Thermally stable polyurethane‐ureas and copolyurethane‐ureas containing zinc and nickel dihydroxysaltrien complexes

New 4,4′‐dihydroxysaltrien metal complexes, (MOHSal₂trien, where M = Zn and Ni) were synthesized and used for the synthesis of metal‐containing polyurethane‐ureas and copolyurethane‐ureas. MOHSal₂trien underwent polymerization reaction with two diisocyanates, namely 4,4′‐diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) to yield polyurethane‐ureas. Copolyurethane‐ureas were synthesized by the reaction between MOHSal₂trien, MDI, and diamines or dialcohols. The diamines or dialcohols employed were 4,4′‐methylenedianiline (MDA), hexamethylenediamine (HMA), bisphenol A (BPO), and hexamethylene glycol (HMO). The polymers were characterized by IR, NMR, elemental analysis, XRD, solubility, and viscosity. Thermal stability and flammability of polymers were studied by thermogravimetric analysis (TGA) in air and by measuring limiting oxygen index (LOI) values, respectively. It was found that the resulting metal‐containing polyurethane‐ureas and copolyurethane‐ureas exhibited good thermal stability. Among all metal‐containing polyurethane‐ureas, NiOHSal₂trien‐MDI was the most thermally stable polymer with char yield of 55% at 600°C. Solubility in DMSO of zinc‐containing copolyurethane‐ureas based on dialcohols was greatly improved when compared with those of zinc‐ and nickel‐containing polyurethane‐ureas. ZnOHSal₂trien‐MDI‐BPO and ZnOHSal₂trien‐MDI‐HMO gave high char yield of 46% at 600°C, which is almost comparable with that of NiOHSal₂trien‐MDI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of highly soluble poly(ether imide)s containing indane moieties in the main chain

A new indane containing unsymmetrical diamine monomer ( 3 ) was synthesized. This diamine monomer leads to a number of novel semifluorinated poly (ether imide)s when reacted with different commercially available dianhydrides like benzene‐1,2,4,5‐tetracarboxylic dianhydride (PMDA), benzophenone‐3,3′, 4,4′‐tetracarboxylic dianhydride (BTDA), 4,4′‐(hexafluoro‐isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐(4,4′‐Isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) by thermal imidization route. All the poly(ether imide)s showed excellent solubility in several organic solvents such as N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), tetrahydrofuran (THF), chloroform (CHCl₃) and dichloromethane (DCM) at room temperature. These light yellow poly (ether imide)s showed very low water absorption (0.19–0.30%) and very good optical transparency. Wide angle X‐ray diffraction measurements revealed that these polymers were amorphous in nature. The polymers exhibited high thermal stability up to 526°C in nitrogen with 5% weight loss, and high glass transition temperature up to 265°C. The polymers exhibited high tensile strength up to 85 MPa, modulus up to 2.5 GPa and elongation at break up to 38%, depending on the exact polymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel polyureas based on benzimidazoline‐2‐one and benzimidazoline‐2‐thione hard segments

Six novel polyureas were prepared from benzimidazolin‐2‐one and benzimidazolin‐2‐thione, which acted as hard segments, with two aromatic diisocyanates (4,4′‐diphenylmethane diisocyanate and toluene 2,4‐diisocyanate) and one aliphatic diisocyanate (hexamethylene diisocyanate). The polymers that formed were fully characterized with Fourier transform infrared spectroscopy, ¹³C‐NMR cross‐polarization/magic‐angle spinning, differential scanning calorimetry, and thermogravimetry. X‐ray diffraction revealed that the polymers contained crystalline and amorphous regions that varied with the nature of the backbone structures. All the polyureas were insoluble in common organic solvents, and this made it difficult to investigate their solution properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 576–583, 2006     

Synthesis and characterization of novel pyridine‐based polyureas with enhanced solubility and high thermal stability

The main aim of this study was the preparation of modified polyureas with improved thermal stability and solubility. Accordingly, a series of aromatic/aliphatic pyridine‐based polyureas was synthesized from the reaction of a novel diamine (DA) with different diisocyanates, including 4,4′‐diphenylmethane diisocyanate, toluene diisocyanate, 1,5‐naphthalene diisocyanate, and isophorone diisocyanate, by a solution polymerization route. The DA monomer was prepared via a two‐step reaction. The nucleophilic substitution reaction of oxydianiline with 6‐chloronicotinoylchloride led to the preparation of a diamide dichloro compound, and the subsequent reaction of this compound with 4‐aminophenol resulted in the preparation of the DA. After polymerization, the structural characterization and physical properties of the polymers were examined. The resulting polymers were soluble in common polar aprotic solvents, and they showed improved thermal stabilities in comparison with common polyureas. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of soluble poly(ether imide)s containing fluorenyl cardo groups

