New PVK‐based nonlinear optical polymers: Enhanced nonlinearity and improved transparency

A series of poly(vinylcarbazole)‐based polymers containing sulfonyl‐based nonlinear optical chromophores as the side chains were prepared conveniently through a postfunctionalization approach. In the polymers, the subtle structure of the chromophore moieties could be easily modified by the introduction of different isolation group, to adjust the property of the resultant polymers. The polymers exhibited good optical transparency, besides their good processability and thermal stability. The poled polymer films exhibited large second harmonic generation (SHG) coefficients of d₃₃ values (up to 28.6 pm/V) with excellent thermal stability (about 90% of the maximal SHG coefficients remain at ～ 110 °C). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2983–2993, 2008     

Second‐harmonic response of a series of chiral polyesters: A joint experimental and theoretical study

A series of polyesters with π‐conjugated donor–acceptor segments was synthesized by the condensation of azobenzene‐4,4′‐dicarbonylchloride with 1,4:3,6‐dianhydro‐D‐sorbitol ([α] = + 42.5°) and biphenolic chromophores, bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylmethane and bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylsulfone. The polymers were characterized by spectral methods (IR, ultraviolet–visible, and NMR), thermal methods (thermogravimetry and differential scanning calorimetry), wide‐angle X‐ray scattering, and polarimetry. The polymers containing isosorbide units were optically active and crystalline. They exhibited glass‐transition temperature values between 100 and 160 °C and were stable up to 400 °C. The second‐harmonic generation (SHG) efficiency of the polymers was experimentally verified by a powder‐reflection technique with 2‐methyl‐4‐nitroaniline as a reference. The SHG efficiencies of the polymers were compared to those of the chromophores and explained as a function of the percentage of chiral composition. The hyperpolarizability β values were also determined by a two‐level model solvatochromic method and computational methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2868–2877, 2002     

Facile synthesis and electro‐optic activities of new polycarbonates containing tricyanofuran‐based nonlinear optical chromophores

Two series of novel electro‐optic (EO) polycarbonates containing two different kinds of nonlinear optical (NLO) chromophores with tricyanofurane (TCF) electron acceptor have been successfully prepared through the facile polycondensation between diol NLO chromophore and bisphenol A bis(chloroformate). These new polycarbonates which were characterized by ¹H‐NMR and Fourier transform infrared exhibited good solubility in common polar organic solvents. They also showed glass transition temperatures (T_g) in the range of 124–156 °C. The morphology studies indicated that these polycarbonates had good film quality before and after corona poling. The EO coefficients (r₃₃) of two polycarbonates films were up to 45 pm/V (PC‐TCFC‐2) and 75 pm/V (PC‐DFTC‐3) at the wavelength of 1310 nm. Moreover, good temporal stability of the poling‐induced dipole alignment was also achieved, and the resulting poled films of PC‐TCFC‐2 and PC‐DFTC‐3 could retain 90 and 80% of the initial EO activities at 85 °C for more than 500 h, respectively. Both EO activity and temporal stability results were better than the guest–host EO polymers containing the same concentration chromophores, which indicated that such kind of polycarbonates could effectively suppress the intermolecular electrostatic interaction and translate microscopic molecular hyperpolarizability into macroscopic EO activity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2841–2849.     

Synthesis of poly(p‐phenylene vinylene)‐ and poly(phenylene ethynylene)‐based polymers containing p‐terphenyl in the main chain with alkoxyphenyl side groups

Starting from the pyrylium salt and following a facile synthetic route, we synthesized and polymerized 4,4″‐diiodo‐2′,6′‐di[4‐(2′‐ethylhexyl)oxy]phenyl‐p‐terphenyl with p‐divinylbenzene or p‐diethynylbenzene. The resulting polymers had moderate molecular weights, were amorphous, and dissolved in tetrahydrofuran and chloroform, with glass‐transition temperatures of 120–131 °C. The polymers behaved as violet‐blue‐emitting materials with photoluminescence maxima around 420 and 450 nm in solution and in thin films, respectively. They possessed well‐defined chromophores resulting from steric interactions in the polymer chain. The photoluminescence quantum yields were up to 0.29. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2591–2600, 2002     

Enhancing the glass‐transition temperature of polyimide copolymers containing 2,2′‐bipyridine units by the coordination of nickel malenonitriledithiolate

