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1.
A series of novel polymers based on 9-alkylcarbazol-3,6-diyl and different aromatic amino groups were synthesized in good yields through modified Ullmann coupling reactions. The resulting polymers were characterized by gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. These polymers possess high thermal stability with onset decomposition temperatures of 320-355 °C. Their glass transition temperatures range from 154 °C to 250 °C. The ionisation potentials of the synthesized polymers established by electron photoemission in air technique are in the range 4.95-5.12 eV.  相似文献   

2.
New aliphatic-aromatic and fully aromatic phosphonate polyamides were prepared by polycondensation reaction of our synthesized aromatic diamine: tetraethyl[(2,5-diamino-3,6-dimethylbenzene-1,4-diyl)dimethanediyl]bis(phosphonate) with the specific di-acylchloride (adipoyl chloride, isophthaloyl chloride and terephthaloyl chloride). The chemical structure of all samples were characterized by (1H and 31P) NMR, MALDI-TOF MS, FT-IR tools, whereas their thermal properties were determined by DSC and TGA techniques. The phosponate polyadipamide (referred as PAP) is a semi-crystalline sample with a melting temperature at about 261 °C and glass transition (Tg) of 71 °C. All polymers show two thermal degradation steps in the temperature range 270-550 °C. Each polymer, independently its structure, shows the first maximum rate of thermal decomposition temperature (PDT) around 300-310 °C, which may be due to thermal degradation of phoshonate groups. MALDI-TOF spectra, beside the linear oligomers terminated with the specific groups expected in accord to the synthesis procedure, reveals the presence of cyclic oligomers in the polyadipamide and polyisophthalamide samples.  相似文献   

3.
New silarylene-siloxane-acetylene polymers have been synthesized by coupling reactions employing 1,3-bis(p-ethynylphenyl)-1,1,3,3-tetraphenyldisiloxane (3) as the key monomer. Their thermal properties have been evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). All of the new polymers showed good thermal stability, with their temperatures at 5% weight loss (Td5) being higher than 540 °C under nitrogen and higher than 460 °C in air. Their char yields at 1000 °C under N2 were above 80%. Broad exothermic peaks, attributable to reaction of the acetylenic units, were observed by DSC analysis in the temperature range 270-450 °C.  相似文献   

4.
A series of novel fluorinated aromatic polyamides derived from a new monomer, 2-(4-trifluoromethylphenoxy)terephthaloyl chloride (TFTPC), with various aromatic diamines were synthesized and characterized. The polyamides were obtained in high yields and moderately high inherent viscosities ranging from 1.07 to 1.16 dL/g. All the polyamides were amorphous and readily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and could afford flexible and tough films via solution casting. The cast films exhibited good mechanical properties with tensile strengths of 82.8-107.3 MPa, elongation at break of 4.1-7.2%, and tensile modulus of 2.26-3.95 GPa. These polyamide films also exhibited good thermal stability with the glass transition temperature of 222-294 °C, the temperature at 5% weight loss of 442-472 °C in nitrogen. They exhibited low dielectric constants ranging from 3.25 to 3.39 (1 MHz), low moisture absorption in the range of 1.32-2.45%, high transparency with an ultraviolet-visible absorption cut-off wavelength in the 330-371 nm range, and excellent electrical properties.  相似文献   

5.
Two kinds of aromatic, unsymmetrical diamines with ether-ketone group, 3-amino-4′-(4-amino-2-trifluoromethylphenoxy)-benzophenone and 4-amino-4′-(4-amino-2-trifluoromethylphenoxy)-benzophenone, were successfully synthesized with two different synthetic routes. Then, they were polymerized with 4,4′-oxydiphthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, and 2,2′-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride to form a series of fluorinated polyimides via a conventional two-step thermal or chemical imidization method. The resulting polyimides were characterized by measuring their solubility, viscosity, mechanical properties, IR-FT, and thermal analysis. The results showed that the polyimides had inherent viscosities of 0.48-0.68 dl/g and were easily dissolved in bipolarity solvents and common, low-boiling point solvents. Meanwhile, the resulting strong and flexible polyimide films exhibited excellent thermal stability, e.g., decomposition temperatures (at 10% weight loss) are above 575 °C and glass-transition temperatures in the range of 218-242 °C. The polymer films also showed outstanding mechanical properties, such as tensile strengths of 86.5-132.8 MPa, elongations at break of 8-14%, and initial moduli of 1.32-1.97 GPa. These outstanding combined features ensure that the polymers are desirable candidate materials for advanced applications.  相似文献   