Two series of poly(ether imide)s (PEIs) containing fluorenyl cardo groups in the main chains were synthesized, which are derived from the polycondensation of 9,9′‐bis(4‐aminophenoxyphenyl)fluorene (BAOFL) or 9,9′‐bis(3‐trifluoromethyl,4‐aminophenoxyphenyl)fluorene (6F‐BAOFL) with four kinds of dianhydrides (3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalicanhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bisphenol‐A dianhydride), respectively. The PEI films and PEI powder were prepared by thermal and chemical imidization, respectively. The PEIs were characterized by FTIR, ¹H‐NMR, differential scanning calorimetry, thermogravimetric analysis, and UV–vis were performed on inherent viscosity, solubility, and tensile tests. The effects of fluorenyl cardo groups and ether linkages on the solubility, tensile properties, thermal stability, and optical properties were investigated in detail. It was found that the PEIs had good solubility in common organic solvents and good optical transparency in visible light region. In addition, the PEI films exhibited excellent tensile and thermal properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of novel processable polyimides derived from N,N‐bis(isocyanatoalkyl)‐1,2,4,5‐benzenetetracarboxylic‐1,2:4,5‐diimides

Two diisocyanate monomers containing methylene groups and built‐in imide structure have been prepared from the parent diacids via the Curtius–Weinstock rearrangement. Polyimides have been synthesized by solution polymerization of these isocyanates with pyromellitic dianhydride (PMDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene‐2,2‐bis(phthalic‐anhydride) (6FDA). All monomers and polymers were characterized by conventional methods, and the physical properties of the polymers, including solution viscosity, solubility, thermal stability and thermal behaviour, were studied. © 2000 Society of Chemical Industry     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Microwave‐promoted rapid synthesis of new optically active poly(amide imide)s derived from N,N′‐(pyromellitoyl)‐bis‐L‐isoleucine diacid chloride and aromatic diamines

A pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) was reacted with L ‐isoleucine in acetic acid, and the resulting imide acid [N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine] (4) was obtained in a high yield. 4 was converted into N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine diacid chloride by a reaction with thionyl chloride. The polycondensation reaction of this diacid chloride with several aromatic diamines, including 1,4‐phenylenediamine, 4,4′‐diaminodiphenyl methane, 4,4′‐diaminodiphenylsulfone (4,4′‐sulfonyldianiline), 4,4′‐diaminodiphenylether, 2,4‐diaminotoluene, and 1,3‐phenylenediamine, was developed with two methods. The first method was polymerization under microwave irradiation, and the second method was low‐temperature solution polymerization, with trimethylsilyl chloride used as an activating agent for the diamines. The polymerization reactions proceeded quickly and produced a series of optically active poly(amide imide)s with good yields and moderate inherent viscosities of 0.17–0.25 dL/g. All of the aforementioned polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 951–959, 2004     

Post and prepolymerization strategies to develop novel photochromic poly(esterimide)s

This paper reports novel photoresponsive, processable poly(esterimide)s functionalized with the azobenzene and tricyanovinylene groups. Post and prepolymerization strategies were utilized for preparation of the new photochromic polymers with imide rings. The postpolymerization method of azopolymer synthesis included a functionalization of precursor poly(esterimide) containing dialkylaminophenyl groups with diazonium salt of aniline. The precursor poly(esterimide) was obtained from synthesized 2,2′[N‐phenylethyloaniline‐di(4‐estro‐1,2‐dicarboxylic)]anhydride and 4,4′‐methylene bis(2,6‐dimethylaniline). The prepolymerization strategy based on polycondesation of 2,4‐diaminoazobenzene with two dianhydrides, that is, with or without the azobenzene group. The new dianhydride with azobenzene unit was obtained. The reaction of post‐tricyanovinylation was carried out for substitution of prepared polymers with tricyanovinylene groups. The synthesized polymers were characterized and evaluated by FTIR, ¹H NMR, X‐ray, UV‐Vis spectroscopies, and DSC. The polymers exhibited glass transition temperatures in the range of 119–208°C and good solubilities in common organic solvents, providing optical‐quality films. Thermal stability of the polymers films was investigated by UV‐Vis spectroscopy. Preliminary investigations of the optical anisotropy in chosen poly(esterimide)s were carried out by photoinduced birefringence measurements. Relatively high photoinduced birefringence (Δn = 0.01) was measured for polyimide with covalently bonded azobenzene substituted with strong acceptor group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dibenzyl structure on the macromolecular chain. XII. Polyureas: structure‐property relatonships

