Synthesis and characterization of novel heat resistant poly(amide imide)s

A series of new poly(amide imide)s was prepared from new diacid containing sulfone, ether, amide and imide groups with various aromatic diamines. The diacid was synthesized via four steps, starting from reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide afforded N-(4-hydroxy phenyl)-4-nitrobenzamide. In the second step, reduction of nitro group resulted in preparation of 4-amino-N-(4-hydroxy phenyl) benzamide. In the next step for the preparation of diamine, the reaction of 4-amino-N-(4-hydroxy phenyl) benzamide with bis-(4-chlorophenyl) sulfone in the presence of K₂CO₃ was achieved. The prepared sulfone ether amide diamine was reacted with two moles of trimellitic anhydride to synthesize related sulfone ether amide imide diacid. The precursors and final monomer were characterized by FT-IR, H-NMR and elemental analysis. Direct polycondensation reaction of the sulfone ether amide imide diacid with different diamines in the presence of triphenyl phosphite afforded five different poly (sulfone ether amide imide amide)s. The obtained polymers were fully characterized and their physical properties including thermal behavior, thermal stability, solubility, and inherent viscosity were studied.     

Poly(sulfone ether amide amide)s as a new generation of soluble, thermally stable polymers

A new sulfone ether amide diamine was synthesized via three steps, starting from reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide afforded N-(4-hydroxy phenyl)-4-nitrobenzamide (HPNB). In the next step, reduction of nitro group resulted in preparation of 4-amino-N-(4-hydroxy phenyl) benzamide (AHPB). Final step in the preparation of diamine was the reaction of AHPB with bis(4-chlorophenyl) sulfone in the presence of K₂CO₃. All the materials were characterized using conventional spectroscopic methods. Poly(sulfone ether amide amide)s were synthesized by polycondensation reactions of prepared diamine with different diacid chlorides (aromatic and aliphatic ones). The obtained polymers were fully characterized and their physical properties including thermal behavior, thermal stability, solubility, and inherent viscosity were studied.     

Novel thermally stable polyimides based on flexible diamine: synthesis, characterization, and properties

A novel diamine with built-in sulfone, ether, and amide structure was prepared via three-step reactions. Nucleophilic reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide led to preparation of N-(4-hydroxy phenyl)-4-nitrobenzamide (HPNB). The nitro group of this compound was reduced with hydrazine and Pd/C to afford 4-amino-N-(4-hydroxy phenyl)benzamide (AHPB). Two moles of AHPB were reacted with bis-(4-chloro phenyl)sulfone to provide a novel sulfone ether amide diamine (SEAD). All the prepared compounds were characterized by common spectroscopic methods. The prepared diamine (SEAD) used to prepare related polyimides by reaction with different aromatic dianhydrides. The obtained poly(sulfone ether amide imide)s were characterized and their properties were studied.     

Synthesis,characterization, and thermal properties of novel arylene sulfone ether polyimides and polyamides

A new aromatic sulfone ether diamine was synthesized by nucleophilic aromatic substitution reaction of 5‐amino‐1‐naphthol with bis(4‐chlorophenyl) sulfone in the presence of potassium carbonate in a polar aprotic solvent. Polycondensation reactions of the obtained diamine with pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic anhydride (6FDA) resulted in preparation of thermally stable poly(sulfone ether imide)s. Poly(sulfone ether amide)s also were prepared by reaction of the diamine with terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC). The prepared monomer and polymers were characterized by conventional methods. Physical and mechanical properties of polymers, including thermal stability, thermal behavior, solution viscosity, solubility behavior, and modulus, also were studied. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1487–1492, 2000     

Aromatic poly(sulfone sulfide amide imide)s as new types of soluble thermally stable polymers