6.
Novel optically active aromatic poly(amide-imide)s (PAIs) were prepared from newly synthesized N,N′-(4,4′-diphthaloyl)-bis-l-isoleucine diacid (3) via polycondensation with various diamines. The diacid was synthesized by the condensation reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (1) with l-isoleucine (2) in a mixture of acetic acid and pyridine (3:2 v/v). All the polymers were obtained in quantitative yields with inherent viscosities of 0.20-0.43 dL g−1. All the polymers were highly organosoluble in solvents like N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran, γ-butyrolactone, cyclohexanone and chloroform at room temperature or upon heating. These poly(amide-imide)s had glass transition temperatures between 198 and 231 °C, and their 10% weight-loss temperatures were ranging from 368 to 398 °C and 353 to 375 °C under nitrogen and air, respectively. The polyimide films had tensile strengths in the range of 63-88 MPa and tensile moduli in the range of 0.8-1.4 GPa. These poly(amide-imide)s possessed chiral properties and the specific rotations were in the range of −3.10° to −72.92°.  相似文献   

7.
A new aromatic unsymmetrical diamine monomer, 1,4-(2′,4″-diaminodiphenoxy)benzene (OAPB), was successfully synthesized in three steps using hydroquinone as starting material and polymerized with various aromatic tetracarboxylic acid dianhydrides, including 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 2,2′-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride (6FDA) and pyromellitic dianhydride (PMDA) via the conventional two-step thermal or chemical imidization method to produce a series of the unsymmetrical aromatic polyimides. The polyimides were characterized by solubility tests, viscosity measurements, IR, 1H NMR, and 13C NMR spectroscopy, X-ray diffraction studies, and thermogravimetric analysis. The polyimides obtained had inherent viscosities ranged of 0.38-0.58 dL/g, and were easily dissolved in common organic solvents. The resulting strong and flexible PI films exhibited excellent thermal stability with the decomposition temperature (at 5% weight loss) of above 505 °C and the glass transition temperature in the range of 230-299 °C. Moreover, the polymer films showed outstanding mechanical properties with the tensile strengths of 41.4-108.5 MPa, elongation at breaks of 5-9% and initial moduli of 1.15-1.68 GPa.  相似文献   

8.
A series of novel polyamide-imides (PAIs) with high glass transition temperature were prepared from diimide-dicarboxylic acid, 2,2′-bis(trifluoromethyl)-4,4′-bis(trimellitimidophenyl)biphenyl (BTFTB), by direct polycondensation with various diamines in N-methyl-2-pyrrolidinone using triphenyl phosphite and pyridine as condensing agents in the presence of dehydrating agent (CaCl2). The yield of the polymers was obtained was high with moderate to high inherent viscosities (0.80-1.03 dL g−1). Gel permeation chromatography (GPC) of the polymers showed number-average and weight-average molecular weights up to 8.6 × 104 and 22 × 104, respectively. The PAIs were amorphous in nature. Most of the polymers exhibited good solubility in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), pyridine, cyclohexanone and tetrahydrofuran. The polymer films had tensile strength in the range of 79-103 MPa, an elongation at break in the range of 6-16%, and a tensile modulus in the range between 2.1 and 2.8 GPa. The glass transition temperatures of the polymers were determined by DMA method and they were in the range of 264-291 °C. The coefficients of thermal expansion (CTE) of PAIs were determined by TMA instrument and they were between 29 and 67 ppm °C−1. These polymers were fairly thermally stable up to or above 438 °C, and lose 10% weight in the range of 446-505 °C and 438-496 °C, respectively, in nitrogen and air. These polymers had exhibited 80% transmission wavelengths which were in the range of 484-516 nm and their cutoff wavelengths were in between 418 and 434 nm. The PAIs with trifluoromethyl group have higher bulk density resulting in higher free volume and then lowering the dielectric constant.  相似文献   