A series of polyureas with dibenzylic structures obtained from 2,2′‐, 2,4′‐ or 4,4′‐dibenzyl diamines and diisocyanates has been synthesized. Branched polyureas derived from a tetrafunctional monomer were also obtained. Their properties are strongly influenced by the isomeric structure of dibenzylic monomers. Polyureas containing symmetrical aromatic radicals like 4,4′‐ or 2,2′‐dibenzyl exhibit low solubility in aprotic polar solvents and, their crystallinity lies in the range 20–66%. Polymers with non‐symmetrical aromatic radicals, especially those with 2,4′‐dibenzyl exhibit, increased solubility in polar solvents; they are amorphous and have film‐forming properties. All polymers were characterized by their solubility and inherent viscosity, as well as IR spectra, thermogravimetric analysis, differential scanning calorimetry and X‐ray diffraction measurements. © 2000 Society of Chemical Industry     

Improvement of thermal stability of new heteroaromatic poly(azomethine urethane)s

New poly(azomethine urethane)s were synthesized in the conventional literature manner by reacting a new bisphenol‐containing azomethine group, N,N′‐bis(4‐hydroxyl‐3‐methoxy benzylidine)‐2,6‐diaminopyridine (I) with various diisocyanates, such as hexamethylene diisocyanate (HDI) (a), methylene‐4,4′‐diphenyl diisocyanate (MDI) (b), and toluene‐2,4‐diisocyanate (TDI) (c). The resulting polymers I(a–c) were confirmed by ¹H‐NMR, FTIR, UV, and CHN analyses. Thermogravimetric analysis (TGA) revealed that the polymers have high thermal stability. A semicrystalline behavior was noticed for polymers by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1198–1204, 2006     

Synthesis of aromatic poly(urea‐imide) with heterocyclic side‐chain structure

The poly(urea‐imide) copolymers with inherent viscosity of 0.81–1.08 dL/g were synthesized by reacting aryl ether diamine or its polyurea prepolymer with various diisocyanate‐terminated polyimide prepolymers. The aryl ether diamine was obtained by first nucleophilic substitution of phenolphthalein with p‐chloronitrobenzene in the presence of anhydrous potassium carbonate to form a dinitro aryl ether, and then further hydrogenated to diamine. The polyimide prepolymers were prepared by using 4,4′‐diphenylmethane diisocyanate to react with pyromellitic dianhydride, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride, or 3,3′,4,4′‐sulfonyldiphthalic anhydride by using the direct one‐pot method to improve their solubility, but without sacrificing thermal property. These copolymers are amorphous and readily soluble in a wide range of organic solvents such as N‐methyl‐2‐pyrrolidone, dimethylimidazole, N,N‐dimethylacetamide, dimethyl sulfoxide, N,N‐dimethylformamide, m‐cresol, and sulfolane. All the poly(urea‐imides) have glass transition temperatures in the range of 205–240°C and show a 10 wt % loss at 326–352°C in nitrogen and 324–350°C in air. The tensile strength, elongation at break, and initial modulus of these copolymer films range from 42 to 79 MPa, 5 to 16%, and 1.23 to 2.02 GPa, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1719–1730, 1999     

New photosensitive poly(amid‐imide)s containing chalcone moiety and hydantoin derivatives in the main chain: Synthesis and characterization

