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1.
A novel hexamethylspirobichroman (HMSBC) unit-containing dicarboxylic acid, 6,6′-bis(4-carboxyphenoxy)-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman ( 3 ), was derived from nucleophilic substitution of p-fluorobenzonitrile with the phenolate ion of 6,6′-dihydroxy-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman ( 1 ), followed by alkaline hydrolysis of the intermediate bis(ether nitrile). Using TPP and pyridine as condensing agents, a series of polyamides with inherent viscosities in the range of 0.82–1.14 dL/g were prepared by the direct polycondensation of dicarboxylic acid 3 with various aromatic diamines. All the obtained polymers were noncrystalline and soluble in various organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP). Except for the polymer derived from benzidine, the other polyamides could be solution cast into transparent and tough films, and their tensile strengths, elongations at break, and tensile moduli were in the range of 56–76 MPa, 4–59%, and 1.6–2.0 GPa, respectively. These polyamides had glass transition temperatures in the range of 183–200°C with 10% weight loss above 420°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1479–1486, 1997  相似文献   

2.
The synthesis of N,N′-bis(4′-amino-4-biphenylene) isophthalamide (BABPI) and its applicability as a new diamine for the preparation of a series of new, high Tg, perfectly alternating poly(amide-imide)s is described. BABPI was synthesized from the catalytic reduction of the corresponding dinitro compound which was prepared by the condensation of isophthaloyl chloride and 4-amino-4′-nitrobiphenyl. The modified selective reduction technique was used for the preparation of 4-amino-4′-nitrobiphenyl from 4,4′-dinitro-biphenyl. Poly(amide-imide)s were synthesized by polycondensation of diamine BABPI with various commercially available aromatic dianhydrides via a conventional two-step procedure. In the first step, poly(amic-acid)s were prepared in a polar aprotic solvent, such as N-methyl pyrrolidone (NMP) at room temperature. Depending on the dianhydride used, intrinsic viscosities of poly(amic-acid)s were found to range between 0.43–0.69 dL/g. Bulk thermal imidization technique was used to obtain fully imidized poly(amide-imide)s at the second step. The synthesized poly(amide-imide)s showed good thermal stability up to 320°C and the 10% weight loss temperatures were recorded in the range of 525–550°C as evidenced by thermogravimetric analysis (TGA). The glass transition temperatures were found to be between 225–235°C from differential scanning calorimeter (DSC) measurements. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1149–1155, 1997  相似文献   

3.
A spirobichroman structure-containing diether anhydride (SBCDA), 6,6′-bis(3,4-dicarboxyphenoxy)-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman dianhydride, was prepared by the nucleophilic nitrodisplacement of 4-nitrophthalonitrile with the phenolate ion of 6,6′-dihydroxy-4,4,4′,4′,7,7′-hexamethyl-2,2′-spirobichroman, followed by alkaline hydrolysis of the intermediate tetranitrile and dehydration of the resulting tetraacid. A series of high molecular weight poly(ether imide)s with inherent viscosities between 0.45 and 1.28 dL/g were synthesized from SBCDA and various aromatic diamines via a conventional two-stage procedure that included ring-opening polyaddition in N,N-dimethylacetamide (DMAc) to give poly(amic acid)s, followed by thermal cyclization to poly(ether imide)s. The intermediate poly(amic acid)s had inherent viscosities of 0.70–1.50 dL/g. Except for the poly(ether imide) obtained from p-phenylenediamine, the other poly(ether imide)s were soluble in various organic solvents and could be solution-cast into transparent, flexible, and tough films. These poly(ether imide)s had glass transition temperatures in the range 175–262°C and showed no significant decomposition below 420°C, with 10% weight loss being recorded above 446°C in nitrogen or air. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2801–2809, 1997  相似文献   

4.
Eleven bis(phenoxy) naphthalene-containing poly(amide-imide)s IIIa–k were synthesized by the direct polycondensation of 2,7-bis (4-aminophenoxy) naphthalene (DAPON) with various aromatic bis (trimellitimide)s IIa–k in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly (amide-imide)s IIIa–k having inherent viscosities of 0.70–1.12 dL/g were obtained in quantitative yields. The polymers containing p-phenylene or bis(phenoxy) benzene units exhibited crystalline x-ray diffraction patterns. Most of the polymers were readily soluble in various solvents such as NMP, N, N-dimethylacetamide, dimethyl sulfoxide, m-cresol, o-chlorophenol, and pyridine, and gave transparent, and flexible films cast from DMAc solutions. Cast films showed obvious yield points in the stress-strain curves and had strength at break up to 87 MPa, elongation to break up to 11%, and initial modulus up to 2.10 GPa. These poly(amide-imide)s had glass transition temperatures in the range of 255–321°C, and the 10% weight loss temperatures were recorded in the range of 529–586°C in nitrogen. The properties of poly(amideimide)s IIIa–k were compared with those of the corresponding isomeric poly (amide-imide)s III′ prepared from 2,7-bis(4-trimellitimidophenoxy) naphthalene and aromatic diamines. © 1994 John Wiley & Sons, Inc.  相似文献   