9.
Soluble fluoro-polyimides have been synthesized by reacting of a fluorine-containing aromatic dianhydride, 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, with aromatic diamine to yield poly(amic acid)s which were then cyclized to yield polyimide by chemical imidization method. The polyimides have excellent solubility both in strong bipolar solvents, such as NMP and DMAc, and in common organic solvents, such as THF and dioxane, etc. The glass transition temperature of these polyimides were determined by DSC and ranged from 281 to 289 °C. Thermogravimetric analysis indicated that these polyimides have good thermal stability with initial thermal decomposition temperature of 520-526 °C. The polyimide asymmetric membranes were prepared by phase inversion method and the inner structure was observed by method of SEM. The pervaporation properties of the prepared polyimides asymmetric membranes for n-heptane/thiophene mixtures were investigated at 40-77 °C and the permeation flux and the sulfur enrichment factor of the polyimide membranes are in the range of 0.56-1.68 kg/m2 h and 3.12-2.24, respectively. The result demonstrated that the pervaporation method could be very effective method for desulfurization by polyimides asymmetric membranes with ultrathin skin.  相似文献   

10.
A new kind of pyridine-bridged aromatic dianhydride monomer, 4-phenyl-2,6-bis[4-(3,4-dicarboxyphenoxy)phenyl]-pyridine dianhydride (PPDA), was successfully synthesized by modified Chichibabin reaction of benzaldehyde and substituted acetophenone, 4-(3,4-dicyanophenoxy)-acetophenone (DCAP), followed by acidic hydrolysis of the intermediate tetranitrile and cyclodehydration of the resulting tetraacid. The pyridine-bridged aromatic dianhydride was employed to synthesized a series of new pyridine-containing polyimides by polycondensation with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) via the conventional two-step method, i.e. ring-opening polycondensation forming the poly(amic acid)s and further thermal or chemical imidization forming polyimides. The inherent viscosities of the resulting polyimides were in the range of 0.49-0.63 dL/g, and most of them were soluble in aprotic amide solvents and cresols, such as N,N-dimethylacetamide (DMAc), NMP, and m-cresol, etc. Meanwhile, strong and flexible polyimide films were obtained, which have good thermal stability with the glass transition temperatures (Tg) of 223-256 °C, the temperature at 5% weight loss of 523-569 °C, and the residue at 700 °C of 52.1-62.7% in nitrogen, as well as have outstanding mechanical properties with the tensile strengths of 70.7-97.6 MPa and elongations at breakage of 7.9-9.7%. Wide-angle X-ray diffraction measurements revealed that these polyimides were predominantly amorphous.  相似文献   

11.
New optically active polyamides were synthesized according to two ways: using a microwave-assisted polycondensation of an optically active isosorbide-derived diacylchloride with different aromatic diamines in NMP and using interfacial polymerization from an isosorbide-derived diamine with different diacylchlorides. The polymers are obtained with inherent viscosities in the range from 0.11 to 1.05 dL/g. The DSC and TGA measurements clearly demonstrate the high thermal stability of these polymers when considering the range of the melting points from 200 °C to 300 °C and the absence of decomposition till 350 °C.  相似文献   

12.
Siloxane-containing poly(oxadiazole-imide)s were prepared by polycondensation reaction of two aromatic diamino-oxadiazoles with a dianhydride containing tetramethylsiloxane moiety. Free-standing flexible films having good mechanical properties were made therefrom. The polyimides exhibited high thermal stability with initial decomposition temperature being above 440 °C and glass transition in the range of 165-183 °C. The dielectric constant values, measured at room temperature and in the frequency domain of 1 Hz-1 MHz, are in the range of 2.69-2.90, being significantly lower in comparison with that of Kapton HN® film, whose dielectric constant values ranged from 3.13 to 3.24. The dielectric loss values are low, in the same range with those of Kapton HN®. The dielectric spectroscopy data corroborated with the dynamo-mechanical analysis ones showed distinct sub-glass transitions for these polymers: γ relaxations with activation energies of 44 and 45 kJ/mol, and a β relaxation with an activation energy of 107 kJ/mol. The dielectric properties are discussed in comparison with those of Kapton HN® film measured under the same conditions.  相似文献   

