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1.
Marie-Florence Grenier-Loustalot Frdric Joubert Philippe Grenier 《Journal of polymer science. Part A, Polymer chemistry》1991,29(11):1649-1660
We have synthesized model compounds representing the repeating units of a polyamic acid prepared from pyromellitic anhydride and an aromatic amine. They were characterized with HPLC, 1H and 13C liquid and solid NMR and FTIR. The Kinetic study of the ring dehydration reaction of model compounds showed that the reaction paths were very different, depending on the experimental conditions (isotherms, liquid, or solid states). They could lead to a deterioration of the polyamic of the polyamic acid by the formation of side reactions. These reactions could predominate as a result of the existence of an equilibrium between the amic acid group and starting monomers. 相似文献
2.
Biju PhilipK. Sreekumar 《European Polymer Journal》2002,38(12):2441-2447
A polyamic acid containing 2,2′-dinitrodiphenylmethane segments in the main chain was synthesized from 4,4′-diamino-2,2′-dinitrodiphenylmethane and pyrromellitic dianhydride. Irradiation of the polyamic acid was done in solution (in a protic solvent, isopropanol, in isopropanol in the presence of a triplet exciter, benzophenone and in acidified isopropanol) and as thin film. The irradiations were done in an immersion type photoreactor using a 125 W high-pressure mercury vapour lamp. The average molecular weights of the polymers were determined by gel permeation chromatography. The polydispersity index of the polyamic acid and the photoproduct showed the absence of photodegradation. The photoproducts were identified by comparing the spectra of polymer photoproducts with that of low molecular weight 2,2′-dinitrodiphenylmethane derivatives under identical conditions. A possible mechanism for the phototransformations is suggested. Evaluation of photoresist behaviour of the polyamic acid was also done. 相似文献
3.
《European Polymer Journal》1986,22(2):97-101
Proton-driven cation transport against cation concentration gradient has been investigated using films of polyamic acid 18-crown-6 (1) and polyamide 18-crown-6 (3)/polyamic acid (5) mixtures as the polymeric membrane. Both membrane systems containing the crown ethers were found to act as efficient alkali metal ion pumps. The ion-transportability of the polyamic acid 18-crown-6 membrane decreased in the order K+ > Cs+ > Na+ > Li+, which is reflected in the cation-complexing ability of the 18-crown-6 moiety. The transport selectivity, however, was varied remarkably by the combined use of polyvinylpyrrolidone with (1) and, therefore, by the resulting increase in hydrophilicity of the membrane. The ion-selectivity in the transport through mixed membranes of (3) and (5) was also dependent on the membrane composition. For the proton-driven cation transport two mechanisms are proposed; in one of the transport mechanisms, the carboxylic group cooperates with the crown ether moiety and in the other the carboxylic group participates independently. 相似文献
4.
J. F. Romanelli J. W. Mayer E. J. Kramer T. P. Russell 《Journal of Polymer Science.Polymer Physics》1986,24(2):263-277
Rutherford backscattering spectrometry with a 2.1-meV He2+ion beam is used to measure the diffusion of iodine into polyamic acid and polyimide films. The iodine diffusion coefficient D decreases from its initial value of about 2X10?13cm2/s in polyamic acid to approximately 1.4 × 10?15cm2/s in partially cured polyimide, but then increases to a value of nearly 1.5 × 10?14 cm2/s in fully cured polyimide. This dramatic increase in D cannot be attributed to the “in-plane” biaxial orientation of the polyimide molecules since indential D's were found with isotropic specimens. Microvoids less than 2 nm in size caused by water and carbon dioxide formation during imidization may, however, give rise to the observed behavior. The results demonstrate that Rutherford backscattering spectrometry with its excellent depth resolution (better than 30 nm) and good sensitivity (50 ppm iodine can be detected) is very useful for measuring the diffusion of slowly diffusing species in glassy polymers. 相似文献
5.