Polyimide copolymers containing 2,2′‐bipyridine were synthesized and characterized. The glass‐transition temperatures (T_g's) of the polymers ranged from 260 to 300 °C. In contrast to most known organic chromophore‐containing polyimides, the polyimide copolymers in this study showed elevated T_g's (270–320 °C) after coordination with nickel malenonitriledithiolate inorganic chromophores. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 498–503, 2000     

Nonlinear optical side‐chain polymers post‐functionalized with high‐β chromophores exhibiting large electro‐optic property

Electro‐optic side‐chain polymers have been synthesized by the post‐functionalization of methacrylate isocyanate polymers with novel phenyl vinylene thiophene vinylene bridge (FTC) nonlinear optical chromophores. For this application, FTC‐based chromophores were modified in their electronic donor structure, exhibiting much larger molecular hyperpolarizabilities compared with the benchmark FTC. Of these new chromophores, absorption spectra, hyper‐Rayleigh scattering experiment, and thermal analysis were carried out to confirm availability as effective nonlinear optical units for electro‐optic side‐chain polymers. The electro‐optic coefficients (r₃₃) of obtained polymers were investigated in the process of in situ poling by monitoring the temperature, current flow, poling field, and electro‐optic signal. Compared with the nonsubstituted analogue, benxyloxy modified FTC chromophore significantly achieved higher nonlinear optical property, exhibiting molecular hyperpolarizability at 1.9 μm of 4600 × 10^?30 esu and an r₃₃ value of 150 pm/V at the wavelength of 1.31 μm. Synthesized electro‐optic polymers showed high glass transition temperature (T_g), so that the temporal stability examination exhibited >78% of the electro‐optic intensity remaining at 85 °C over 500 h. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of photocrosslinkable,side‐chain,second‐order nonlinear optical poly(ester imide)s with great film‐forming ability and long‐term dipole orientation stability

A series of photocrosslinkable, side‐chain, second‐order nonlinear optical (NLO) poly(ester imide)s (PEIs) based on a chromophore‐containing dianhydride, 2,2′‐{4‐[(4‐nitrophenyl)‐azo]phenyl}iminobis(ethyl benzene‐1,2‐dicarboxylic acid anhydride‐4‐carboxylate), benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride, and 4,4′‐diamino‐3,3′‐dimethyl diphenylmethane were prepared. The resulting PEIs exhibited many useful physical characteristics, such as good organosolubility, excellent film‐forming properties, high glass‐transition temperatures (186–229 °C), and high thermal decomposition temperatures. The electrooptic coefficient value of PEI3 at 650 nm was 11.5 pm/V, and high long‐term stability of the NLO chromophore alignment in the poled PEI3 film at 120 °C was observed. The temporal stability of the dipole orientation at 150 °C was further enhanced by ultraviolet irradiation because of photocrosslinking. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 303–312, 2003     

Polyimides based on 2,5‐bis(4‐aminophenoxy)biphenyl

A diamine monomer II , 2,5‐bis(4‐aminophenoxy)biphenyl, was prepared through a nucleophilic substitution reaction of phenylhydroquinone and p‐chloronitrobenzene in the presence of potassium carbonate in N,N‐dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C. A series of all‐aromatic, organosoluble polyimides bearing pendent phenyl groups were synthesized from the diamine with six kinds of commercial dianhydrides via a conventional two‐stage process. For improving solubility of polypyromellitimide, copolypyromellitimides with arbitrary solubilities were prepared from II and a pair of dianhydrides, which were mixed at certain molar ratios. These polymers showed good solubilities in N‐methyl‐2‐pyrrolidone and m‐cresol. The softening temperatures of these polyimides were recorded between 206 and 269 °C. Polymers had glass‐transition temperatures at 230–286 °C and 10% weight‐loss temperatures above 521 °C in air or nitrogen atmospheres. Their films had high tensile moduli and strengths. Excellent properties of these polyimides are attributed to the incorporation of the pendent phenyl group in diamine II . © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 429–438, 2002; DOI 10.1002/pola.10116     

Synthesis and characterization of luminescent polyethers with 2,5‐distyrylthiophene and aromatic oxadiazole chromophores