Six new poly(amid‐imide)s containing chalchone and hydantoin moieties in the main chain were synthesized through the polycondensation reaction of 1,3‐bis[4,4′‐bis(trimellityimido)phenyl]‐2‐propenone 6 with six hydantoin derivatives 7a‐f in a medium consisting of triphenyl phosphite, calcium chloride, pyridine, and N‐methyl‐2‐pyrrolidone. The polycondensation reaction produced a series of novel poly(amid‐imide)s 8a‐f in high yields with inherent viscosities between 0.26 and 0.42 dL/g. The resulting polymers were characterized by elemental analysis, viscosity measurements, solubility test, thermo gravimetric analysis (TGA and DTG), FTIR, and UV‐Vis spectroscopy. 1,3‐bis[4,4′‐bis(trimellityimido)phenyl]‐2‐propenone 6 was prepared from a three‐step reaction by using 4‐nitro benzaldehyde 1 and 4‐nitro acetophenone 2 as precursors. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Highly fluorinated poly(ether‐imide)s derived from 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether and aromatic dianhydrides

A new diamine, 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′‐diiodo‐4,4′‐dinitrodiphenyl ether with 3,4,5‐trifluorophenylboronic acid to produce 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐dinitrodiphenyl ether (FPNPE), followed by palladium‐catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all‐aromatic poly(ether‐imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 °C were measured through the extrapolation of the concentrations used to zero. M_n and M_w of these polymers were about 10 000 and 25 000 g mol^?1, respectively. The polymers showed a good film‐forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X‐ray diffraction measurements showed that the fluoro‐containing polymers have a nearly amorphous nature. The resulting polymers had T_g values higher than 340 °C and were thermally stable, with 10% weight loss temperatures being recorded above 550 °C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials. Copyright © 2011 Society of Chemical Industry     

Properties of Waterborne Polyurethane Adhesives with Aliphatic and Aromatic Diisocyanates

A series of waterborne polyurethane (WBPU) adhesives were prepared with various ratios of aliphatic/aromatic diisocyanates, namely 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI) as an aliphatic diisocyanate and 4,4′-diphenylmethane diisocyanate (MDI) as an aromatic diisocyanate with poly(tetramethyleneoxideglycol) (PTMG), ethylene diamine (EDA) and dimethylol propionic acid (DMPA). ¹H-NMR spectroscopy was utilized to investigate the side reaction at the dispersion step during synthesis of WBPU dispersions with respect to aliphatic, aromatic and mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%), storage modulus, glass transition temperature and adhesive strength were measured with respect to aliphatic/aromatic diisocyanate contents. The adhesive strength was maximum using mixed diisocyanates containing 25 mol% MDI in WBPU adhesives.     

Aliphatic-aromatic poly(ester-imide)s from diisocyanates containing ester groups and aromatic dianhydrides

Summary Four new ester group containing diisocyanates, viz., 3,3′-(glutaryldioxy)diphenyl diisocyanate, 4,4′-(glutaryldioxy)diphenyl diisocyanate, 3,3′-(adipoyldioxy)diphenyl diisocyanate, and 4,4′-(adipoyldioxy)diphenyl diisocyanate were synthesized from the corresponding dicarboxylic acids via the Curtius rearrangement reaction. These diisocyanates were polycondensed with pyromellitic dianhydride (PMDA) and benzo-phenonetetracarboxylic dianhydride (BTDA) in dimethylacetamide to yield eight aliphatic-aromatic polyimides containing ester groups in the backbone with inherent viscosities in the range 0.25–0.70 dL/g. These poly(ester-imide)s were semicrystalline in nature and exhibited no weight loss below 300°C in air. N.C. L. Commun. No. 5330     

Probing effects of alternately‐embedded phenoxy phenyl lateral groups on properties of novel aromatic poly(ether‐urea)s

A new class of alternate aromatic poly(ether‐urea)s having bulky phenoxy phenyl lateral groups was prepared by the reaction of 2,2′‐bis[(p‐phenoxy phenyl)]‐4,4′‐diaminodiphenyl ether (PPAPE) with two diisocyanates, isophorone diisocyanate and 2,4‐tolylene diisocyanate. The limited viscosity values as well as M _n and M _w values of the resulting polymers were determined. The resulting poly(ether‐urea)s could be easily cast into optically‐transparent, flexible, and light color films. The cut‐off wavelength values and the percentage of transmittance at 800 nm were found to be at about 415 nm and 85%, respectively. PPAPE‐derived poly(ether‐urea)s showed a low‐crystallinity and had excellent solubility in polar organic solvents. T_onset, T_g, T_d5%, and T_d10% values of the PPAPE‐derived polymers measured from their DSC and TGA thermograms were up to 270, 280, 315, and 340°C, respectively. Surface morphology of the resulted poly(ether‐urea)s were also evaluated by their scanning electron microscopy images. Excellent organo‐solubility, satisfactory film quality, moderate T_g values, and good thermal stability make this class of poly (ether‐urea)s promising high‐performance polymeric materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel poly(thiourea‐ether‐imide)s derived from 4,4′‐oxydiphenyl‐bis(thiourea): probing the possibility for high‐temperature applications