C. C. Walker 《Journal of polymer science. Part A, Polymer chemistry》1988,26(6):1649-1657
Molecular weight studies of polyamic acids are complicated by polyelectrolyte effects. Although early work on the molecular weight determination of polyamic acids employed salts to suppress this polyelectrolyte effect, recent publications reveal that such salts can cause precipitation of polyamic acids from solution, however, a mobile phase consisting of 0.03M LiBr/0.03M H3PO4/1% vol THF in dimethyl formamide was reported to successfully suppress the noted polyelectrolyte effect without causing the precipitation of polyamic acid and give satisfactory size exclusion chromatograms using columns packed with “macro-porous” glasses. However, the development time was long (ca. 4 h) and considering the lability of the polyamic acids, the results must be viewed with skepticism. We find that use of a similar “mixed” mobile phase with Zorbax® PSM-Bimodal columns using size exclusion chromatography in the high performance mode (HPSEC) provides well resolved and reproducible chromatograms and molecular weight data with development times of < 15 min. Aside from the avoidance of long development times, which can lead to questionable results, this procedure permits the facile routine analysis of polyamic acid on a daily basis. The procedure has great utility as an analytical tool to support fundamental studies of polyamic acid chemistry and two examples of this application are given. 相似文献
6.
Robert M. Jennings Richard J. Farris 《Journal of Polymer Science.Polymer Physics》1994,32(8):1457-1464
A high-pressure curing technique was developed to help determine the effects of solvent presence during the thermal curing of the polyimide poly (N,N'-bis-phenoxyphenylpyro-mellitimide) (PMDA-ODA). A powder form of this aromatic polyimide was produced from a polyamic acid solution using the high-pressure thermal curing technique. Preliminary characterization of the powder indicates a high degree of crystallinity with a measured density of 1.46 ± 0.01 g/cm3 and a distinct melting point of 594°C. The addition of chemical curing agents to the polyamic acid solution prior to thermal treatment reduced the amount of crystallinity observed in the cured material. Molecular weight measurements of the polyamic acid precursor and powder suggest that the high degree of order observed in the powder is a result of degradation during cure. © 1994 John Wiley & Sons, Inc. 1 This article is a US Government work and, as such, is in the public domain in the United States of America 相似文献
7.
Franois Basset Alain Lefrant Thierry Pascal Bernard Gallot Bernard Sillion 《先进技术聚合物》1998,9(3):202-209
Highly crystalline polyimide powders were prepared from diluted solutions of polyamic acid in N-methyl-2-pyrrolidone (NMP) which were cured at 200°C for 4 hr with a high heating rate. The chemical structures of the repetitive units were chosen to obtain rigid polymeric backbones precluding any solubility in polar aprotic solvents. Therefore the starting polyamic acids were produced by polycondensation from an equimolar ratio of the following pairs of monomers: pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA); 3,3′,4,4′-biphenyl tetracarboxylic dianhydride and ODA; PMDA and p-phenylenediamine. After optimizing the reaction conditions, the resulting powders were first characterized by scanning electronic microscopy and granulometric analysis. Well-divided particles with a spherulitic shape and average particle size of 5 μm were observed. The X-ray diffraction patterns and the solid-state 13C nuclear magnetic resonance spectra together revealed a highly organized structure. The degree of imidization of the powder is nearly complete as demonstrated by Fourier transform infrared analysis and the inherent viscosity after dissolution in concentrated sulfuric acid is about 0.8 dl/g. © 1998 John Wiley & Sons, Ltd. 相似文献
8.
Siu‐Ming Yuen Chen‐Chi M. Ma Chin‐Lung Chiang Yao‐Yu Lin Chih‐Chun Teng 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3349-3358
Precursor of polyimide, polyamic acid has been prepared sucessfully. Acid‐modified carbon nanotube (MWCNT) was grafted with soluble polyimide then was added to the polyamic acid and heated to 300 °C to form polyimide/carbon nanotube composite via imidation. Morphology, mechanical properties and electrical resistivity of the MWCNT/polyimide composites have been studied. Transmission electron microscope microphotographs show that the diameter of soluble polyimide‐grafted MWCNT was increased from 30–60 nm to 200 nm, that is a thickness of 70–85 nm of the soluble polyimide was grafted on the MWCNT surface. PI‐g‐MWCNT was well dispersed in the polymer matrix. Percolation threshold of MWCNT/polyimide composites has been investigated. PI‐g‐MWCNT/PI composites exhibit lower electrical resistivity than that of the acid‐modified MWCNT/PI composites. The surface resistivity of 5.0 phr MWCNT/polyimide composites was 2.82 × 108 Ω/cm2 (PI‐g‐MWCNT) and 2.53 × 109 Ω/cm2 (acid‐modified MWCNT). The volume resistivity of 5.0 phr MWCNT/polyimide composites was 8.77 × 106 Ω cm (PI‐g‐MWCNT) and 1.33 × 1013 Ω cm (acid‐modified MWCNT).Tensile strength and Young's modulus increased significantly with the increase of MWCNT content. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3349–3358, 2007 相似文献
9.