Two new luminescent copolyethers ( P1 and P2 ) with isolated 2,5‐distyrylthiophene‐emitting segments and electron‐transporting 2,5‐diphenyl‐1,3,4‐oxadiazole chromophores were successfully synthesized by the Horner–Wadworth–Emmons reaction. The solubility, optical, and electrochemical properties of the polymers were investigated and correlated with nonlinear thiophene and 1,3,4‐oxadiazole groups. P2 with pendant 1,3,4‐oxadiazole was soluble in common organic solvents such as chloroform, tetrahydrofuran, and C₂H₂Cl₄. Thermogravimetric analysis and differential scanning calorimetry showed that the copolyethers were thermally stable below 345 °C, with glass‐transition temperatures higher than 110 °C. They were yellow‐greenish emitting materials with a band gap of 2.57–2.58 eV estimated from the onset absorption. Incorporating the thiophene moiety narrowed the band gaps of the copolyethers. The photophysical and electronic properties of the polymer and the preliminary electroluminescent device made from the polymer demonstrate that the polymer may be a potential candidate material for the fabrication of polymeric light‐emitting devices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2927–2936, 2002     

Synthesis and characterization of new highly organosoluble poly(etherimide)s derived from 1,1‐bis{4‐[4‐(3,4‐dicarboxyphenoxy)phenyl]‐4‐phenylcyclohexane} dianhydride

A new bulky pendent bis(ether anhydride), 1,1‐bis[4‐(4‐dicarboxyphenoxy)phenyl]‐4‐phenylcyclohexane dianhydride, was prepared in three steps, starting from the nitrodisplacement of 1,1‐bis(4‐hydroxyphenyl)‐4‐phenylcyclohexane with 4‐nitrophthalonitrile to form bis(ether dinitrile), followed by alkaline hydrolysis of the bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s were prepared from the bis(ether anhydride) with various diamines by a conventional two‐stage synthesis including polyaddition and subsequent chemical cyclodehydration. The resulting poly(ether imide)s had inherent viscosities of 0.50–0.73 dL g^?1. The gel permeation chromatography measurements revealed that the polymers had number‐average and weight‐average molecular weights of up to 57,000 and 130,000, respectively. All the polymers showed typical amorphous diffraction patterns. All of the poly(ether imide)s showed excellent solubility in comparison with the other polyimides derived from adamantane, norbornane, cyclododecane, and methanohexahydroindane and were readily dissolved in various solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide, pyridine, cyclohexanone, tetrahydrofuran, and even chloroform. These polymers had glass‐transition temperatures of 226–255 °C. Most of the polymers could be dissolved in chloroform in as high as a 30 wt % concentration. Thermogravimetric analysis showed that all polymers were stable up to 450 °C, with 10% weight losses recorded from 458 to 497 °C in nitrogen. These transparent, tough, and flexible polymer films could be obtained by solution casting from DMAc solutions. These polymer films had tensile strengths of 79–103 MPa and tensile moduli of 1.5–2.1 GPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2066–2074, 2002     

Polyterephthalamides with naphthoxy‐pendent groups

A series of new aromatic polyamides having pendent naphthoxy groups were synthesized by the triphenyl phosphite‐activated polycondensation of (2‐naphthoxy)terephthalic acid (NOTPA) with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), pyridine, and calcium chloride. The diacid monomer NOTPA was prepared from the nitro displacement of dimethyl 2‐nitroterephthalate with the potassium naphthoxide of β‐naphthol, followed by base‐induced ester hydrolysis. All the resulting polymers were noncrystalline and readily soluble in aprotic polar solvents such as NMP and N,N‐dimethylacetamide. Almost all the polymers could be solution‐cast to tough, creasable amorphous films with good mechanical properties, the values of tensile strengths ranging from 90 to 124 MPa with initial moduli ranging from 1.72 to 2.51 GPa. Except for two examples, all the other polyamides displayed discernible glass transitions between 189 and 248 °C in the differential scanning calorimetric traces. These polyamides showed insignificant decomposition below 400 °C in nitrogen or air. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1781–1789, 2002     

Postfunctionalization of poly(propargyl methacrylate) using copper catalyzed 1,3‐dipolar Huisgen cycloaddition: An easy route to electro‐optic materials

