Thermotropic copolyamides from triethyleneglycol bis(4-carboxyphenyl)ether,aromatic diamines,and p-aminobenzoic acid modified by the monomer sequences in the copolyamides

Copolycondensations of triethyleneglycol bis(4-carboxyphenyl)ether (PEG₃), p-amino-benzoic acid (PABA), and p-phenylenediamine (PPD) were studied in order to examine the effect of monomer sequences in the copolyamides upon the transition temperatures of the resulting copolymers. Random copolymerization of these monomers resulted in the copolymers exhibiting a nematic mesophase in a wide range of PABA content. On the other hand, the sequential copolymers composed of PABA/PPD = 1/1 and 2/1, which were prepared from 4,4′-diaminobenzanilide (DABA) and N,N′-bis(4-aminobenzoyl)-p-phenylenediamine (BAB-PPD), respectively, did not show a mesophase. The copolymers of a diamine combination of DABA and PPD exhibited a nematic mesophase, despite the lack of a mesophase for each homopolymer. The combinations of DABA and other diamines were also examined. © 1994 John Wiley & Sons, Inc.     

Thermotropic copolyamides from triethyleneglycol bis(4-carboxyphenyl)ether and two kinds of aromatic diamines

Thermotropic copolyamides were prepared from triethyleneglycol bis(4-carboxy-phenyl)ether (PEG₃) and two types of diamines, substituted p-phenylenediamines and 4,4'-diaminodiphenyls, and depression of melting point and isotropization temperature of the copolymers produced were measured as a function of diamine combination. The depression was not practically observed by the combinations of homologous diamines with several kinds and numbers of substituents, but significant by those of the diamines with different lengths of the mesogenic segments, and by the molar ratios of the diamines employed. The effect was discussed in terms of deviation of interchain hydrogen bonding between amide bonds in the main chain. © 1994 John Wiley & Sons, Inc.     

Thermotropic copolyamides from triethylene glycol bis(4-carboxyphenyl) ether and o-tolidine modified by kinking monomers

Copolymers of triethylene glycol bis(4-carboxyphenylether) (PEG₃), 4,4′-diamino-3,3′-dimethylbiphenyl (o-tolidine, OT), and several kinking comonomers of dicarboxylic acids and diamines were prepared to investigate which of the comonomers is more effective to lower melting points (T_ms) and clearing temperatures (T_is) of the resulting thermotropic copolyamides. In general, diamine modifiers were more effective than dicarboxylic acid ones even having the same chemical structures. All of diamines examined depressed their transition temperatures linearly with the modifier content whereas the dicarboxylic acid modifiers yielded copolymers having different profiles. m-Aminobenzoic acid, another type of comonomer producing the polyamide of the AB structure, was also examined. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 363–368, 1999     

Thermotropic copolyamides from polyethyleneglycol bis(4-carboxyphenyl)ethers with different oxyethylene units

Copolymerizations of polyethyleneglycol bis(4-carboxyphenyl)ethers (PEG_n) with different n values were found to significantly lower the anisotropic transition temperature (T_m) of the copolymers produced, and the thermotropic copolyamides of thermally more stable nematic phases were obtained. The effect was investigated in terms of PEG_m/PEG_n molar ratios, the number of oxyethylene units, and the even—odd character of the flexible segment. Several modes of copolymerization were carried out to investigate the effect of monomer (PEG_n sequence on T_m. By these copolymerizations thermally stable copolyamides even from p-phenylenic diamines such as methyl-p-phenylenediamine and p-phenylenediamine were obtained. © 1993 John Wiley & Sons, Inc.     

Thermotropic liquid crystalline polyamides from polyethyleneglycol bis(4-carboxyphenyl)ethers

New thermotropic liquid crystalline polyamides were prepared from polyethyleneglycol bis(4-carboxyphenyl)ether (PEG_n, n = 2, 3, 4) and aromatic diamines by using triphenyl phosphite in pyridine as the condensing agent. Substituted p-phenylenediamines and 4,4′-diaminobiphenyls were successfully used; melting points and isotropization temperatures of the polyamides were changed by the kind and number of the substituents. Copolymerization of long chain aliphatic dicarboxylic acids was carried out at the lower melting point of the copolymer. Kink monomers were also incorporated into the polymer backbone. © 1993 John Wiley & Sons, Inc.     