Marie-Florence Grenier-Loustalot Marguerite Gillard Frdrric Joubert Philippe Grenier 《Journal of polymer science. Part A, Polymer chemistry》1993,31(11):2839-2854
We have synthesized and studied the ring dehydration mechanisms and kinetics of polyamic acid models in solution and in the solid state using 13C-NMR (solid and liquid), HPLC, FTIR, and x-ray diffraction. Results obtained in solution show the role of temperature, catalysts, and the basicity of the amine in ring dehydration mechanisms and kinetics, as well as conformation and intramolecular bonds in the amic acid bond in the solid state. © 1993 John Wiley & Sons, Inc. 相似文献
10.
Christian Schramm Beate Rinderer Richard Tessadri Heinz Duelli 《Journal of Sol-Gel Science and Technology》2010,53(3):579-586
Based on differential scanning calorimetry data, it was shown that the reaction of (3-triethoxysilylpropyl)succinic anhydride
and (3-amino)propyltriethoxysilane at 110 °C resulted in the formation of polyamic acid, whereas the thermal treatment at
220 °C led to the generation of an aliphatic monoimide-bridged polysilsesquioxane as proved by FT-IR. X-ray powder diffraction
studies showed a prominent reflection at 2θ = 6.66° (d = 1.32 nm) revealing that a crystalline area is formed. 29Si CP-MAS-NMR and 13C CP-TOSS-MAS-NMR measurements proved that no cleavage of the Si–C bond occurred, and a highly condensed material was obtained. 相似文献
11.
Evgenia Minko Petr Sysel Michal Hauf Jiří Brus Libor Kobera 《Macromolecular Symposia》2010,295(1):88-93
Summary: The novel hyperbranched polyimide - silica hybrid materials containing theoretically 16 wt% of an inorganic phase were prepared via a sol-gel process. An amine terminated polyimide precursor (hyperbranched polyamic acid) was prepared from commercially available monomers 4,4′,4″-triaminotriphenylmethane and 4,4′-oxydiphthalic anhydride in molar ratio 1:1. Tetramethoxysilane and/or 3-glycidoxypropyltrimethoxysilane (also used as a coupling agent) were used as silica precursors. During thermal exposition the polyimide precursor was transformed to hyperbranched polyimide and hydrolyzed alkoxy groups reacted mutually to form silica. The final products were self-standing films, whose structure was characterized by using IR and 13C and 29Si solid state NMR spectroscopy. The influence of the amount of silica and/or coupling agent on their structure and thermal properties was described. 相似文献
12.
G. Maggioni S. Carturan M. Tonezzer A. Quaranta E. Negro G. Della Mea 《European Polymer Journal》2008,44(11):3628-3639
Thin films of porphyrin-containing polyimide were produced by high vacuum co-evaporation of 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), 3,3′-diaminodiphenyl sulfone (DDS) and 5,10,15,20 meso-tetraphenyl porphyrin (TPP). The films were characterized by FT-IR analysis, optical absorption and emission spectroscopy. FT-IR analysis shows that the film matrix is comprised of only unreacted monomers. The conversion of monomers to polyamic acid and the following condensation to polyimide were studied by curing the samples at temperatures up to 240 °C. The amount of polyamic acid increases from room temperature to 120 °C, while at higher temperature it starts to condense to polyimide. Optical analysis shows that TPP is incorporated in the film matrix and its chemical state is determined by the interaction with the monomers, polyamic acid and polyimide. After curing the TPP molecules are finely dispersed in the polyimide matrix and their absorption and fluorescence properties are wholly preserved. 相似文献
13.