5.
New bis(phenoxy)naphthalene-containing poly(amide-imide)s having an inherent viscosity in the range of 0.62–1.09 dL/g were prepared by the direct polycondensation of 1,5-bis(4-trimellitimidophenoxy) naphthalene ( I ) and various aromatic diamines using triphenyl phosphite and pyridine as condensing agents in N-methyl-2-pyrrolidone (NMP) in the presence of calcium chloride. The diimide-diacid (I) was prepared by the condensation of 1,5-bis(4-aminophenoxy) naphthalene and trimellitic anhydride. Most of the polymers were soluble in aprotic solvents such as NMP and N,N-dimethylacetamide (DMAc), and afforded transparent, flexible and tough films upon casting from DMAc solutions. Measurements of wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or oxyphenylene groups were characterized as crystalline polymers. Tensile strength and initial moduli of the polymer films ranged from 61–86 MPa and 1.83–2.21 GPa, respectively. Glass transition temperatures of the polymers were in the range of 231–340°C. The melting points of the crystalline polymers ranged from 375–430°C. The 10% weight loss temperatures were above 512°C in nitrogen and 481°C in air. © 1993 John Wiley & Sons, Inc.  相似文献   

6.
The new polymer-forming diimide-diacid, 2,3-bis(4-trimellitimidophenoxy) naphthalene (I), was readily obtained by the condensation reaction of 2,3-bis (4-aminophenoxy) naphthalene with trimellitic anhydride. A series of novel aromatic poly (amide-imide)s were prepared by the direct polycondensation of diimide-diacid I with various aromatic diamines using triphenyl phosphite in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. The resultant polymers have inherent viscosities in the range of 0.65–1.02 dL/g at 30°C in N, N-dimethylacetamide. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed tensile strength at break up to 86 MPa, elongation to break of 5–9%, and initial moduli up to 2.35 GPa. The wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or p-oxyphenylene group are partially crystalline, and the other polymers are evidenced as amorphous patterns. These polymers show a glass transition in the range of 213–290°C in their differential scanning calorimetry (DSC) traces. The thermal stability of the polymers was evaluated by thermogravimetry analysis, which showed the 10% weight-loss temperatures in the range of 508–565°C in nitrogen and 480–529°C in air atmosphere. © 1994 John Wiley & Sons, Inc.  相似文献   

7.
Polycondensation of α, ω-bis(-4-aminophenoxy) alkanes with trimellitic anhydride chloride (TMA-Cl) in m-cresol yielded a new class of poly(amideimide)s. Starting from the same diamine spacers poly(amideimides) with a more regular sequence of amide and imide groups were prepared by another synthetic method. All these poly(amide-imide)s are semi-crystalline and melt in the range of 250–300°C. They form a smectic-A phase over a narrow temperature range and suffer thermal degradation at the isotropization temperature (330–350°C). The smectic-A phase was characterized by optical microscopy (“batonnet texture”) and by synchrotron radiation measurements conducted at a heating rate of 20°C. Furthermore, it is demonstrated that slight variation of the chemical structure, such as methyl substituents or meta positions in the spacer prevent the formation of a LC phase. © 1995 John Wiley & Sons, Inc.  相似文献   

8.
A series of novel soluble poly(amide-imide)s were prepared from the diimide-dicarboxylic acid, 2,2-bis[N-(4-carboxyphenyl)-phthalimidyl]hexafluoropropane, with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone containing CaCl2 using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 0.78–1.63 dL g−1. The polymers were amorphous and readily soluble in aprotic polar solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide as well as in less polar solvents such as pyridine and γ-butyrolactone, and also in tetrahydrofuran. The polymer films had tensile strength of 84–129 MPa, an elongation at break range of 6–22%, and a tensile modulus range of 2.0–2.7 GPa. The glass transition temperatures of the polymers were determined by DSC method and they were in the range of 240–282°C. These polymers were fairly stable up to a temperature around or above 400°C, and lose 10% weight in the range of 450–514°C and 440–506°C in nitrogen and air, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2629–2635, 1999  相似文献   