A one‐pot synthetic route based on copper‐catalyzed Huisgen reaction has been developed to functionalize a methacrylate propargylic polymer with azido‐substituted moieties. This procedure was used for the preparation of electro‐optic materials containing well‐known Disperse Red One (DR1) chromophores along with bulky adamantyl moieties (Adam). The postfunctionalization of the propargylic polymer was successfully achieved using different molar ratios of DR1/Adam. These novel polymers exhibit high glass transition temperature owing to the rigid structure of adamantyl units. Moreover, the second harmonic generation measurements demonstrated the effectiveness of adamantyl groups to act as insulating shield limiting thus the electrostatic interactions between chromophores. Indeed, higher optimal chromophore concentration (50 mol %) than in conventional DR1‐containing polymers (30 mol %) allowed us to increase the d₃₃ coefficient up to 92 pm/V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5652–5660, 2009     

Synthesis of poly(o‐cresol) by oxidative coupling polymerization of o‐cresol

The oxidative coupling polymerization of o‐cresol was investigated using various 2‐substituted pyridine/CuCl catalysts under an oxygen atmosphere, in which 2‐phenylpyridine/CuCl and 2‐(p‐tolyl)pyridine/CuCl catalysts yielded poly(o‐cresol)s with higher regioselectivity for 1,4‐coupling. These polymerizations produced branched and crosslinked polymers in the later stages of polymerization. These polymers showed good thermal properties, such as 5% weight loss temperatures of up to 406 °C and glass transition temperatures of up to 151 °C. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 878–884     

Ring‐opening metathesis polymerization of new norbornene‐based monomers containing various chromophores

Pure exo‐functional norbornene monomers containing various chromophores such as fluorene, pyrene, and carbazole were successfully prepared via the Diels–Alder reaction and condensation reaction. The living ring‐opening metathesis polymerization (ROMP) of a fluorene‐containing monomer, exo‐2‐(fluorene‐9‐ylcarboxymethyl)norborn‐5‐ene (exo‐1), was observed and confirmed by the formation of a diblock copolymer and a linear relationship between the number‐average molecular weight and [M]/[I] ratios ([M] = monomer concentration; [I] = initiator concentration). The synthesis and characteristics of novel fluorene‐containing polymers based on pure exo‐1 are reported with Grubbs catalyst I {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂} with a high molecular weight of 3.18 × 10⁴ in 90 s ([M]/[I] = 100). However, the ROMP of pyrene‐ and carbazole‐containing monomers [exo‐5‐(pyrene methoxy carbonyl)bicyclo[2.2.1]hept‐2‐ene and exo‐5‐(carbazole ethoxy carbonyl)bicyclo[2.2.1]hept‐2‐ene, respectively] were carried out in a nonliving fashion. All the chromophore‐containing polymers showed excellent solubility in various organic solvents, particularly in chloroform, N‐methyl‐2‐pyrrolidinone, and 1,2‐dichlorobenzene. The glass transition temperatures of polynorbornenes containing various chromophores were determined to be 80–109 °C (by differential scanning calorimetry) higher than that of ring‐opened polynorbornene (glass transition temperature = 35 °C), indicating that the incorporation of the pendant aromatic moieties (e.g., fluorene, pyrene, and carbazole) could enhance the transition temperature for segmental motions of polymer chains. The photoluminescence spectra of all polymer solutions showed a strong emission in the blue region of the visible spectra. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3022–3031, 2007     

Synthesis and properties of polyimides derived from 9,10‐dialkyloxy‐1,2,3,4,5,6,7,8‐octahydro‐2,3,6,7‐anthracenetetracarboxylic 2,3:6,7‐dianhydrides

A series of new polyimides containing alicyclic units and alkyloxy side chains were prepared from 9,10‐dialkyloxy‐1,2,3,4,5,6,7,8‐octahydro‐2,3,6,7‐anthracenetetracarboxylic 2,3:6,7‐dianhydrides and various aromatic diamines. Their physical properties and structures were investigated. Polymers were obtained with inherent viscosities of 0.24–0.53 dL/g. In comparison with the aromatic polyimides, most polymers were readily soluble in common organic solvent such as N‐methylpyrrolidone and m‐cresol. These polymers had glass‐transition temperatures between 111 and 296 °C depending on the structure of the repeating unit and 10% weight‐loss temperatures of 418–477 °C in nitrogen. Wide‐angle X‐ray diffractometry for as‐polymerized samples revealed very low crystallinity and layered structures, which were better developed in the polymers with longer side chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1764–1774, 2002     

Synthesis and properties of soluble and light‐colored poly(amide‐imide‐imide)s on the basis of tetraimide‐dicarboxylic acid condensed from 4,4′‐oxydiphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane,and m‐aminobenzoic acid,and various aromatic diamines

