Poly(arylene thioether) synthesis via nitro‐displacement reaction

High molecular weight poly(arylene thioether)s containing trifluoromethyl groups were prepared through the aromatic nucleophilic nitro‐displacement reaction of a dinitro monomer with aromatic dithiols. The high reactivity of the monomer, 4,4′‐dinitro‐3,3′‐bis(trifluoromethyl)biphenyl(1), activated by o‐trifluoromethyl groups and complete exclusion of oxygen was critical for the successful polymerization without any disulfide formation. The resulting trifluoromethylated poly(arylene thioether)s ( P1 and P2 ) were amorphous, dissolved in common organic solvents, and showed superior thermal properties compared to commercial poly(phenylene sulfide). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2440–2447, 2006     

Synthesis of fluorene‐based high performance polymers. I. Poly(arylene thioether)s with excellent solubility and high refractive index

Several poly(arylene thioether)s ( PTEs ) containing a fluorene moiety were synthesized by the polycondensation of masked dithiols such as 9,9‐bis(4‐(N,N‐dimethyl‐S‐carbamoyl)phenyl)fluorene and various difluoroarenes. All PTEs were obtained in quantitative yields. The PTEs showed good thermal stability: the 10% weight loss temperature was over 480 °C under both nitrogen and air atmosphere by TGA, and glass temperature was within a range of 204–275 °C by DSC. Most PTEs exhibited remarkably high refractive index values in a range of 1.66–1.72 at 589 nm, whereas they had a very low degree of birefringence properties. Furthermore, the PTEs showed high solubility in ordinary organic solvents such as chloroform, N‐methylpyrrolidone, and tetrahydrofuran. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3073–3082, 2007     

Poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s derived from a dihydroxy(imidoarylene) monomer

Novel poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s were synthesized from the dihydroxy(imidoarylene) monomer 1 . The syntheses of poly(arylene ether)s were carried out in DMAc in the presence of anhydrous K₂CO₃ by a nucleophilic substitution reaction between the bisphenol and activated difluoro compounds. Poly(arylene thioether)s were synthesized according to the recently discovered one-pot polymerization reaction between a bis(N,N′-dimethyl-S-carbamate) and activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃. The bis(N,N′-dimethyl-S-carbamate) 3 was synthesized by the thermal rearrangement reaction of bis(N,N′-dimethylthiocarbamate) 2 , which was synthesized from 1 by a phase-transfer catalyzed reaction. The poly(arylene thioether)s were further oxidized to form poly(arylene sulfone)s, which would be very difficult, if not impossible, to synthesize by other methods. All of the polymers described have extremely high T_gs and thermal stability as determined from DSC and TGA analysis. Poly(arylene sulfone)s have the highest T_gs and they are in the range of 298–361°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1201–1208, 1998     

Poly(arylene ether)s and poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)- phthalazinone moiety

A series of new high molecular weight poly(arylene ether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have been synthesized. The inherent viscosities of these polymers are in the range of 0.33–0.64 dL/g. They are amorphous and readily soluble in chloroform, DMF, and DMAc. The glass transition temperatures of the polymers range from 241 to 320°C and the 5% weight loss temperatures in nitrogen atmosphere range from 473 to 517°C. The hydroxy group in the monomer 1,2-dihydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one has been selectively transformed into the N,N′-dimethylthiocarbamate group, which was then rearranged to give the S-(N,N′-dimethylcarbamate) group via the Newman–Kwart rearrangement reaction. A series of poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have also been synthesized via two types of reactions, a N C coupling reaction and a one-pot reaction between the S-(N,N′-dimethylcarbamate) and activated dihalo compounds, in diphenyl sulfone in the presence of a cesium carbonate and calcium carbonate mixture. These poly(arylene thioether)s also have high glass transition temperatures (ranging from 217–303°C) and high thermal stabilities. Compared with their poly(ether) analogs, the poly(arylene thioether)s have glass transition temperatures several degrees lower, which is attributed to the more flexible C S C bonds. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 455–460, 1998     

Synthesis and proton conductivities of phosphonic acid containing poly‐(arylene ether)s