Preparation and properties of new random and block copolyamides derived from 1,3-bis(3-aminopropyl)tetramethyldisiloxane,aromatic diamines,and isophthaloyl chloride

Random and block disiloxane-containing copolyamides were prepared through one- and two-step procedures, respectively, by the low temperature solution polycondensation in chloroform containing triethylamine hydrochloride starting from 1,3-bis(3-aminopropyl)tetramethyldisiloxane, an aromatic diamine [3,4'-diaminodiphenyl ether (ODA) or m-phenylenediamine], and isophthaloyl chloride. The random copolyamides exhibited composition-dependent single glass transition temperature (T_g), and gave transparent and tough films by solution casting or hot pressing. The ODA-based block copolyamides had two T_g's, and the solvent-cast transparent films exhibited microphase separated morphology. The block copolymers gave better quality films than the single-phase random copolymers. © 1992 John Wiley & Sons, Inc.     

Synthesis and characterization of aromatic poly(ether sulfone imide)s derived from sulfonyl bis(ether anhydride)s and aromatic diamines

Two sulfonyl group-containing bis(ether anhydride)s, 4,4′-[sulfonylbis(1,4-phenylene)dioxy]diphthalic anhydride ( IV ) and 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]diphthalic anhydride (Me- IV ), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of the bisphenolate ions of 4,4′-sulfonyldiphenol and 4,4′-sulfonylbis(2,6-dimethylphenol) with 4-nitrophthalonitrile in N,N-dimethylformamide (DMF). High-molar-mass aromatic poly(ether sulfone imide)s were synthesized via a conventional two-stage procedure from the bis(ether anhydride)s and various aromatic diamines. The inherent viscosities of the intermediate poly(ether sulfone amic acid)s were in the ranges of 0.30–0.47 dL/g for those from IV and 0.64–1.34 dL/g for those from Me- IV. After thermal imidization, the resulting two series of poly(ether sulfone imide)s had inherent viscosities of 0.25–0.49 and 0.39–1.19 dL/g, respectively. Most of the polyimides showed distinct glass transitions on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 223–253 and 252–288°C, respectively. The results of thermogravimetry (TG) revealed that all the poly(ether sulfone imide)s showed no significant weight loss before 400°C. The methyl-substituted polymers showed higher T_g's but lower initial decomposition temperatures and less solubility compared to the corresponding unsubstituted polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1649–1656, 1998     

Soluble, thermally stable poly(ester amide)s derived from terephthalic acid bis(carboxydiphenyl methyl)ester and different diamines

Terephthalic acid bis(carboxydiphenyl methyl)ester (TBE) as a new monomer for the preparation of polyamides was synthesized through the nucleophilic substitution reaction of benzilic acid with terephthaloyl chloride. This diester-diacid (TBE) was characterized using conventional spectroscopic methods. Polycondensation reactions of TBE with different aromatic and semi-aromatic diamines via Yamazaki method resulted different poly(ester amide)s. All the polymers were characterized and their physical and thermal properties were studied.     

Wholly aromatic thermotropic liquid crystalline polyesters of 3,3′-bis(phenyl)-4,4′-biphenol with 4,4′-benzophenone dicarboxylic acid