A new diamine monomer containing flexible sulfone, sulfide, and amide units was prepared via three steps. Nucleophilic chloro displacement reaction of 4‐aminothiophenol with 4‐nitrobenzoyl chloride in the presence of propylene oxide afforded N‐(4‐mercapto‐phenyl)‐4‐nitrobenzamide and subsequent reduction of the nitro intermediate led to 4‐amino‐N‐(4‐mercapto‐phenyl)benzamide. Two moles of this amino thiophenol compound was reacted with bis‐(4‐chloro phenyl)sulfone to provide a novel diamine monomer. The diamine was reacted with aromatic dianhydrides to form polyimides via a two‐step polycondensation method, formation of poly(amic acid)s, followed by chemical imidization. The resulting polymers were characterized and their physical properties including thermal behavior, thermal stability, solubility and inherent viscosity were studied. Copyright © 2007 John Wiley & Sons, Ltd.     

Novel pyridine-based ether ester diamine and resulting thermally stable poly (ether ester amide)s

A novel pyridine-based ether ester diamine was prepared in three steps. Reaction of 1,5-dihydroxy naphthalene with 4-nitrobenzoyl chloride afforded 5-hydroxy-1-naphthyl-4-nitrobenzoate (HNNB). Reduction of nitro group resulted in preparation of an amino compound named 5-hydroxyl-1-naphthyl-4-aminobenzoate (HNAB). The diamine was synthesized by nucleophilic substitution reaction of 5-hydroxyl-1-naphthyl-4-aminobenzoate with 2,6-dichloropyridine in the presence of K₂CO₃. The obtained diamine was fully characterized and used to prepare novel thermally stable poly (ether ester amide)s via polycondensation reaction with different aromatic and aliphatic diacid chlorides. All the polymers were characterized and their physical and thermal properties were studied.     

Novel ferrocene modified poly(amide ether amide)s and investigation of physical and thermal properties

A new diamine containing ferrocene group with preformed ether and amide units was prepared via reaction of 1,1′-ferrocenedicarbonyl chloride with two moles of 2,6-bis(5-amino-1-naphthoxy)pyridine. Polycondensation reactions of the prepared diamine with different aromatic and aliphatic diacid chlorides in the presence of trimethylchlorosilane (TMSCl) resulted in preparation of novel ferrocene modified poly(amide ether amide)s. The monomer and polyamides were characterized and the effect of trimethylchlorosilane (TMSCl) as activating agent on the polymerization reaction was studied. The physical and thermal properties of the polyamides including inherent viscosity, solubility, thermal stability and behavior, flame-retardancy and crystallinity of the polymers were studied. The polymers showed good thermal stability and flame-retardancy, and also improved solubility in polar aprotic solvents.     

Synthesis and characterization of heat resistant, pyridine-based polyimides with preformed ether and ester groups

A pyridine-based diamine as a building block for the preparation of heat resistant polyimides was prepared. Reaction of 1,5-dihydroxy naphthalene with 4-nitrobenzoyl chloride resulted in preparation of 5-hydroxy-1-naphthyl-4-nitrobenzoate (HNNB). 5-Hydroxyl-1-naphthyl-4-aminobenzoate (HNAB) was prepared via reduction of nitro group of HNNB. The diamine with built-in ether and ester groups was synthesized by nucleophilic substitution reaction of HNAB with 2,6-dichloropyridine in the presence of K₂CO₃. The obtained diamine was fully characterized and its polycondensation reaction with different aromatic dianhydrides led to preparation of novel heat resistant poly (ether ester imide)s. All the polymers were characterized and their physical and thermal properties were studied.     

Novel thermally stable poly(sulfone ether ester imide)s

A novel sulfone ether ester diamine was prepared by a three-step method. Reaction of 1,5-dihydroxy naphthalene with 4-nitrobenzoyl chloride afforded 5-hydroxy-1-naphthyl-4-nitrobenzoate. Reduction of nitro group by iron powder and HCl resulted in preparation of 5-hydroxyl-1-naphthyl-4-aminobenzoate. Reaction of this compound (two moles) with bis (4-chlorophenyl) sulfone led to preparation of a novel sulfone ether ester diamine. Three novel aromatic poly(sulfone ether ester imide)s were synthesized by polycondensation reactions of the prepared diamine with aromatic dianhydrides. Conventional methods were used to characterize the structure of the monomer and polymers. Physical properties of the polymers were also studied. The polyimides showed high thermal stability.     