A novel phosphonic acid containing bisphenol was successfully synthesized from phenolphthalein and m‐aminophenylphosphonic acid. A series of homo‐ and copoly‐(arylene ether)s containing phosphonic acid groups were prepared by solution nucleophilic polycondensation. These phosphonic acid containing polymers can readily be dissolved in common organic solvents, such as dimethyl sulfoxide, N‐methyl‐2‐pyrrolidinone, and N‐cyclohexylpyrrolidinone, and can be cast into tough and smooth films. The presence of phosphonic acid pendants in the poly‐(arylene ether)s was confirmed by NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and conductivity measurements. This is the first report on the attachment of phenylphosphonic acid groups as side chains to aromatic polyethers. These poly‐(arylene ether)s had very high glass‐transition temperatures ranging from 254 to >315 °C and high molecular weights. The conductivities of the synthesized polymers were analyzed by the Cole–Cole method, and they ranged from 10^?5 to 10^?6 Scm^?1. The synthesized polymers also exhibited good solution processability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3218–3226, 2001     

Synthesis and characterization of poly(arylene ether)s derived from 4,4′‐bishydroxybiphenyl and 4,4′‐bishydroxyterphenyl

A series of poly(arylene ether)s were successfully prepared by aromatic, nucleophilic substitution reactions with various perfluoroalkyl‐activated bisfluoromonomers with 4,4′‐bishydroxybiphenyl and 4,4′‐bishydroxyterphenyl. 4,4′‐Bishydroxyterphenyl was synthesized through the Grignard coupling reaction of magnesium salt of 4‐bromoanisole with dibromobenzene followed by demethylation with pyridine–hydrochloride. The products obtained by the displacement of fluorine atoms exhibited good inherent viscosity, up to 0.77 dL/g, and number‐average molecular weights up to 69,300. These poly(arylene ether)s showed very good thermal stability, up to 548 °C for 5% weight loss according to thermogravimetric analysis under synthetic air, and high glass‐transition temperatures, up to 259 °C according to differential scanning calorimetry, depending on the exact repeat unit structure. These polymers were soluble in a wide range of organic solvents, such as N‐methylpyrrolidone, dimethylformamide, tetrahydrofuran, toluene, and CHCl₃, and were insoluble in dimethyl sulfoxide and acetone. Thin films of these poly(arylene ether)s showed good transparency and exhibited tensile strengths up to 132 MPa, moduli up to 3.34 GPa, and elongations at break up to 84%, depending on their exact repeating unit structures. These values are comparable to those of high‐performance thermoplastic materials such as poly(ether ether ketone) (PEEK) and Ultem poly(ether imide) (PEI). These poly(arylene ether)s exhibited low dielectric constants. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 55–69, 2002     

Synthesis of Poly(arylene ether amine)s from a Monomer Containing an Electron‐Donating Amine Group in a Nucleophilic Aromatic Substitution Reaction

Summary: Poly(arylene ether amine)s were synthesized by a nucleophilic aromatic substitution polycondensation of bis[4‐fluoro‐3‐(trifluoromethyl)phenyl]amine with several bisphenols. Even though the monomer has an electron‐donating diphenylamine moiety, which normally deactivates a nucleophilic aromatic substitution (S_NAr) reaction, the polymerization proceeded by a S_NAr reaction to give high‐molecular‐weight polymers. The polymers show good solubility in common organic solvents and have T_gs in the range of 123 °C to 177 °C.

High‐molecular‐weight poly(arylene ether amine)s synthesized by a S_NAr reaction with the monomer containing an electron‐donating diphenylamine moiety.     

Poly(arylene thioether)s containing 9,9′‐spirobifluorene moieties in the main chain: Masked dithiol‐based synthesis and excellent optical properties

Poly(arylene thioether)s ( PTEs ) containing 9,9′‐spirobifluorene moieties were synthesized in high yields from 9,9′‐spirobifluorene‐2,2′‐bis(N,N‐dimethylcarbamothioate) 4 as the masked dithiol and various difluoroarenes as electrophilic monomers. All PTEs showed high thermal stability: The 10% weight loss temperature as evaluated by thermogravimetric analysis was over 470 °C under both nitrogen and air atmospheres. The glass transition temperature estimated by DSC was in the range 210–270 °C. The PTEs showed high solubility in ordinary organic solvents, such as CHCl₃, NMP, and THF. Most PTEs exhibited remarkably high refractive indices ranging from 1.69 to 1.73 at 587.6 nm, whereas no or little birefringence was observed for the PTEs . © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4192–4199, 2010     

Synthesis and sulfonation of poly(arylene ether)s containing tetraphenyl methane moieties

Novel poly(arylene ether)s with sulfonic acid containing pendent groups were successfully synthesized by the nucleophilic displacement of aromatic dihalides with bisphenols in an aprotic solvent in the presence of excess potassium carbonate followed by sulfonation with chlorosulfonic acid. The sulfonation took place only at the controlled positions on the phenyl rings due to the novel bisphenol structures designed. The sulfonic acid group containing polymers were very soluble in common organic solvents, such as dimethyl sulfoxide, N,N′‐dimethylacetamide, and dimethylformamide, but swelled only slightly in water. These sulfonic acid group containing polymers were readily cast into tough and smooth films from organic solvents. The synthesized polymers had high glass‐transition temperatures of 171.0–240.7 °C and high molecular weights of 15,600–33,000 Da. These films could potentially be used as proton‐exchange membranes for fuel cells. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1779–1788, 2004     