13.
A new kind of pyridine-containing aromatic diamine monomer, 4-phenyl-2,6-bis[3-(4′-amino-2′-trifluoromethyl-phenoxy) phenyl] pyridine (m-PAFP), was successfully synthesized by a modified Chichibabin reaction of 3-(4′-nitro-2′-trifluoro-methyl-phenoxy)-acetophenone with benzaldehyde, followed by a catalytic reduction. A series of fluorinated pyridine-bridged aromatic poly(ether-imide)s were prepared from the resulting diamine monomer with various aromatic dianhydrides via a conventional two-step thermal or chemical imidization method. The inherent viscosities values of these polyimides were in the range of 0.56-1.02 dL/g, and they could be cast and thermally converted into transparent, flexible, and tough polyimide films. The polyimides displayed higher solubility in polar solvents such as NMP, DMSO and m-cresol. The polyimides had good thermal stability, with the glass transition temperatures (Tg) of 187-211 °C, the temperatures at 5% weight loss of 511-532 °C, and the residue at 800 °C in air was higher than 50%. These films also had dielectric constants of 2.64-2.74 at 10 MHz and low water uptake 0.53-0.66%. Wide-angle X-ray diffraction measurements revealed that these polyimides were predominantly amorphous. Moreover, the polymer films of these novel polyimides showed outstanding mechanical properties with the tensile strengths of 90.1-96.6 MPa, elongations at breakage of 8.9-10.7% and tensile modulus of 1.65-1.98 GPa.  相似文献   

14.
A novel pyridine-containing aromatic diamine monomer, 4-(4-trifluoromethylphenyl)-2,6-bis[4-(4-aminophenoxy)phenyl]pyridine (FAPP), was synthesized via the modified Chichibabin pyridine synthesis of 4-(4-nitrophenoxy)-acetophenone with 4-trifluoromethyl-benzaldehyde, followed by a catalytic reduction. A series of fluorinated pyridine-bridged aromatic poly(ether-imide)s were prepared from the resulting diamine monomer with various aromatic dianhydrides via a conventional two-step process. The resulting polyimides exhibited good solubility in aprotic amide solvents and m-cresol, such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., which possessed the inherent viscosities of 0.76-0.91 dL/g. Strong and flexible poly(ether-imide) films were obtained, which showed excellent thermal properties with the glass transition temperatures of 268-353 °C, the temperature at 5% weight loss of 547-595 °C, and the residue at 700 °C of 65-74% in nitrogen, good mechanical properties with the tensile strengths of 87.6-104.2 MPa and elongations at breakage of 8.9-12.6%, and good optical transparency with the cut-off wavelengths of 357-380 nm, as well as low dielectric constants in the range of 2.49-3.04 at 1 MHz and low water uptake 0.43-0.69%. Furthermore, the resulted polyimides derived from FAPP were compared with non-fluorinated analogous polyimides and fluorinated analogous polyimides with trifluoromethyl groups in different positions, and the effects of substituents were also investigated and discussed.  相似文献   

15.
A novel diimide-diacid (DIDA) monomer, 4-{4-[(4-methyl phenyl) sulphonyl]}-1,3-bis-trimellitoimido benzene containing sulphone and bulky pendant groups was successfully synthesized and used to synthesize a series of wholly aromatic poly(amide-imide)s (PAIs) by direct polycondensation method. The direct polycondensation of newly synthesized DIDA with different diamines was carried out via Yamazaki’s phosphorylation method using triphenyl phosphite and pyridine system. The resulting poly(amide-imide)s were obtained in quantitative yields with inherent viscosities 0.36-0.47 dl/g in DMAc at 30 ± 0.1 °C. The poly(amide-imide)s were amorphous and were readily soluble in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), and pyridine. Tough and flexible films were obtained by casting their DMAc solution. According to thermogravimetric analysis, the polymers were fairly stable up to temperature around 396 °C, and 10% weight losses in the temperature range of 476-511 °C that showed good thermal stabilities of these polymers.  相似文献   

