene) dibenzoyl chloride(TDTBM-DC) and diamine which contained thioether(―S―) and sulfone units.They showed good thermal stabilities such as a relatively high glass transition temperature of 206-233 °C and a 5% weight-loss temperature(T5%) of 376-395 °C.The optical transmittance of the polymer at 450 nm is higher than 83%.The heterocycle units and plural ―S― linkages provide the polymer with a high refractive index of 1.716-1.725 at 633 nm and a low birefringence of 0.003-0.004.Also they showed improved solubility in polar aprotic solvents and could form moderate strength films with tensile strength of 72.8-83.1 MPa and storage modulus of 1.0-1.8 GPa(at 200 °C).     

Synthesis of poly(benzoxazole)s by direct polycondensation of dicarboxylic acids with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid as condensing agent and solvent

A convenient method for the synthesis of poly(benzoxazole)s of high molecular weights has been developed. These polymers were prepared readily by direct polycondensation of aromatic dicarboxylic acids containing phenyl either structure with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid (PPMA) as condensing agent and solvent. Polycondensations proceeded fast and was completed within 5 h at 140°C and produced poly(benzoxazole)s with inherent viscosities up to 4.6 dL/g. Model compound work was performed in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(benzoxazole)s showed 10% weight loss in air and nitrogen at 450–505°C and 465–535°C, respectively.