Novel family of triphenylamine‐containing,hole‐transporting,amorphous, aromatic polyamides with stable electrochromic properties

We report the preparation and characterization of a series of novel electrochromic, aromatic poly(amine amide)s with pendent triphenylamine units. The synthesis proceeded via direct phosphorylation polycondensation between a novel diamine, N,N‐bis(4‐aminophenyl)‐N′,N′‐diphenyl‐1,4‐phenylenediamine, and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability and 10% weight‐loss temperatures above 540 °C. Their glass‐transition temperatures were 263–290 °C. These polymers in N‐methyl‐2‐pyrrolidinone solutions exhibited strong ultraviolet–visible absorption peaks at 307–358 nm and photoluminescence peaks around 532–590 nm in the green region. The hole‐transporting and electrochromic properties were studied with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of poly(amine amide) films prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at 0.65 and 1.03 V versus Ag/AgCl in an acetonitrile solution. All the poly(amine amide)s showed excellent stability with respect to their electrochromic characteristics; the color of the films changed from pale yellow to green and then blue at 0.85 and 1.25 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2085–2098, 2005     

Synthesis and properties of new soluble aromatic polyamides and polyimides on the basis of N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new N‐phenylated amide (N‐phenylamide) unit containing aromatic diamine, N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 3‐nitrobenzoyl chloride, followed by catalytic reduction. Two series of organosoluble aromatic poly(N‐phenylamide‐imide)s and poly(N‐phenylamide‐amide)s with inherent viscosities of 0.58–0.82 and 0.56–1.21 dL/g were prepared by a conventional two‐stage method and the direct phosphorylation polycondensation, respectively, from the diamine with various aromatic dianhydrides and aromatic dicarboxylic acids. All polyimides and polyamides are amorphous and readily soluble in many organic solvents such as N,N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with high tensile strengths. These polyimides and polyamides had glass‐transition temperatures in the ranges of 230–258 and 196–229 °C, respectively. Decomposition temperatures of the polyimides for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2564–2574, 2002     

Novel thermally stable poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s for luminescent and electrochromic materials

We describe the preparation, characterization, and luminescence of four novel electrochromic aromatic poly(amine hydrazide)s containing main‐chain triphenylamine units with or without a para‐substituted N,N‐diphenylamino group on the pendent phenyl ring. These polymers were prepared from either 4,4′‐dicarboxy‐4″‐N,N‐diphenylaminotriphenylamine or 4,4′‐dicarboxytriphenylamine and the respective aromatic dihydrazide monomers via a direct phosphorylation polycondensation reaction. All the poly(amine hydrazide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent and flexible films with good mechanical properties. These poly(amine hydrazide)s exhibited strong ultraviolet–visible absorption bands at 346–348 nm in N‐methyl‐2‐pyrrolidone (NMP) solutions. Their photoluminescence spectra in NMP solutions or as cast films showed maximum bands around 508–544 and 448–487 nm in the green and blue region for the two series of polymers. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. All obtained poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s exhibited two reversible oxidation redox couples at 0.8 and 1.24 V vs. Ag/AgCl in acetonitrile solution and revealed excellent stability of electrochromic characteristics, changing color from original pale yellow to green and then to blue at electrode potentials of 0.87 and 1.24 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3245–3256, 2005     

Synthesis and properties of novel poly(arylene ether)s and poly(arylene thioether)s based on a pyridazine biphenol or a phthalazine biphenol

Novel sulfur‐containing biphenol monomers were prepared in high yields by the reaction of 4‐mercaptophenol with chloropyridazine or chlorophthalazine compounds. High‐molecular‐weight poly(arylene ether)s were synthesized by a nucleophilic substitution reaction between these sulfur‐containing monomers and activated difluoro aromatic compounds. The inherent viscosities of these polymers ranged from 0.34 to 0.93 dL/g. The poly(pyridazine)s exhibited glass‐transition temperatures greater than 165 °C. The poly(phthalazine)s showed higher glass‐transition temperatures than the poly(pyridazine)s. A polymer synthesized from a bisphthalazinebiphenol and bis(4‐fluorophenyl)sulfone had the highest glass‐transition temperature (240 °C). The thermal stabilities of the poly(pyridazine)s and poly(phthalazine)s showed similar patterns of decomposition, with no significant weight loss below 390 °C. The poly(phthalazine)s were soluble in chlorinated solvents such as chloroform, and the poly(pyridazine)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(pyridazine)s and poly(phthalazine)s could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 262–268, 2007     