A series of wholly aromatic, thermotropic polyesters, derived from 3,3′-bis(phenyl)-4,4′-biphenol (DPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various linear comonomers, were prepared by the melt polycondensation reaction and characterized for their thermotropic properties by a variety of experimental techniques. The homopolymer of DPBP with 4,4′-BDA had a fusion temperature (T_f) at 265°C, exhibited a nematic phase, and had a liquid crystalline range of 105°C. All of the copolyesters of DPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), or 50 mol % terephthalic acid (TA), 2,6-naphthalenedicarboxylic acid (2,6-NDA) had low T_f values in the range of 220–285°C, exhibited a nematic phase, and had accessible isotropization transitions (T_i) in the range of 270–420°C, respectively. Their accessible T_i values would enable one to observe a biphase structure. Each of the copolymers with HBA or HNA had a much broader range of liquid crystalline phase. In contrast, each of the copolymers with TA or 2,6-NDA had a relatively narrow range of liquid crystalline phase. Each of these polyesters had a glassy, nematic morphology that was confirmed with the DSC, PLM, WAXD, and SEM studies. As expected, they had higher glass transition temperatures (T_g) in the range of 161–217°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (T_d) in the range of 494–517°C, respectively. Despite their noncrystallinity, they were not soluble in common organic solvents with the exception that the homopolymer and its copolymer with TA had limited solubility in CHCl₃. However, they were soluble in the usual mixture of p-chlorophenol/1,1,2,2-tetrachloroethane (60/40 by weight) with the exception of the copolymer with 2,6-NDA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 769–785, 1997     

Synthesis and properties of aromatic polyamides based on a benzonorbornane bis(ether carboxylic acid)

A set of new aromatic polyamides containing ether and benzonorbornane units were synthesized by the direct phosphorylation polycondensation of 3,6‐bis(4‐carboxyphenoxy)benzonorbornane with various aromatic diamines. The polymers were produced in high yields and moderate to high inherent viscosities (0.64–1.70 dL/g). The polyamides derived from rigid diamines such as p‐phenylenediamine and benzidine were semicrystalline and insoluble in organic solvents. The other polyamides were amorphous and organosoluble and afforded flexible and tough films via solution casting. These films exhibited good mechanical properties, with tensile strengths of 95–101 MPa, elongations at break of 13–25%, and initial moduli of 1.97–2.33 GPa. The amorphous polyamides showed glass‐transition temperatures between 176 and 212 °C (by differential scanning calorimetry) and softening temperatures between 194 and 213 °C (by thermomechanical analysis). Most of the polymers did not show significant weight loss before 450 °C in nitrogen or in air. Some properties of these polyamides were also compared with those of homologous counterparts without the pendent norbornane groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 947–957, 2002     

Synthesis and Characterization of （4R,5R）-1,3-dioxolance-4,5-bis（2-pyridineacrboxylic acid）

The title compound, (4R,5R)-1,3-dioxolance-4,5-bis(2-pyridineacrboxylic acid), has been synthesized and characterized by single-crystal X-ray diffraction, IR, NMR, and MS analyses. Crystal structure of the title compound was grown from ETOH by slow diffusion at room temperature. The title compound crystallizes in monoclinic, space group C2 with a = 17.805(3), b = 11.459(3), c = 11.1656(17) , β = 113.066(4)°, V = 2095.9(6) 3, Z = 4, F(000) = 880, Dc = 1.332 Mg/m-3, C23H20N2O6, Mr = 420.41 and μ = 0.10 mm-1     

Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of new poly(amide‐imide)s based on 1,4‐bis(4‐trimellitimidophenoxy)naphthalene and aromatic diamines

A diimide dicarboxylic acid, 1,4‐bis(4‐trimellitimidophenoxy)naphthalene (1,4‐BTMPN), was prepared by condensation of 1,4‐bis(4‐aminophenoxy)naphthalene and trimellitic anhydride at a 1 : 2 molar ratio. A series of novel poly(amide‐imide)s (IIa–k) with inherent viscosities of 0.72 to 1.59 dL/g were prepared by triphenyl phosphite‐activated polycondensation from the diimide‐diacid 1,4‐BTMPN with various aromatic diamines (Ia–k) in a medium consisting of N‐methyl‐2‐pyrrolidinone (NMP), pyridine, and calcium chloride. The poly(amide‐imide)s showed good solubility in NMP, N,N‐dimethylacetamide, and N,N‐dimethylformamide. The thermal properties of the obtained poly(amide‐imide)s were examined with differential scanning calorimetry and thermogravimetry analysis. The synthesized poly(amide‐imide)s possessed glass‐transition temperatures in the range of 215 to 263°C. The poly(amide‐imide)s exhibited excellent thermal stabilities and had 10% weight losses at temperatures in the range of 538 to 569°C under a nitrogen atmosphere. A comparative study of some corresponding poly(amide‐imide)s also is presented. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1–8, 2000     