A new type of tetraimide‐dicarboxylic acid ( I ) was synthesized starting from the ring‐opening addition of m‐aminobenzoic acid, 4,4′‐oxydiphthalic anhydride, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane at a 2:2:1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP), followed by cyclodehydration to the diacid I . A series of soluble and light‐colored poly(amide‐imide‐imide)s ( III _a–j) was prepared by triphenyl phosphite‐activated polycondensation from I with various aromatic diamines ( II _a–j). All films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 390 nm (374–390 nm) and b* values between 25.26 and 43.61; these polymers were much lighter in color than the alternating trimellitimide series. All of the polymers were readily soluble in a variety of organic solvents such as NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even in less polar m‐cresol and pyridine. Polymers III _a–j afforded tough, transparent, and flexible films that had tensile strengths ranging from 96 to 118 MPa, elongations at break from 9 to 11%, and initial moduli from 2.0 to 2.5 GPa. The glass‐transition temperatures of the polymers were recorded at 240–268 °C. They had 10% weight loss at a temperature above 540 °C and left more than 55% residue even at 800 °C in nitrogen. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 707–718, 2002; DOI 10.1002/pola.10153     

Preparation of side‐on bisazobenzene‐containing homopolymers and block copolymers via ATRP and studies on their photoisomerization and photoalignment behaviors

The preparation of a series of novel homopolymers and copolymers containing bisazobenzene chromophores with side‐on structure in the side chains via atom transfer radical polymerization (ATRP) were presented. UV–vis spectra of the thin films of these polymers under irradiation of 488 nm Ar⁺ laser suggested that the photoisomerization of the bisazobenzene chromophores happened mainly on one of the two azo groups in the bisazobenzene chromophores with similar probability due to their side‐on structure. Good photoalignment behaviors of these polymers were proved by photoinduced birefringence measurements because side‐on structure permitted the two azo groups in the bisazobenzene chromophores both participated in the trans–cis–trans photoisomerization cycles equally to induce the whole chromophore reorientation. Furthermore, the reorientation axis located at the middle of chromophore decreased the sweep volume during photoalignment. The impetus for this study was to evaluate the photoisomerization and photoalignment process of side‐on bisazobenzene‐containing polymers and to find possible applications in the photosensitive devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3460–3472, 2007     

Deep‐red emissive conjugated poly(2,6‐BODIPY‐ethynylene)s bearing alkyl side chains

Novel deep‐red emissive poly(2,6‐BODIPY‐ethynylene)s bearing dodecyl side chains (polymers A , B , and C ) have been prepared by palladium‐catalyzed Sonogashira polymerization of 2,6‐diiodo‐functionalized BODIPY monomers with 2,6‐diethynyl‐functionalized BODIPY monomers. These polymers emit in the deep‐red region with emission maxima at up to 690 nm, and exhibit significant red shifts (up to 166 and 179 nm) of both absorption and emission maxima compared with their parent BODIPY dyes due to significant extension of π‐conjugation. These polymers possess good thermal stability with decomposition temperature between 270 and 360 °C. The polymers exhibit a little larger Stokes shifts and shorter lifetime than their corresponding BODIPY dyes. The solid state thin films of polymers A , B , and C emit in near‐infrared region between 723 and 743 nm, and show significantly red shifts (up to 57 nm) in absorption and emission maxima relative to their polymer solution. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5354–5366, 2009     

Synthesis and properties of novel polyurethanes containing 3,4‐dioxybenzylidenecyanoacetate group as a nonlinear optical chromophore

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d₃₃) of the poled polymer films were around 6.9 × 10^?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002     

Synthesis and characterization of novel soluble triphenylamine‐containing aromatic polyamides based on N,N′‐bis(4‐aminophenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine, N, N′‐bis(4‐aminophenyl)‐N, N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 4‐fluoronitrobenzene, followed by catalytic reduction. A series of novel aromatic polyamides with triphenylamine units were prepared from the diamine and various aromatic dicarboxylic acids or their diacid chlorides via the direct phosphorylation polycondensation or low‐temperature solution polycondensation. All the polyamides were 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 good mechanical properties. They had useful levels of thermal stability associated with relatively high glass‐transition temperatures (257–287 °C), 10% weight‐loss temperatures in excess of 550 °C, and char yields at 800 °C in nitrogen higher than 72%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2810–2818, 2002