V. N. Artem'eva V. V. Kudryavtsev E. M. Nekrasova V. P. Sklizkova N. G. Belnikevich L. M. Kaluzhnaya I. G. Silinskaya O. P. Shkurko V. P. Borovik 《Russian Chemical Bulletin》1993,42(10):1673-1676
A comparative study of the behavior of polypyromellitamic acids based on 2,5-bis(p-aminophenyl)pyrimidine and 4,4″-diaminoterphenyl in concentrated dimethylacetamide solutions was carried out by the light-scattering method. It was shown that mutual ordering of the scattering elements is much higher for the pyrimidine-containing polyamic acids than for benzenoid polyamic acids. The Flory-Huggins parameters of the polymer-solvent interaction thus determined indicate that the polymer-polymer interactions increase when a pyrimidine ring is introduced into the polyamic acid or polyimide. Hence, the hypothesis postulating that the amide solvent is displaced by the pyrimidine ring during the shear packing of pyrimidine-containing polymers is confirmed. 相似文献
14.
Takashi Iizawa Tsutomu Ogasa 《Journal of polymer science. Part A, Polymer chemistry》1996,34(1):63-71
A model reaction of o-(N-phenylcarbamoyl)benzoic acid (amic acid) with threefold amounts of 1-phenylethyl bromide (PEB) and 1,8-diazabicyclo-[5,4,0]-7-undecene (DBU) was carried out in NMP. The reaction gave N-[m-(1-phenylethoxycarbonyl)phenyl]phthalimide in almost quantitative yield at room temperature for 2 h. Polyimide containing pendant 1-phenylethyl ester (P-1a) was also prepared from polyamic acid with PEB using DBU according to the model reaction. The obtained polymer was exactly consistent with P-1a synthesized stepwise from the esterification of the corresponding polyimide containing pendant carboxylic acid with PEB. Therefore, the reaction of polyamic acid bearing pendant carboxylic acid with alkyl bromide proceeded quantitatively to give polyimide containing pendant ester in the presence of DBU. Also, this method was applied to the synthesis of polyimide containing 1-phenylethyl ether. However, the polyimide with quantitative etherification was not synthesized. The acid-catalyzed deesterification of P-1a film was carried out by heating the irradiated polymer film containing 10 wt % of p-nitrobenzyl 9,10-diethoxyanthracene-2-sulfonate, which produced sulfonic acid by irradiation, at various temperatures. Although thermal deesterification of P-1a started at 220°C without any acid catalyst, the deesterification occurred when the irradiated film was heated at the lower temperature. The degree of esterification can be determined from the disappearance of absorption at 700 cm−1. The deesterification obeyed first-order kinetics. © 1996 John Wiley & Sons, Inc. 相似文献
15.
Hüseyin Deligöz Mesut Yılmazoğlu Serpil Yılmaztürk Yavuz Şahin Kemal Ulutaş 《先进技术聚合物》2012,23(8):1156-1165
The paper deals with the synthesis and characterization of a new series of anhydrous conducting acid‐doped complex membranes based on polyimide (PI) and ionic liquid (IL) for high‐temperature fuel cells via a new route. For this purpose, three imidazolium‐based ILs (RIm+BF4?) with different alkyl chain lengths (R=methyl, ethyl, and butyl) are added into polyamic acid (PAA) intermediate prepared from the reaction of benzophenonetetracarboxylic dianhydride and diaminodiphenylsulfone in different –COOH/imidazolium molar ratios (n = 0.5, 1, and 2). Then, the thermally imidized complex membrane was doped with H2SO4. The conductivities of acid‐doped PI/IL complex membranes prepared by taking n of 1 are found to be in the range of 10?4?10?5 S cm?1 at 180°C, whereas the acid‐free PI/IL complex membranes show the conductivity at around 10?9?10?10 S cm?1. Thermogravimetric analysis results reveal that the acid‐doped PI/IL complex membranes are thermally stable up to 250°C. Dynamic mechanical analysis results of the acid‐doped ionically interacted complex membrane show that the mechanical strengths of the PI/IL complex membranes including 1‐methyl imidazolium tetrafluoroborate (MeIm‐BF4) and 1‐ethyl 3‐methyl imidazolium tetrafluoroborate (EtIm‐BF4) are comparable with those of pristine PI until 200°C. Furthermore, it can be clearly emphasized that the ionic interaction between carboxylic acid groups of PAA's and IL's cations offers a positive role in long‐term conductivity stability by preventing the IL migration at high temperatures. On the other hand, preliminary methanol permeability tests of the acid‐doped membranes show that they can also be considered as an alternative for direct methanol fuel cells. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
16.
