Synthesis and properties of poly(amide-imide)s based on the diimide-diacid condensed from 2,2′- bis(4-aminophenoxy)biphenyl and trimellitic anhydride

A new dicarboxylic acid having a kinked structure was synthesized from the condensation of 2,2′-bis(4-aminophenoxy)biphenyl and trimellitic anhydride. A series of biphenyl-2,2′-diyl-containing aromatic poly(amide-imide)s having inherent viscosities of 0.23–0.94 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid II with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including NMP and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films of these polymers could be cast from DMAc or NMP solutions. The glass transition temperatures of these polymers were in the range of 227–261°C and the 10% weight loss temperatures were above 520°C in nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1169–1177, 1998     

Synthesis and properties of a novel perfluorononenyloxy group containing polyarylates

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

Synthesis of new ethynylene-containing aromatic polyamides by palladium-catalyzed polycondensation of aromatic diiodides with aromatic diethynyl compounds having amide units

New ethynylene-containing aromatic polymides were synthesized by the carbon–carbon crosscoupling polycondensation of aromatic diiodides with aromatic amide-bearing diethynyl compounds in the presence of a palladium catalyst, cuprous iodide, and an organic base. The polymers having sulfone linkages were soluble in various organic solvents and their weight average molecular weights were in the range of 12,500 and 26,500. The polymers with the highest inherent viscosity were obtained, when the monomer ratio of a diethynyl compound to a diiodide was 1.01. The polymers showed no detectable glass transition temperature and no weight loss up to around 300° C in nitrogen. The thermal crosslinking of the polymers occurred at 280°C through the existing internal ethynylene group. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of soluble aromatic polyimides from 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride and aromatic diamines

Aromatic tetracarboxylic dianhydride having crank and twisted noncoplanar structure, 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with 2,2′-dihydroxy-1,1′-binaphthyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). Binaphthyl-2,2′-diyl–containing novel aromatic polyimides having inherent viscosities up to 0.67 dL/g were obtained by the one-step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and pyridine. These aromatic polyimides had glass transition temperatures in the range of 280–350°C, depending on the nature of the diamine moiety. All polymers were stable up to 400°C, with 10% weight loss being recorded above 485°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1937–1943, 1998     

Preparation and properties of aromatic polyamides from 1,4-bis(p-carboxyphenoxy)naphthyl and aromatic diamines

A new aromatic dicarboxylic acid, 1,4-bis (p-carboxyphenoxy)naphthyl ( 3 ), was synthesized by the reaction of p-fluorobenzonitrile with 1,4-naphthalenediol, followed by hydrolysis. Aromatic polyamides having inherent viscosities of 1.27–2.22 dL/g were prepared by the triphenyl phosphite activated polycondensation of diacid 3 with various aromatic diamines. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including N,N-dimethyl-acetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and m-cresol. Transparent, tough, and flexible films of these polymers could be cast from the DMAc or NMP solutions. The cast films had tensile strengths ranging from 64–104 MPa, elongations-at-break from 6 to 10%, and initial moduli from 1.52 to 2.14 GPa. These polyamides had glass transition temperatures in the range of 195 to 240°C. Almost all polymers were thermally stable up to 400°C, with 10% weight loss being recorded above 480°C in air and nitrogen atmospheres. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2273–2280, 1997     

Efficient and rapid synthesis of polyureas and polythioureas from the reaction of urea and thiourea with diamines under microwave irradiation

Polyureas and polythioureas were readily synthesized by the reaction of aromatic and aliphatic amines with urea and thioureas, respectively, in good to excellent yields under microwave irradiation. The effects of the microwave irradiation time and power, the nature of the solvent, and the solid content of the monomers on the inherent viscosity of the polymers were investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2106–2111, 2004     

Preparation and properties of new soluble aromatic polyimides from 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and aromatic diamines

A new aromatic tetracarboxylic dianhydride having a crank and twisted noncoplannar structure, 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with biphenyl-2,2′-diol, followed by hydrolysis and cyclodehydration. The biphenyl-2,2′-diyl-containing aromatic polyimides having inherent viscosities up to 0.66 dL/g were obtained by the conventional two-step procedure starting from the dianhydride monomer and various aromatic diamines. Most of the polyimides were readily soluble in amide-type solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The aromatic polyimides had glass transition temperatures in the range of 205–242°C, and began to lose weight around 415°C, with 10% weight loss being recorded at about 500°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2021–2027, 1998     