16.
A series of new poly(arylene ether sulfone)s has been obtained by solution condensation polymerisation starting from 1,5- and 2,6-bis-(4-fluorosulfonyl)naphthalene with various aromatic dihydroxy compounds. The polymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.68 dl g−1, had good thermal stability (10% weight loss temperatures were above 405 and 420 °C respectively in nitrogen and air) and high glass transition temperatures (in the range 217-258 °C). They have been characterised by elemental and infrared analyses, GPC and wide-angle X-ray diffraction. The properties of these poly(arylene ether sulfone)s have been compared with those of the corresponding poly(arylene ether ketone)s.  相似文献   

17.
New poly(1,3,4-oxadiazole-imide)s containing dimethylsilane units have been prepared by solution polycondensation reaction of an aromatic dianhydride incorporating dimethylsilane group, namely bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, with different aromatic diamines having preformed 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2,5-bis[p-(3-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-fluorophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole, and 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidinone, N,N-dimethylformamide, and pyridine, as well as in less polar organic solvents, such as tetrahydrofuran and chloroform. Very thin coatings deposited on silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy investigations. The polymers showed high thermal stability with decomposition temperature being above 415 °C.They exhibited a glass transition in the temperature range of 202-282 °C, with reasonable interval between glass transition and decomposition temperature. Solutions of the polymers in N,N-dimethylformamide exhibited fluorescence, having maximum emission wavelength in the range of 353-428 nm.  相似文献   

18.
A series of meltable oligoimide resins with controlled molecular weights by reactive phenylethynyl endcapping groups have been prepared by the thermal polycondensation of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) with the aromatic diamine mixtures consisting of different mole ratios of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (1,4,4-6FAPB) and 3,4′-oxydianiline (3,4′-ODA) in the presence of 4-phenylethynylphthalic anhydride (PEPA) as molecular weight-controlling and reactive endcapping reagent. Experimental results indicated that the molecular weight-controlled oligoimide resins were mixtures containing a series of biphenylethynyl-endcapped oligoimides with different chemical structures and different molecular weights. The typical oligoimide resins could be melted at temperatures of 300 °C to yield stable molten fluid with melt viscosity of 13.4 Pa s, which was suitable for melt processing. The molten oligoimide resins could be further polymer chain extended and crosslinked by thermal curing of the reactive phenylethynyl groups to give strong and tough thermosetted polyimides. Thus, the oligoimide resin with calculated molecular weight of 2500 exhibited not only good meltability with low melt viscosity, but also high melt stability and fluidability at temperatures of <300 °C. After thermal curing, the obtained thermosetted polyimide showed high glass transition temperature (>316 °C, DMA), excellent thermal stability with initial thermal decomposition temperature of 588 °C and good mechanical properties with flexural strength of 159.1 MPa, flexural moduli of 3.3 GPa, tensile strength of 94.7 MPa and elongation at breakage of 9.0%.  相似文献   

19.
A series of organo-soluble polyimides were prepared from a novel fluorinated diamine monomer, 4-phenyl-2,6-bis[4-(4′-amino-2′-trifluoromethylphenoxy)phenyl]pyridine and various commercial aromatic dianhydrides. These polyimides had good solubility in common organic solvents. The obtained strong and flexible PI films exhibited excellent thermal stability with the decomposition temperature (at 5% weight loss) of above 561 °C and the glass transition temperature in the range of 258-312 °C. Moreover, the polymer films showed good electrical insulating property, low dielectric constant and low water uptake due to the introduction of fluorinated substitutes in the polymer backbone. The remarkable combined features ensure these polymers to be ideal candidate materials for advanced microelectronic industry and other related applications.  相似文献   

20.
New aromatic polyamides containing 1,3,4-oxadiazole or benzonitrile units in the main chain and 5-(4-acetoxybenzamido) groups in the side chain have been synthesized and their properties have been characterized and compared with those of related polyamides and polyoxadiazole-amides. These polymers show good thermal stability, with initial decomposition temperature being at about 300 °C and glass transition temperature in the range of 260-280 °C. They are easily soluble in certain solvents such as N-methylpyrrolidinone (NMP), N,N-dimethylacetamide (DMA) and N,N-dimethylformamide (DMF) and can be cast from solutions into thin flexible films. The polymer films had tensile strengths in the range of 77-97 MPa, tensile moduli in the range of 2.3-2.6 GPa and elongation at break values ranging from 6% to 24%. One of the polymers containing the 1,3,4-oxadiazole ring exhibited blue fluorescence.  相似文献   

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