Sanjeev Jain Rajani Saktimayi Madhu Dubey Suresh Kumar Nema 《Macromolecular Symposia》1999,148(1):361-371
A novel polyimide-epoxy or PI-EP alloys are prepared by the modification of polyamic acid in the concentration range of 1.54×10−6 to 1.54×10−2 mol/L. The methanol sorption for these alloys at 24 hrs and at equilibrium conditions are determined and the residual solvent in fully cyclized polyimides were calculated. The presence of the residual solvent is visualized in fully imidized polymer and a structure containing partly imidized amic acid moiety is proposed and their concentration (in percentage) is calculated. The water sorption for these alloys at 24 hrs and at equilibrium conditions and the values of the water diffusion coefficient are determined from absorption isotherms. The PI-EP alloys have shown comparatively lower water sorption and higher diffusion coefficient than the unmodified polyimide. The mechanistic aspects of water sorption and diffusion are discussed. 相似文献
17.
Organic compounds such as antibiotics that are not effectively removed by modern-day treatment technology are a growing threat to water quality and health. The emergence of antibiotics in the aquatic environment is a matter of concern as they may induce bacterial resistance, a major threat to health-care management and an increasing economic crisis. The current methods that are used to detect antibiotics are expensive and time consuming due to the sample preparation necessary for the determination of low concentrations of antibiotics in water and the instruments used. Electrochemical sensors and biosensors are simple systems, with high selectivity and sensitivity for individual measurements and low cost. In this study, we present a novel polyamic acid/graphene oxide electrode that was prepared for electrochemical screening of selected antibiotic residues in aqueous solution. Polyamic acid and graphene oxide were synthesized independently and characterized using microscopic, spectroscopic, and voltammetric approaches. A polyamic acid/graphene oxide/screen-sprinted carbon electrode was prepared in situ by electrochemical deposition of polyamic acid/graphene (0.03?mg/mL 50:50 mass ratio) on screen-printed carbon electrodes using five cycles between ?1000 and 1000?mV at 50?mV/s. The polyamic acid/graphene oxide/screen-printed carbon electrode provided limits of detection of 0.034?µM for norfloxacin and 1.07?µM for neomycin. Recovery studies on synthetic urine showed good inter-day and intra-day coefficients of variation (n?=?3). 相似文献
18.
K. Shikano H. Yonezawa T. Shigematsu 《Journal of Radioanalytical and Nuclear Chemistry》1993,173(2):409-417
The charged particle activation analysis of ultra-trace carbon in boron-doped silicon with the12C(d,n)13N reaction has been developed. In order to apply13N substoichiometric separation to determine carbon in silicon, we studied the rapid dissolution of silicon using nitric acid as the13N carrier. Its amounts were as small and definite as possible and the nitrogen oxide gas produced during the dissolution was collected. Silicon was dissolved for 6 min in a mixture of hydrofluoric acid, acetic acid and phosphoric acid, which contained potassium nitrate as the13N carrier and nitrogen oxide was collected in the sodium hydroxide solution. In order to combine the dissolution method with13N substoichiometric separation, the conditions for steam distillation as pre-separation were also refined in relation to increases in the amount of carrier. Nitrogen-13 was separated substoichiometrically after silicon dissolution and steam distillation. This analytical procedure was used to determine carbon in boron-doped CZ–Si. Carbon at 0.7–12.7·1015 atoms/cm3 was determined with good reproducibility. It took less than 30 min to start the radioactivity measurement after the end of iradiation. The detection limit was 2·1013 atoms/cm3 (0.2 ppb). 相似文献
19.
Anhydride terminated polyamic acid prepolymer was prepared from pyromellitic dianhydride and a diamine (para-phenylene diamine/benzidine) in dimethyl formamide. The prepolymer was reacted with the other diamine to obtain (AnB)m block copolymic acid. The polyamic acid was converted to the polyimide by thermal cyclodehydration. The properties of block copolyimides were compared with those of random copolyimides prepared by conventional routes. 相似文献
20.
A one‐step procedure is proposed for synthesizing 2‐acyl benzopyrano[2,3‐c]pyrazoles and 2‐aryl benzopyrano[2,3‐c]pyrazoles. The method is based on the condensation of 2‐iminocoumarin‐3‐carbonitriles with hydrazides and hydrazines in acid as catalysts. A mechanism of reaction is proposed. All prepared compounds are identified by FTIR, 1H NMR, 13C NMR, mass spectroscopy, and elemental analysis. 相似文献