Preparation and properties of polyesters derived from 4,4′-sulfonyl dibenzoyl chloride by solution polycondensation

Sulfone-containing polyesters of 18 kinds having inherent viscosities of 1.19–0.16 dL g⁻¹ were prepared derived from 4,4′-sulfonyl dibenzoyl chloride by solution polycondensation from various aromatic and aliphatic diols in nitrobenzene at 82°C. The polyesters were examined with IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. Polyester (PE-7) with the greatest inherent viscosity may reflect that bisphenol A having a electron-releasing group increases nucleophilic properties of the phenolate anion. Diols such as bisphenol AF (PE-13) and brominated diols (PE-4, PE-10, and PE-16) gave less favorable results. The diffractograms showed that all polyesters were essentially amorphous except that obtained from bisphenol S and its derivatives. Almost all polyesters except PE-1 and PE-2 were soluble in DMF, THF, tetrachloroethane and phenol/sym-tetrachloroethane (60/40 by mass) but insoluble in typical organic solvents such as acetone, toluene, and chloroform. These polymers obtained from aromatic bisphenols lost no mass below 309°C, but 10% loss of mass was recorded above 380°C in nitrogen. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of polycarbonates based on bisphenol S by melt transesterification

Several sulfone-containing polycarbonates, having inherent viscosity 0.25–0.30 dL g⁻¹ in N,N-dimethylformamide (DMF), were prepared by melt polycondensation of diphenyl carbonate (DPC) with various aromatic and aliphatic diols, in the presence of zinc acetate as transesterification catalyst. The polycarbonates were examined with IR spectra, inherent viscosity, solubility, tensile strength, contact angle, DSC and TGA. Almost all polymers were soluble in DMF, pyridine, N-methyl pyrrolidinone (NMP), THF, phenol and dimethylsulfoxide (DMSO), partially soluble in nitrobenzene, but insoluble in acetone. Polycarbonate with introduced ether linkages leads to enhanced flexibility and elongation strength. The contact angle of the polycarbonate based on bisphenol S was found in the range 42–80°, smaller than that of polycarbonates based on bisphenol AF and bisphenol A. The wettability of polycarbonate films based on bisphenol S remarkably increased with increasing oxyethylene unit in polymer chain. The smaller values of T_d of PC-3-PC-7 than of PC-1 is attributed to the flexible ether linkage. The thermal stability of a brominated aromatic polycarbonate (PC-2) is less than that of the unbrominated one (PC-1). The brominated aromatic polycarbonate (PC-2) has good flame retardency, as indicated by the large limiting oxygen index 56. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2453–2460, 1997     

High-pressure synthesis and properties of aliphatic–aromatic polyimides via nylon-salt-type monomers derived from aliphatic diamines and benzophenonetetracarboxylic acid

Aliphatic polyimides (P-XBTA) having inherent viscosities of 0.4–1.4 dL/g were readily synthesized by the high-pressure polycondensation of the salt monomers, composed of aliphatic diamines having various methylene chain lengths (X = 4–12) and 3,3′,4,4′-benzophenonetetracarboxylic acid (BTA), under 200–250 MPa at 200–320°C. The salt monomers with odd-numbered methylene units were found to be more susceptible to crosslinking than those containing even-numbered methylene chains. The polyimides having even-numbered methylene units were highly crystalline, whereas those with odd-numbered methylene chains were crosslinked and therefore amorphous with only one exception, i.e., P-11BTA. The thermal behavior of these polymers was also studied. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 39–47, 1998     

Synthesis and properties of new soluble N-phenyl–substituted aromatic-aliphatic and all aromatic polyamides derived from 4,4′-dianilinobiphenyl

New N-phenylated aromatic-aliphatic and all aromatic polyamides were prepared by the high-temperature solution polycondensation of 4,4′-dianilinobiphenyl with both aliphatic (methylene chain lengths of 6–11) and aromatic dicarboxylic acid chlorides. All of the aromatic-aliphatic polyamides and the wholly aromatic polyamides exhibited an amorphous nature and good solubility in amide-type and chlorinated hydrocarbon solvents, except for those aromatic polyamides containing p-oriented phenylene or biphenylylene linkages in the backbone; the latter were crystalline and insoluble in organic solvents except m-cresol. The N-phenylated aromatic-aliphatic polyamides and aromatic polyamides had glass transition temperatures in the range of 79–116°C and 207–255°C, respectively, and all the polymers were thermally stable with decomposition temperatures above 400°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2193–2200, 1998     