9.
A new dicarboxylic acid, 2,4-bis(N-trimellitoyl)triphenylamine, bearing two preformed imide rings was synthesized from the condensation of 2,4-diaminotriphenylamine and trimellitic anhydride at 1:2 molar ratio. A series of poly(amide-imide)s (PAIs) with inherent viscosities of 0.38-0.66 dl/g were prepared by triphenyl phosphite-activated polycondensation from the diimide-dicarboxylic acid with various aromatic diamines. All the resulting PAIs were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. These PAIs have useful levels of thermal stability associated with moderately high glass-transition temperatures (259-314 °C) and 10% weight loss temperatures in excess of 530 °C in nitrogen or in air.  相似文献   

10.
Novel aromatic poly(amide-imide)s with high inherent viscosities were prepared by direct polycondensation reaction of 2,5-bis(4-trimellitimidophenyl)-3,4-diphenylthiophene ( IV ) and aromatic diamines using triphenyl phosphite in the N-methyl–2-pyrrolidone (NMP)/pyridine solution containing dissolved CaCl2. The diimide-diacid IV was readily obtained by the condensation reaction of 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene ( III 1) with trimellitic anhydride. The obtained poly(amide-imide)s showed high thermostability. Their decomposition temperatures at 10% weight loss in nitrogen atmospheres were above 550°C and the anaerobic char yield at 800°C ranged from 48 to 68%. Almost all the poly(amide-imide)s showed high glass transition temperatures above 300°C by differential scanning calorimetry (DSC) measurements. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed obvious yield points in the stress-strain curves and had strength at break up to 74.2 MPa, elongation to break up to 70.1%, and initial modulus up to 4.56 GPa. The factors affecting the reaction of diimide-diacid IV and 4,4′-oxydianiline in view of monomer concentration, reaction temperature, and amount of CaCl2 were also investigated. © 1992 John Wiley & Sons, Inc.  相似文献   

11.
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  相似文献   

12.
L-丙氨酸与均苯四甲酸二酐经缩合反应制得手性酰亚胺(1);1与二苯基甲烷二异氰酸酯聚合制得新型的以L-丙氨酸为手性源的聚酰胺酰亚胺(2),其结构经1H NMR和FT-IR表征.用DSC和TGA研究了2的结晶性能和热稳定性,同时对2的溶解性能进行了探讨.结果表明,2的Tm为357.6℃,失重5%的分解温度为215℃;2在常温下溶于DMF,DMAc,DMSO和NMP.  相似文献   

13.
Aromatic poly(amide-imide)s were synthesized using direct 2,2-bis[N-(4-carboxyphenyl)-phthalimidyl] hexafluoropropane (6FDIA) polycondensation with various diamines containing flexible ether groups and bulky substituents. The oxygen and nitrogen gas transport in the poly(amide-imide) membranes was investigate at 35 °C with the pressure between the interval at 2-10 atm. The proposed method is expected to promote the gas permeability of the poly(amide-imide) membrane and maintain the gas selectivity. It was found that both gas permeability and selectivity of poly(amide-imide) membranes increased with increasing fractional free volume and d-spacing. The gas permeability had good correlation with the γ-transition temperature. The bulky pendent group introduced into diamine moiety of poly(amide-imide) could efficiently promote the gas permeability. For the behaviors of gas separation, the gas diffusivity coefficient and solubility selectivity controlled the gas permeability and selectivity, respectively. The sorption behavior of the aromatic poly(amide-imide) membranes can be well explained using the dual mode sorption model. The Langmuir capacity constant and Henry’s law constant increase with FFV increasing. 6F-TBAPS has the best O2/N2 separation performance among the poly(amide-imide) membranes.  相似文献   

14.
Six new optically active poly(amide-imide)s(5a-f) were synthesized through the direct polycondensation reaction of N,N'-(4,4'- diphthaloyl)-bis-L-leucine(3) with six hydantoin derivatives(4a-f).Triphenyl phosphite(TPP)/pyridine in the presence of calcium chloride(CaCl_2) and N-methyl-2-pyrrolidone(NMP) were successfully applied for direct polycondensation.The polycondensation reactions produce a series of new poly(amide-imide)s(5a-f) in high yields,and inherent viscosity between 0.42 and 0.55 dL/g.The re...  相似文献   

15.
Fifteen bis(phenoxy) fluorene-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BAPPF) with var-ious aromatic bis(trimellitimide)s II in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III having inherent vis-cosities up to 1.45 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 263–315°C and the 10% weight loss temperatures were above 510°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III ′ prepared from 9,9-[4-(4-trimellitimidophenoxy)phenyl]fluorene and various aromatic diamines. © 1995 John Wiley & Sons, Inc.  相似文献   

16.
A series of novel bis(phenoxy)phthalimidine-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalimidine (BAPP) with various aromatic bis(trimellitimide)s in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III , having inherent viscosities up to 1.36 dL/g, were obtained in quantitative yields. All resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 267–322°C and the 10% weight loss temperatures were above 490°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III′ prepared from 3,3-[4-(4-trimellitimidophenoxy)phenyl]-phthalimidine and various aromatic diamines. © 1996 John Wiley & Sons, Inc.  相似文献   