Our interest in the fabrication of high‐performance polyimides has led to thiourea‐substituted poly(thiourea‐ether‐imide)s (PTEIs) with good retention of thermal properties along with flame retardancy. A new aromatic monomer, 4,4′‐oxydiphenyl‐bis(thiourea) (ODPBT), was efficiently synthesized and polymerized with various dianhydrides (pyromellitic dianhydride, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride and 4,4′‐(hexafluoroisopropylidene)diphthalic dianhydride) via two‐stage chemical imidization to fabricate a series of PTEIs. The structural characterization of ODPBT and the polymers was carried out using Fourier transform infrared, ¹H NMR and ¹³C NMR spectral techniques along with crystallinity, organosolubility, inherent viscosity and gel permeation chromatographic measurements. PTEIs bearing C?S and ? O? moieties in the backbone demonstrated an amorphous nature and were readily soluble in various amide solvents. The novel polymers had inherent viscosities of 1.16–1.23 dL g^?1 and molecular weights of ca 90 783–96 927 g mol^?1. Their thermal stability was substantiated via 10% weight loss in the temperature range 516–530 °C under inert atmosphere. The polyimides had glass transition temperatures of 260–265 °C. Incorporation of thiourea functionalities into polymer backbones is demonstrated to be an effective way to enhance their thermal properties and flame retardancy. Thus, ODPBT can be considered as an excellent candidate for use in the synthesis of high‐performance polymeric materials. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of novel optically active poly(imide–urethane)s derived from N,N′‐(pyromellitoyl)‐bis‐(L‐leucine) diisocyanate and aromatic diols

N,N′‐(Pyromellitoyl)‐bis‐(L ‐leucine) diacid was reacted with ethyl chloroformate in the presence of triethylamine followed by reaction with activated sodium azide and gave N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diacylazide in high yield. This diacylazide was heated in dry benzene and gave the unstable N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diisocyanate ( 5 ) in quantitative yield. Thus, diisocyanate 5 was generated in situ and polycondensation reaction of this monomer with several aromatic diols, such as 4,4′‐dihydroxybiphenyl, 1,4‐hydroquinone, bisphenol A, phenolphthalein and 1,4‐dihydroxyanthraquinone, was performed in dry toluene under refluxing in the presence of 1,4‐diazabicyclo[2.2.2]octane (triethylenediamine) as a catalyst. The polymerization reactions proceeded within 48 h, producing a series of optically active poly(imide–urethane)s with good yield and moderate inherent viscosity in the range 0.18–0.28 dl g^?1. All of the above polymers were fully characterized by infrared spectra, elemental analyses and specific rotation. Some structural characterization and physical properties of these optically active poly(imide–urethane)s are reported Copyright © 2003 Society of Chemical Industry     

Reduction and cyclization to form poly(benzimidazole amide imide) copolymers

Poly(amide imide) copolymers were synthesized with different molar ratios of 4,4‐diphenylmethane diisocyanate, two types of aromatic dianhydrides (pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐sulfonyl diphthalic anhydride (DSDA)), and a diacid, which was derived from 3,3′‐dinitrobenzidine and isophthaloyl chloride in a previous work. In this study, the copolymers were further reacted with a reducing agent, and the nitro groups in the copolymers were hydrogenated into amine groups. Then, the amine‐group‐containing poly(amide imide) copolymers were cyclized at 180°C to form the poly(benzimidazole imide amide) copolymers in poly(phosphoric acid), which acted as a cyclizing agent. The resultant copolymers were soluble in sulfuric acid and poly(phosphoric acid) at room temperature and in sulfolane or N‐methyl‐2‐pyrrolidone under heating to 100°C with 5% lithium chloride. According to wide‐angle X‐ray diffraction, all the copolymers were amorphous. According to thermal analysis, the glass‐transition temperature ranged from 270 to 322°C, and the 10% weight‐loss temperature ranged from 460 to 541°C in nitrogen and from 441 to 529°C in air. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 378–386, 2004