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1.
Chin‐Ping Yang Ruei‐Shin Chen Kuei‐Hung Chen 《Journal of polymer science. Part A, Polymer chemistry》2003,41(7):922-938
To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF3 groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003 相似文献
2.
Aiqing Zhang Xiangdan Li Changwoon Nah Keejun Hwang Myong‐Hoon Lee 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):22-29
A soluble aromatic polyimide was chloromethylated via a reaction with chloromethyl methyl ether in the presence of tin(IV) chloride to produce a new starting material for the modification of aromatic polyimides. The chemical structure of the resulting polymer was confirmed by 1H NMR and Fourier transform infrared spectroscopy. The maximum number of chloromethyl groups per repeat unit was 1.81. The chloromethylated polyimide was stable up to 250 °C and soluble in both chloroform and tetrahydrofuran. So that its utilization for further modification could be demonstrated, cinnamic acid was reacted with the formed polyimide, and it produced a new photosensitive polyimide with a cinnamoyl side chain. The photosensitivity of the resulting polyimide was investigated with ultraviolet spectroscopic methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 22–29, 2003 相似文献
3.
P. Banu Ganga Radhakrishnan 《Journal of polymer science. Part A, Polymer chemistry》2004,42(2):341-350
The phase‐separation behavior of thermoplastic poly(ester‐imide) [P(E‐I)] multiblock copolymers, (A‐B)n, was investigated by a stepwise variation of the imide content. All the multiblock copolymers were synthesized by solution polycondensation with dimethylformamide as a solvent. P(E‐I)s were prepared with anhydride‐terminated polyester prepolymer and diisocyanates. Polyester prepolymers were prepared by the reaction of pyromellitic dianhydride and two different polyols [poly(tetramethylene oxide glycol) (PTMG) and polycaprolactone diol (PCL)]. Structural determination was done with Fourier transform infrared spectroscopy and Fourier transform NMR, and the molecular weight was determined by gel permeation chromatography. The effect of the imide content on the thermal properties of the synthesized P(E‐I)s was investigated by thermogravimetric analysis and differential scanning calorimetry. The polymers were also characterized for static and dynamic mechanical properties. Thermal analysis data indicated that the polymers based on PTMG were stable up to 330 °C in nitrogen atmosphere and exhibited phase‐separated morphology. Polymers based on PCL showed multistage decomposition, and the films derived from them were too fragile to be characterized for static and dynamic mechanical properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 341–350, 2004 相似文献
4.
Chin‐Ping Yang Sheng‐Huei Hsiao Che‐Yu Tsai Guey‐Sheng Liou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(10):2416-2431
Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004 相似文献
5.
Sang‐Uk Kim Choonkeun Lee Saimani Sundar Wonbong Jang Seung‐Jin Yang Haksoo Han 《Journal of Polymer Science.Polymer Physics》2004,42(23):4303-4312
A series of polyimides were synthesized from 2,2‐Bis(3,4‐dicarboxyphenyl)hexafluoropropane, 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane, and 4,4′‐oxydianiline by chemical imidization. The effects of the diamine ratios on the properties of the films were evaluated through the study of their thermal, electrical, and morphological properties. All the polymers exhibited better solubility in most of the organic solvents and hence were easily processable. Polyimides with more 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane exhibited better solubility and a low refractive index, which is highly desired for microelectronic applications. The dielectric constant and birefringence were strongly dependent on the fluorine content. With an increase in the fluorine substitution, both the dielectric constant and birefringence decreased. All the polymers exhibited high thermal stability (>400 °C). The absence of crystalline melting in differential scanning calorimetry and broad wide‐angle X‐ray diffraction patterns revealed the amorphous nature of the polymers, which was due to the presence of bulky CF3 groups and hinged ether linkages of the diamine component. The residual stress values decreased with an increase in the 4,4′‐oxydianiline content, and the results were in agreement with the dielectric constant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4303–4312, 2004 相似文献
6.
The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH4 > N2 > O2 > CO2. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO2 decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO2‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004 相似文献
7.
There is considerable interest in protein adsorption onto microspheres because of its importance in a wide range of biomedical applications, such as artificial tissues and organs, drug delivery systems, biosensors, solid-phase immunoassays, immunomagnetic cell separation and immobilized enzymes or catalyst. It has been well known that the interaction between proteins and microspheres plays important roles in this process. Major interaction involved in the adsorption can be classified as electrostatic, hydrophobic and hydrogen-bonding. Indeed, adsorption of proteins onto microspheres is a complex process and often can involve many dynamic steps, from the initial attachment of the protein on the surface of microspheres to the equilibrium. Also the conformation of proteins probably occurs to a certain degree of deformation or structural change due to the large area of contact. Recently, much interest has been shown in sulfonated microspheres, since sulfonate-group itself is one of components in bio-bodies, as well as is sensitive to the change of pH or ionic strength. Indeed, so far, scanty investigations have been performed in the full range. Also few researches have involved the data on adsorption rate and the maximum amount of protein adsorbed, or the reversibility of the process and conformational change of protein adsorbed as well.In present study, BSA (bovine serum albumin) was chosen as the model protein and sulfonated PMMA [poly(methyl methacrylate)] microspheres as the matrix to investigate the adsorption process.The purpose is to show some information especially the intrinsic information involved by the adsorption process Adsorption of BSA onto sulfonated microspheres (MS) has been investigated as a function of time, protein concentration and pH. The adsorption appears to be a reversible process and the presence of sulfonate groups can play important roles in the adsorption process, so as to increase the amount of protein adsorbed and influences the interaction of BSA molecules. Fig. 1 also shows that the reciprocation between unadsorbed and adsorbed BSA or rearrangement of adsorbed BSA molecules does not produce visible change in the properties of the adsorbed protein. Close to the isoelectric point of BSA (pI 4.7), the amount of protein adsorbed exhibits a maximum. A higher or lower pH results in the significant decrease of the adsorption amount. This is related to the dependence of BSA conformations at different pH conditions. 相似文献
8.
The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc. 相似文献
9.
H. Okumura T. Takahagi N. Nagai S. Shingubara 《Journal of Polymer Science.Polymer Physics》2003,41(17):2071-2078
The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003 相似文献
10.
Boena N. Kolarz Maria Wojaczyska Jan Kaczmarczyk Teresa Siemieniewska Kazimierz Tomkw 《Journal of Polymer Science.Polymer Physics》1994,32(12):1977-1990
Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca2+ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m2/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m2/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc. 相似文献