Synthesis and Structural Characterization of Cu（pic）2[CO（NH2）2]2 and （picH2）2[Cu（pic）2（SCN）2]

1 INTRODUCTION The picolinic acid (picH), also called pyridine- 2-carboxylic acid, has a broad spectrum of physio- logical effects on the activity functions of both ani- mal and plant organisms. It is attributed increasing interest due to its ability to …     

Synthesis of poly(ether ketone amide)s containing 4‐aryl‐2,6‐ diphenylpyridine moieties by a heterogeneous palladium‐catalyzed polycondensation of aromatic diiodides,aromatic diamines,and carbon monoxide

New aromatic poly(ether ketone amide)s containing 4‐aryl‐2,6‐diphenylpyridine units were prepared by the heterogeneous palladium‐catalyzed carbonylative polymerization of aromatic diiodides with ether ketone units, aromatic diamines bearing pyridine groups, and carbon monoxide. Polymerizations were performed in N,N‐dimethyl‐ acetamide (DMAc) at 120°C in the presence of a magnetic nanoparticles‐supported bidentate phosphine palladium complex [Fe₃O₄@SiO₂‐2P‐PdCl₂] as catalyst with 1,8‐diazabicycle[5,4,0]‐7‐undecene (DBU) as base and generated poly(ether ketone amide)s with inherent viscosities up to 0.79 dL/g. All the polymers were soluble in many organic solvents. These polymers showed glass transition temperatures between 219°C and 257°C and 10% weight loss temperatures ranging from 467°C to 508°C in nitrogen. These polyamides could be cast into transparent, flexible, and strong films from DMAc solution with tensile strengths of 86.4 to 113.7 MPa, tensile moduli of 2.34 to 3.19 GPa, and elongations at break of 5.2% to 6.9%. These polymers also exhibited good optical transparency with an ultraviolet‐visible absorption cut‐off wavelength in the 371 to 384‐nm range. Importantly, the new heterogeneous palladium catalyst can easily be recovered from the reaction mixture by simply applying an external magnet and recycled at least 8 times without significant loss of activity. Our catalytic system not only avoids the use of an excess of PPh₃ and prevents the formation of palladium black, but also solves the basic problems of palladium catalyst recovery and reuse.     

Synthesis and properties of novel aromatic poly(o-hydroxy amide)s and polybenzoxazoles based on the bis(ether benzoyl chloride)s from hydroquinone and its methyl-, tert-butyl-, and phenyl-substituted derivatives

Four series of poly(o-hydroxy amide)s were prepared by the low-temperature solution polycondensation of the bis(ether benzoyl chloride)s extended from hydroquinone and its methyl-, tert-butyl-, or phenyl-substituted derivatives with three bis(o-aminophenol)s. Most of the poly(o-hydroxy amide)s displayed an amorphous nature, were readily soluble in various polar solvents such as N,N-dimethylacetamide (DMAc), and could be solution-cast into flexible and tough films. These poly(o-hydroxy amide)s had glass transition temperatures (T_g) in the range of 152–185°C and could be thermally cyclodehydrated into the corresponding polybenzoxazoles approximately in the region of 200–400°C, as evidenced by the DSC thermograms. The thermally converted benzoxazole polymers exhibited T_gs in the range of 215–247°C and did not show significant weight loss before 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2129–2136, 1999     

Copper(II), nickel(II) and cobalt(II) complexes of 4-cyanobenzonic acid: syntheses, crystal structures and spectral properties