17.
Poly(arylene ether)s containing N-arylenebenzimidazole groups were prepared by the aromatic nucleophilic displacement reaction of two new bis(hydroxyphenyl-N-arylenebenzimidazole)s with activated aromatic difluorides in sulfolane at 200°C in the presence of anhydrous potassium carbonate. The bis(hydroxyphenyl-N-arylenebenzimidazole)s were prepared from bis(o-aminoanilino) arylenes and phenyl-4-hydroxybenzoate. The polymers were soluble in N-methyl-2-pyrrolidinone and m-cresol and exhibited inherent viscosities from 0.37–0.86 dL/g and glass transition temperatures from 219–289°C. Thermogravimetric analyses showed 5% weight losses from 463–506°C in air and 467–522°C in nitrogen. Unoriented thin films exhibited tensile strengths, moduli, and break elongations at 23°C of 10.2–12.5 ksi, 318–365 ksi, and 4–7%, respectively, and at 177°C of 5.1–6.9 ksi, 256–296 ksi, and 1–5%, respectively. A 50 : 50 random copolymer prepared from 1,3-bis(4-fluorobenzoyl) benzene, 1,1'-(4,4'-biphenylene)-bis[2-(4-hydroxyphenyl)benzimidazole], and 5,5'-bis[2-(4-hydroxyphenyl)benzimidazole] exhibited higher moisture absorption and lower tensile properties than those predicted by a rule of mixtures relationship. The chemical, physical, and mechanical properties of these polymers are discussed. © 1993 John Wiley & Sons, Inc.?  相似文献   

18.
Four bis(ether anhydride)s, 4,4′‐(1,4‐phenylenedioxy)diphthalic anhydride (IV), 4,4′‐(2,5‐tolylenedioxy)‐diphthalic anhydride (Me‐IV), 4,4′‐(2‐chloro‐1,4‐phenylenedioxy)diphthalic anhydride (Cl‐IV), and 4,4′‐(2,5‐biphenylenedioxy)diphthalic anhydride (Ph‐IV), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 4‐nitrophthalonitrile with the potassium phenoxides of hydroquinone and various substituted hydroquinones such as methylhydroquinone, chlorohydroquinone, and phenylhydroquinone in N,N‐dimethylformamide, followed by alkaline hydrolysis and dehydration. Four series of poly(ether imide)s were prepared from bis(ether anhydride)s with various aromatic diamines by a classical two‐step procedure. The inherent viscosities of the intermediate poly(amic acid)s were in the range of 0.40–2.63 dL/g. Except for those derived from p‐phenylenediamine and benzidine, almost all the poly(amic acid)s could be solution‐cast and thermally converted into transparent, flexible, and tough polyimide films. Introduction of the chloro or phenyl substituent leads to a decreased crystallinity and an increased solubility of the polymers. The glass transition temperatures (Tg) of these polyimides were recorded in the range of 204–263°C. In general, the methyl‐ and chloro‐substituted polyimides exhibited relatively higher Tgs, whereas the phenyl‐substituted ones exhibited slightly lower Tgs compared to the corresponding nonsubstituted ones. Thermogravimetric analysis (TG) showed that 10% weight loss temperatures of all the polymers were above 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 665–675, 1999  相似文献   

19.
A dicarboxylic acid ( 1 ) bearing two pre-formed imide rings, was prepared from the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.53–1.68 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide—diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these poly(amide-imide)s were in the range of 237–293°C and the 10% weight loss temperatures were above 508°C in nitrogen. © 1993 John Wiley & Sons, Inc.  相似文献   

20.
Various dicarboxylic acids with preformed imide rings were readily obtained by the condensation of ω-amino acids and aminobenzoic acids with trimellitic anhydride, and omega;-amino acids with pyromellitic dianhydride. New tetraphenylthiophene-containing poly(amide-imide)s having inherent viscosities of 0.58-1.54 dL/g were prepared by the direct polycondensation reaction of 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene with the imide-containing dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. These polymers were amorphous and readily soluble in a variety of solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF), and N-methyl–2-pyrrolidone (NMP), and could be easily solution cast into transparent, flexible, and tough films. Most of the poly(amide-imide)s showed clear glass transition on the heating traces of differential scanning calorimetry (DSC) in the range of 146–244°C. Almost all the poly(amide-imide)s exhibited no appreciable decomposition below 400°C, with 10% weight loss being recorded above 420°C in nitrogen. © 1992 John Wiley & Sons, Inc.  相似文献   

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