Novel species of soluble thermally stable poly(keto ether ether amide)s: preparation,characterization, and properties

A new diamine containing one keto and four ether groups was prepared through a three‐step reaction: first, hydroquinone was reacted with 1‐fluoro‐4‐nitrobenzene and 4‐(4‐nitrophenoxy) phenol was obtained. The next step was reduction of nitro group to amino group in which 4‐(4‐aminophenoxy) phenol was prepared. In the final step, the new diamine named as bis(4‐(4‐(4‐aminophenoxy)phenoxy)phenyl) methanone was synthesized through reaction of the later compound with 4,4′‐difluoro benzophenone. All prepared materials were fully characterized by spectroscopic methods and elemental analysis. Novel species of poly(keto ether ether amide)s were synthesized via polymerization reaction of the diamine with different diacid chlorides including terephthaloyl chloride, isophthaloyl chloride, and adipoyl chloride. All polyamides were characterized, and their properties such as thermal behavior, thermal stability, solubility, viscosity, water uptake, and crystallinity were investigated and compared together. The glass transition temperatures of the polymers were about 204–232°C, and their 10% weight losses were in the range of 396–448°C. Polymers showed high thermal stability and enhanced solubility that mainly resulted from incorporation of the diamine structure containing keto, ether, and aromatic units into polyamide backbones. Copyright © 2014 John Wiley & Sons, Ltd.     

New poly(ester amide ether amide)s from a novel flexible diamine and different diacid chlorides using TMSCl for in situ silylation

A novel flexible diamine with built-in ester, amide and ether groups named terephthalic acid bis(4-{2-[2-(2-amino ethoxy)ethoxy]ethyl carbamoyl}phenyl) ester (TABE), was synthesized via two steps. Nucleophilic reaction of 4-hydroxybenzoic acid with terephthaloyl chloride in the presence of NaOH yielded terephthaloyl bis (4-oxybenzoic) acid (TOBA). The diamine (TABE) was prepared via two direct and indirect methods. In the indirect method TOBA was converted to related diacid chloride and reacted with 1,8-diamino-3,6-dioxaoctane (DADO). Direct method was achieved through the reaction of TOBA with DADO via Yamazaki method. TOBA and TABE were fully characterized and TABE was used to prepare new poly(ester amide ether amide)s through polycondensation with different diacid chlorides in the presence of trimethylchlorosilane (TMSCl). The polymers were characterized using conventional methods and their physical properties including inherent viscosity, thermal behavior, thermal stability, crystallinity, and solubility were studied. The polymers showed good thermal stability and improved solubility.     

A new category of thermally stable poly(ether amide ether imide)s with increased solubility

Two new poly(ether amide ether imide)s (PEAEIs) were prepared from a new diamine (DA) containing ether, aliphatic, amide, naphthyl and pyridine functional groups that resulted flexible and thermally stable ultimate polymers. The DA was synthesized via two steps, starting from nucleophilic substitution reaction of 1,8‐diamino‐3,6‐dioxaoctane with 6‐chloronicotinoyl chloride in the presence of propylene oxide which, afforded dichloro‐diamide (DCDA) compound. In the second step for the preparation of DA, reaction of DCDA compound with 5‐amino‐1‐naphthol in the presence of K₂CO₃ was achieved. The new DA was then polycondensed with 2,2'‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride to produce PEAEIs. The precursor, monomer and obtained polymers were entirely characterized by FT‐IR and ¹H‐NMR spectroscopy and elemental analysis techniques. The physical properties of the polymers including solubility, thermal behavior, thermal stability, inherent viscosity, morphology and mechanical properties were studied. The new PEAEIs exhibited favorable balance of physical and thermal properties, and their solubility was improved without sacrificing their thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyarylene sulfide sulfone/ketone amide