New poly(amide–imide) syntheses. XXI. Synthesis and properties of aromatic poly(amide–imide)s based on 2,6-bis(4-trimellitimidophenoxy)naphthalene and aromatic diamines

A novel polymer-forming diimide–diacid, 2,6-bis(4-trimellitimidophenoxy)naphthalene, was prepared by the condensation reaction of 2,6-bis(4-aminophenoxy)naphthalene with trimellitic anhydride (TMA). A series of novel aromatic poly(amide–imide)s containing 2,6-bis(phenoxy)naphthalene units were prepared by the direct polycondensation of the diimide–diacid with various aromatic diamines using triphenyl phosphite (TPP) in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. Thirteen of the obtained polymers had inherent viscosities above 1.01 dL/g and up to 2.30 dL/g. Most of polymers were soluble in polar solvents such as DMAc and could be cast from their DMAc solutions into transparent, flexible, and tough films. These films had tensile strengths of 79–117 MPa, elongation-at-break of 7–61%, and initial moduli of 2.2–3.0 GPa. The wide-angle X-ray diffraction revealed that some polymers are partially crystalline. The glass transition temperatures of some polymers could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range 232–300°C. All the poly(amide–imide)s exhibited no appreciable decomposition below 450°C, and their 10% weight loss temperatures were recorded in the range 511–577°C in nitrogen and 497–601°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 919–927, 1998     

Synthesis and properties of new organo‐soluble and strictly alternating aromatic poly(ester‐imide)s from 3,3‐bis[4‐(trimellitimidophenoxy)phenyl]phthalide and bisphenols

A series of new strictly alternating aromatic poly(ester‐imide)s having inherent viscosities of 0.20–0.98 dL/g was synthesized by the diphenylchlorophosphate (DPCP) activated direct polycondensation of the preformed imide ring‐containing diacid, 3,3‐bis[4‐(trimellitimidophenoxy)phenyl]phthalide (I), with various bisphenols in a medium consisting of pyridine and lithium chloride. The diimide–diacid I was prepared from the condensation of 3,3‐bis[4‐(4‐aminophenoxy)phenyl]phthalide and trimellitic anhydride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents such as N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc). Transparent and flexible films of these polymers could be cast from their DMAc solutions. The cast films had tensile strengths ranging 66–105 MPa, elongations at break from 7–10%, and initial moduli from 1.9–2.4 GPa. The glass‐transition temperatures of these polymers were recorded between 208–275 °C. All polymers showed no significant weight loss below 400 °C in the air or in nitrogen, and the decomposition temperatures at 10% weight loss all occurred above 460 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1090–1099, 2000     

Synthesis and properties of new soluble aromatic polybenzoxazoles from 4,4′-diamino-3,3′-dihydroxytriphenylamines and aromatic dicarboxylic acids

Two new triphenylamine-based bis (o-aminophenol) monomers, 4,4′-diamino-3,3′-dihydroxytriphenylamines, were successfully synthesized by the cesium fluoride-mediated condensation of 2-(benzyloxy)-4-fluoronitrobenzene with aniline derivatives, followed by simultaneous deprotection and reduction. Aromatic polybenzoxazoles having inherent viscosities of 0.58–1.05 dL/g were obtained by the low-temperature solution polycondensation of the bis(aminophenol)s with various aromatic dicarboxylic acid chlorides and the subsequent thermal cyclodehydration of the resultant poly(hydroxyamide)s. All the polybenzoxazoles were amorphous, and most of them were soluble in organic solvents such as m-cresol and o-chlorophenol. Flexible and tough films of polybenzoxazoles could be cast from the DMAc solutions of some aromatic poly(hydroxyamide)s, followed by thermal cyclodehydration. The glass transition temperatures and 10% weight loss temperatures of the polybenzoxazoles under nitrogen were in the range of 262–327 and 610–640°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1987–1994, 1998     

Polyethers derived from bisphenols and highly fluorinated aromatics

A series of fluorinated aromatic polyethers was synthesized via aromatic nucleophilic substitution of highly fluorinated aromatics (1,2,4,5-tetrafluorobenzene, hexafluorobenzene, and decafluorobiphenyl) with bisphenol AF or bisphenol A. Polymerization with 1,2,4,5-tetrafluorobenzene was not observed, and polymerization of hexafluorobenzene with bisphenol proceeded only if the potassium carbonate–bisphenol ratio was carefully controlled. The polymer condensed from decafluorobiphenyl and bisphenol AF was prepared in 77% yield with an inherent viscosity of 1.01 dL/g. The polymer prepared from the condensation of decafluorobiphenyl with bisphenol A was obtained in 48% yield with an inherent viscosity of 0.28 dL/g. These polymers were very soluble in common organic solvents, formed clear, colorless films, and were thermally stable (> 450°C by TGA). The fully fluorinated polymer exhibited low water uptake (0.3%) and dielectric constant (2.17). © 1992 John Wiley & Sons, Inc.     