Synthesis and characterization of soluble,fluorescent poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s containing 1,3,5‐triphenylbenzene segments

The bisphenol 4,4″‐dihydroxy‐5′‐phenyl‐m‐terphenyl ( 4 ), containing a 1,3,5‐triphenylbenzene moiety, was synthesized from a pyrylium salt obtained by the reaction of benzaldehyde with p‐methoxyacetophenone with boron trifluoride etherate as a condensing agent. Polymers were obtained from 4 by a nucleophilic displacement reaction with various activated difluoro monomers and with K₂CO₃ as a base. A series of new poly(arylene ether)s ( 8a – 8f ) were obtained that contained phenyl‐substituted m‐terphenyl segments in the polymer chain. Polymers with inherent viscosities of 0.41–0.99 dL/g were obtained in yields greater than 96%. The polymers were soluble in a variety of organic solvents, including nonpolar solvents such as toluene. Clear, transparent, and flexible films cast from CHCl₃ showed high glass‐transition temperatures (T_g = 198–270 °C) and had excellent thermal stability, as shown by temperatures of 5% weight loss greater than 500 °C. 4 was converted via N,N‐dimethyl‐O‐thiocarbamate into the masked dithiol 4,4″‐bis(N,N′‐dimethyl‐S‐thiocarbamate)‐5′‐phenyl‐m‐terphenyl and was polymerized with activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃ as a base in diphenyl sulfone as a solvent. A series of new poly(arylene thioether)s ( 9a – 9e ) were obtained with T_g values similar to those of 8a – 8e . 9a – 9e were further oxidized into poly(arylene sulfone)s with T_g values 40–80 °C higher than those for 8a – 8e and 9a – 9e . These polymers also had good solubility in organic solvents. A sulfonic acid group was selectively introduced onto the pendent phenyl group of polymers 8a and 8f by reaction with chlorosulfonic acid. The polymers were soluble in dipolar aprotic solvents and formed films via casting from dimethylformamide. Polymers 8a – 8f , 11a , and 11f showed blue and red fluorescence under ultraviolet–visible light with emission maxima at 380–440 nm. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 496–510, 2002; DOI 10.1002/pola.10136     

Fluoride‐terminated hyperbranched poly(arylene ether phosphine oxide)s via nucleophilic aromatic substitution

A series of AB_x‐type triarylphosphine oxide monomers, bis‐(4‐fluorophenyl)‐(4‐hydroxyphenyl)phosphine oxide ( 4a ), bis‐(3,4‐difluorophenyl)‐(4‐hydroxyphenyl)phosphine oxide ( 4b ), and 4‐hydroxyphenyl‐bis‐(3,4,5‐trifluorophenyl)phosphine oxide ( 4c ) were prepared, characterized, and polymerized under nucleophilic aromatic substitution conditions [N‐methylpyrrolidone (NMP), K₂CO₃] to provide the corresponding hyperbranched poly(arylene ether phosphine oxide)s with number‐average molecular weights ranging from 9200 to 14,600 Da. NMR spectroscopic analysis indicated the presence of highly branched products with an approximate degree of branching of 0.57. The polymers were soluble in a variety of typical organic solvents and displayed excellent thermal stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1456–1467, 2002     

Synthesis and properties of new crystalline poly(arylene ether)s containing pendant benzoyl groups

Poly(arylene ether)s ( 3 ) containing pendant benzoyl groups were prepared by the aromatic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone (2) with hydroquinone ( 1a ) and methylhydroquinone ( 1b ) in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.8 dL/g. The polymer ( 3b ) derived from methylhydroquinone was quite soluble in common organic solvents and could be processed into uniform films from solutions. On the other hand, the polymer ( 3a ) derived from hydroquinone was only soluble in pentafluorophenol and methanesulfonic acid and had a high crystallinity. These polymers showed 10% weight losses at around 420 and 490°C in nitrogen. Polymer 3b also showed good tensile strength and tensile moduli. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 605–611, 1997     

Aromatic polyamides derived from unsymmetrical diamines containing the phthalazinone moiety