High-molecular-weight polyarylene sulfide sulfone amide (PASSA) and polyarylene sulfide ketone amide (PASKA) were synthesized from diamine monomers containing sulfone or ketone group by a low temperature solution polycondensation reaction in anhydrous N-methylpyrrolidone (NMP). The structures of the monomers and corresponding polymers were identified by IR-spectra and UV spectra. The maximum intrinsic viscosities of the polymers were 0.72 dL/g in NMP (PASSA) and 0.62 dL/g in H₂SO₄ (PASKA) at 30 ± 0.1°C, respectively. The polymers possess excellent thermal properties with the glass transition temperature (T _g) for PASSA and PASKA are 274.9°C and 195.2°C, respectively. The initial degradation temperatures (T _i) for PASSA and PASKA are 461.55°C and 467.08°C, respectively, which suggests that PASSA and PASKA are excellent heat-resistant materials. The dissolvability experiments show that PASSA and PASKA are also corrosion resistance materials. __________ Translated from Journal of Ji Lin University (Science Edition), 2008, 46 (1) (in Chinese)     

Synthesis and properties of novel aromatic polyamides based on 4-aryl-2,6-bis(4-chlorocarbonylphenyl) pyridines

A facile synthesis of three new diacid chlorides containing pyridine ring bearing aromatic type pendant groups on its 4-position is described. The monomers were characterized by FTIR, 1HNMR, mass spectroscopies and elemental analysis. Polycondensation reactions of the prepared diacid chlorides with different commercially available diamines resulted in the preparation of novel polyamides. Optimal conditions for polyamidations were obtained via study of the model compounds. The polymers were characterized by FTIR, 1HNMR, and elemental analysis and their physical properties including solution viscosity, solubility properties, thermal stability and thermal behavior were studied as well. The polyamides show excellent thermal stability and solubility in polar aprotic solvents.     

Preparation of silicon containing polymers. II.. Effect of structure on the thermal stability of organosilicon aramids

Two silicon-containing acid dichlorides, bis(4-chlorocarbonylphenyl)dimethylsilane and bis(4-chlorocarbonylphenyl)diphenylsilane, were synthesized and reacted with 1,3-phenylene diamine, 1,4-phenylene diamine, 4,4′-diaminodiphenyl, 4,4′-diaminodiphenyl methane 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl sulfone in the preparation of 12 structurally different high molecular weight aromatic polyamides. A low-temperature interfacial polycondensation technique was used. Most of the polyamides formed tough, transparent, flexible films and were characterized by solubility, solution viscosity, infrared spectroscopy (IR), and glass transition temperature (T_g). The thermal behavior of these aramids was studied by dynamic thermogravimetry. The effect of diamine and acid dichloride structure on the aramids properties is also discussed.     

Synthesis and characterization of new poly(ether amide)s based on a new cardo monomer

A new cardo diamine monomer 3, 3‐bis‐[4‐{2′trifluoromethyl 4′‐(4″‐aminophenyl) phenoxy} phenyl]‐2‐phenyl‐2, 3‐dihydro‐isoindole‐1‐one ( 4 ) has been synthesized from potentially cheap phenolphthalein as the starting material. This diamine was used for the synthesis of a new poly(ether amide) and two co‐poly(ether amide)s using 4, 4′‐diaminodiphenyl ether (ODA) as co‐monomer by direct solution polycondensation with 5‐t‐butyl iso‐phthalic acid. These new polymers showed inherent viscosities of 0.48–0.62 dL g^?1. The resulting poly(ether amide) and co‐poly(ether amide)s were readily soluble in polar aprotic solvents like NMP, DMF, DMAc, DMSO, and pyridine. The polymers have been fully characterized by ¹H and ¹³C NMR, FTIR spectroscopy, and elemental analysis. These polymers showed glass transition temperatures in the range of 267–310°C. Thermogravimetric analysis indicated high thermal stability of these polymers at 5 and 10% weight loss temperature in air above 357°C and 419°C, respectively. The poly(ether amide) films cast from DMAc were flexible with tensile strength up to 91 MPa, elongations at break up to 11%, and modulus of elasticity up to 1.82 GPa. X‐ray diffraction measurements indicate the amorphous nature of the poly(ether amide)s. Copyright © 2009 John Wiley & Sons, Ltd.     