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 characterization of poly(benzazoles) containing the bicyclo[2.2.2]octane moiety

Poly(benzobisoxazoles) (PBOs), poly(benzobisthiazoles) (PBTs) and copolymers thereof containing the 2,5-dihydroxybicyclo[2.2.2]octane moiety have been prepared and studied. The homopolymers were synthesized by the polycondensation of 2,5-dihydroxybicyclo[2.2.2]octane-1,4-dicarboxylic acid with 4,6-diamino-1,3-benzenediol dihydrochloride or 2,5-diamino-1,4-benzenedithiol dihydrochloride in poly(phosphoric acid). Random and block copolymers (PBO–PBT) were also prepared. The polymers were characterized by solubility, X-ray diffraction, spectroscopy (infrared and solid-state ¹³C nuclear magnetic resonance), and thermal analysis such as differential scanning calorimetry and thermogravimetric analysis. Thermogravimetric analysis showed thermal stability of the polymers above 375°C in air and under argon atmosphere. The polymers exhibited high resistance to organic and inorganic solvents. The polymers were converted to the more stable aromatic polymers via dehydration and retro Diels–Alder reactions of the 2,5-dihydroxybicyclo[2.2.2]octyl moiety by pyrolysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 277–281, 1998     

Synthesis and properties of aromatic polyamide-benzoxazoles from trimethylsilyl-substituted 2,4-diaminophenol and aromatic dicarboxylic acid chlorides

Aromatic poly(o-hydroxy amide)s having inherent viscosities of 0.6–2.2 dL/g were readily synthesized by the low-temperature solution polycondensation of N,N′,O-tris(trimethylsilyl)-substituted 2,4-diaminophenol with aromatic dicarboxylic acid chlorides in various organic solvents. The viscosity values were much higher than those of the polymers obtained by a conventional method using parent 2,4-diaminophenol. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s at 280°C under vacuum afforded the corresponding aromatic polyamide-benzoxazoles. Most of the poly(o-hydroxy amide)s dissolved readily in amide-type solvents, whereas the polyamide-benzoxazoles were quite insoluble in organic solvents. The polyamide-benzoxazoles, which gave yellow, transparent, and tough films, had glass transition temperatures of 260–300°C and were stable up to 400°C in air.     

Synthesis and characterization of new soluble aromatic polyimides from diaminotetraphenylimidazolinone and aromatic tetracarboxylic dianhydrides

A series of new soluble aromatic polyimides with inherent viscosities of 0.65–1.12 dL/g were synthesized from 1,3-bis(4-aminophenyl)-4,5-diphenylimidazolin-2-one and various aromatic tetracarboxylic dianhydrides by the conventional two-step procedure that included ring-opening polyaddition and subsequent thermal cyclodehydration. These polyimides could also be prepared by the one-pot procedure in homogeneous m-cresol solution. Most of the tetraphenyl-pendant polyimides were soluble in organic solvents such as N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, and m-cresol. Some polyimides gave transparent, flexible, and tough films with good tensile properties. The glass transition temperatures and 10% weight loss temperatures under nitrogen of the polyimides were in the range of 287–326 and 520–580°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1767–1772, 1998     

New organo‐soluble aromatic polyimides based on 3,3′,5,5′‐tetrabromo‐2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and aromatic diamines

New aromatic tetracarboxylic dianhydride, having isopropylidene and bromo‐substituted arylene ether structure 3,3′,5,5′‐tetrabromo‐2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride, was synthesized by the reaction of 4‐nitrophthalonitrile with 3,3′,5,5′‐tetrabromobisphenol A, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). The novel aromatic polyetherimides having inherent viscosities up to 1.04 dL g⁻¹ were obtained by either a one‐step or a conventional two‐step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), pyridine, and even in less polar solvents like chloroform and tetrahydrofuran (THF). These aromatic polyimides had glass transition temperatures in the range of 256–303°C, depending on the nature of the diamine moiety. Thermogravimetric analysis (TGA) showed that all polymers were stable, with 10% weight loss recorded above 470°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1673–1680, 1999