Two unsymmetrical and kink non‐coplanar heterocyclic diamines, 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)phenyl](2H)phthalazin‐1‐one and 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(4‐aminophenoxy)‐3,5‐dimethylphenyl](2H) phthalazin‐1‐one, were successfully synthesized by readily available heterocyclic bisphenol‐like monomers through two steps in high yields. A series of novel poly(arylene ether amides)s containing the phthalazinone moiety with inherent viscosities of 1.16–1.67 dL/g were prepared by the direct polymerization of novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N,N‐dimethylformamide, N,N‐dimethylacctamide, dimethyl sulfoxide, N‐methyl‐2‐pyrrolidone, and even in pyridine, chloroform and m‐cresol. The glass‐transition temperatures were in the range of 291–329 °C, and the temperatures for 5% weight loss in nitrogen were above 490 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3489–3496, 2002     

A series of new high‐performance materials based on poly[4′‐fluorophenyl‐bis(4‐phenyl)phosphine oxide]

A new series of high‐performance poly(arylene phosphine oxide) (PAPO) materials were synthesized postpolymerization from fluorinated poly(arylene phosphine oxide) (f‐PAPO). The new materials had increased solubility and film‐forming ability over the parent f‐PAPO. With the careful choice of the nucleophile, the thermal stability was also increased. The parent polymer f‐PAPO was synthesized via Ni(0) coupling from aromatic chloride and mesylate monomers. Both monomers were polymerized successfully to create polymers with intrinsic viscosities of 0.235 and 0.123 dL/g, respectively. The higher molecular weight f‐PAPO gave a glass transition of 320 °C and a char yield of 54% at 650 °C in air. The substitution of f‐PAPO via nucleophilic aromatic substitution produced PAPO thermoplastics with significant changes in the properties. The largest increase in the thermal stability relative to f‐PAPO was from 563 to 600 °C 10% weight‐loss values in nitrogen after the displacement of fluoride by 4‐aminophenol, which yielded poly[4‐(4‐aminopheonxyphenyl)bis(4′‐phenyl)phosphine oxide]. Additionally, the char yield increased from 54 to 71% in air at 650 °C. The solubility of the parent polymer was improved after substitution with 3‐tert‐butylphenol, n‐nonylamine, and poly(ethylene glycol)monomethyl ether. All of these became soluble in chloroform, N,N‐dimethylacetamide, and dimethyl sulfoxide. Copolymers were synthesized with 2,5‐dichloro‐4′‐fluorobenzophenone to improve the solubility of f‐PAPO without the loss of thermal stability. These copolymers also underwent nucleophilic aromatic substitution to create an epoxy cure agent that was used with the DEN 431 resin. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2277–2287, 2003     

Poly(arylene ether)s with pendant diphenyl phosphoryl groups: Synthesis,characterization, and thermal properties

A series of poly(arylene ether)s, (PAEs), carrying a pendant diphenyl phosphoryl group were prepared via the nucleophilic aromatic substitution (NAS) reactions of 3,5‐difluorotriphenylphosphine oxide, 6 . The difluoro monomer 6 was synthesized via two‐step reaction sequence and subsequently characterized by ¹H, ¹³C, ¹⁹F, and ³¹P NMR spectroscopy, GC/MS, and elemental analysis. The reactivity of the electrophilic sites in 6 , activated by only a diphenylphosphoryl group located in the meta‐position, in 6 was probed via NMR spectroscopy and model reactions and was determined to be sufficient to undergo typical NAS reactions. High molecular weight, amorphous, organic soluble poly(arylene ether)s, bearing a pendant diphenylphosphoryl group, were prepared via the reaction of 6 with a variety of bis‐phenols under typical NAS conditions. The poly(arylene ether)s were characterized for structure via the use of ¹H, ¹³C, and ³¹P NMR spectroscopy while their thermal properties were evaluated using DSC and TGA analysis. The glass transition temperatures (T_g) of the synthesized PAEs ranged from 143 to 175 °C, while their 5% weight loss temperatures ranged from 467 to 510 °C under nitrogen and from 470 to 526 °C in air. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of novel poly(amide urea)s,materials with outstanding mechanical properties

Four novel A‐B condensation monomers containing an amine and a carboxylic acid function are described, along with their polymerization to give main chain aromatic poly(amide urea)s. The monomers, and the polymer structural unit, are N,N′‐diphenylurea derivatives. When comparing wholly aromatic polyamides, or aramids, with the poly(amide urea)s described herein, we find that the chemical resistance to hydrolysis of the later polymers increases and their thermal resistance is diminished due to the main chain urea groups, whereas their water uptake is not greatly modified. The most striking result of the new poly(amide urea)s is their outstanding mechanical resistance: their Young's modulus rises as high as 5.5 GPa and their tensile strengths as high as 170 MPa for unoriented films prepared at laboratory scale by casting. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5398–5407, 2007