Heat-resistant pyridine-based poly(ether-ester)s: Synthesis, characterization and properties

A pyridine-based diacid was synthesized via nucleophilic substitution reaction of 4-hydroxy benzoic acid with 2,6-dichloropyridine in the presence of potassium carbonate. The diacid was characterized using FT-IR and 1H-NMR spectroscopic methods and also with elemental analysis. Polycondensation reaction of the diacid with different diols including 1,4-dihydroxy benzene, 1,5-dihydroxy naphthalene, bis-phenol A and bis-phenol-P resulted in preparation of pyridine-based poly(ether-ester)s. The polymers were characterized and their physical and thermal properties including inherent viscosity, molecular weight, solubility, thermal stability, thermal behavior and crystallinity were studied. They revealed high heat-resistance and improved solubility in polar solvents. Structure-property relations for the prepared polyester were also studied.     

Novel poly(amide-imide)s from 2,6-bis(5-amino-1-naphthoxy) pyridine

Reaction of 5-amino-1-naphthol with 2,6-dichloropyridine resulted in preparation of 2,6-bis(5-amino-1-naphthoxy) pyridine (AN). This pyridine-based ether diamine was reacted with two moles of trimellitic anhydride (TMA) to synthesize related diimide-diacid (DIDA). Direct polycondensation reaction of DIDA with different diamines in the presence of triphenyl phosphite (TPP) afforded seven different poly(amide-imide)s. All the polymers were characterized and their physical and thermal properties were studied. The inherent viscosity of the polymers was about 0.44-0.50 dl g⁻¹ and they showed high thermal stability.     

Organosoluble Aliphatic-Aromatic Poly（ether-amide）s Based on Pyridine Moiety in the Main Chain： Synthesis,Characterization and Thermal Studies

A series organosoluble and heterocyclic poly（ether-amide）s （PEA）s were synthesized from a new diamine containing pyridine moiety and four aliphatic-aromatic dicarboxylic acids by direct polycondensation reactions. Dicarboxilic acids 4a-4d containing ether groups were synthesized in two step reactions. At first, dialdehydes 3a-3d were synthesized from four dibromo alkanes la-ld and 4-hydroxybenzaldehyde 2, then dicarboxilic acids 4a-4d were synthesized from dialdehydes 3a-3d and malonic acid in a solvent free reaction. On the other hand, the new diamine 8 containing pyridine ring was synthesized in two step reactions. The structures of synthesized monomers and polymers were proven by FTIR, NMR spectroscopy and elemental analysis. Also all of the above polymers were fully characterized by inherent viscosity, solubility tests, gel permeation chromatography （GPC）, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The resulted PEAs have shown good inherent viscosities, solubility and thermal properties.     

Miscibility studies of PVC/Aramid blends

Blends containing PVC and aramid (Ar) matrices were probed for their miscibility. In this respect, Ar chains were synthesized by aromatic diamine and diacid chloride in amide solvent. The Ar thus synthesized was characterized through Fourier transform infrared (FTIR) spectroscopy and molecular weight determination. Blend system Ar/PVC was investigated over a range of Ar/PVC ratios. Their mechanical profiles in terms of maximum stress, maximum strain, toughness, and initial moduli have been explored. Thermal properties and morphology of the blends were estimated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). A good correlation was observed between thermal, mechanical, and morphological properties of the blends. The presence of hydrogen bonding among polymers was evaluated through FTIR spectroscopy, which is believed to be responsible for the blend miscibility. Optimal thermal and mechanical profiles were depicted by the blend containing 40-wt% PVC in the Ar matrix.