Three new metal complexes, Cu(4-Hcba)₂(4-cba)₂(Py)₂ (4-Hcba=4-cyanobenzoic acid) 1 and M[H(4-cba)₂]₂(Py)₂ (M=Ni 2, Co 3), have been prepared by the treatment of 4-Hcba with the respective metal nitrate M(NO₃)₂ (M=Cu, Ni, Co) in the presence of pyridine (Py). Single-crystal X-ray diffraction analyses (3 is isostructural to 2) show that the obtained complexes are of isolated mononuclear and the metal atoms have distorted octahedral coordination environment. Two different types of intramolecular hydrogen bonds exist: asymmetrical O–HO for 1 and symmetrical OHO for 2 and 3. The crystal packing between the molecular complexes is controlled mainly by T-shaped C–Hπ interactions between pyridine and phenyl rings. Preliminary discussions on IR, UV–VIS and fluorescent spectra have also been carried out.     

含3-甲基苯基-2,3-二氮杂萘-1-酮结构聚醚酰胺的合成、表征与性能

合成了一种新型芳香二胺双-(4-氨基苯基)-4-(3-甲基-4-苯氧基)-2,3-二氮杂萘-1-酮(1)[2-(4-aminophenyl)-4-(3-methyl-4-phenoxy)-2,3-phthalazinone-1,DAMPP].采用Yamazaki体系,二胺(1)能与多种芳香二酸进行溶液亲核缩聚反应,制得一类新型聚芳醚酰胺,其特性粘度为0.40～0.60dL/g;以MS,FTIR和¹HNMR等分析手段研究了新型二胺单体及其聚合物的结构;利用DSC和TGA研究了聚合物的耐热性能,结果表明,新型聚芳酰胺具有高的玻璃化转变温度为598～620K,N2气气氛中10%热质量损失温度在673K以上.聚合物2a～2c的表面电阻系数为3.75×10¹⁴～9.87×10¹⁵Ω,体积电阻系数为1.39×10¹⁶～4.09×10¹⁶Ω·cm.聚合物在二甲基甲酰胺、1-甲基吡咯烷酮和间甲酚等极性有机溶剂中可溶解,并经浇注得到透明、韧性薄膜.     

Synthesis and characterization of fluorinated poly(amide imide)s derived from 1,4‐bis(2′‐trifluoromethyl‐4′‐trimellitimidophenoxy)benzene and aromatic diamines

A series of fluorinated poly(amide imide)s were prepared from 1,4‐bis(2′‐trifluoromethyl‐4′‐trimellitimidophenoxy)benzene and various aromatic diamines [3,3′,5,5′‐tetramethyl‐4,4′‐diaminediphenylmethane, α,α‐bis(4‐amino‐3,5‐dimethyl phenyl)‐3′‐trifluoromethylphenylmethane, 1,4‐bis(4′‐amino‐2′‐trifluoromethylphenoxy)benzene, 4‐(3′‐trifluoromethylphenyl)‐2,6‐bis(3′‐aminophenyl)pyridine, and 1,1‐bis(4′‐aminophenyl)‐1‐(3′‐trifluoromethylphenyl)‐2,2,2‐trifluoroethane]. The fluorinated poly(amide imide)s, prepared by a one‐step polycondensation procedure, had good solubility both in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and cyclopentanone, and in common organic solvents, such as tetrahydrofuran and m‐cresol. Strong and flexible polymer films with tensile strengths of 84–99 MPa and ultimate elongation values of 6–9% were prepared by the casting of polymer solutions onto glass substrates, followed by thermal baking. The poly(amide imide) films exhibited high thermal stability, with glass‐transition temperatures of 257–266 °C and initial thermal decomposition temperatures of greater than 540 °C. The polymer films also had good dielectric properties, with dielectric constants of 3.26–3.52 and dissipation factors of 3.0–7.7 × 10^?3, and acceptable electrical insulating properties. The balance of excellent solubility and thermal stability associated with good mechanical and electrical properties made the poly(amide imide)s potential candidates for practical applications in the microelectronics industry and other related fields. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1831–1840, 2003