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1.
Porous interior structured polyimide (PI) films with a hierarchical surface are fabricated from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride and 4,4′‐oxydianiline by a water vapor induced phase separation process under a humid environment. Superhydrophobic properties with a water contact angle of 161° are obtained using the hierarchical surface morphology, which can be adjusted from flower‐like to wrinkle‐shape particles facilely by changing the relative humidity. The dielectric constant (k) of the PI film decreases sharply from 2.8 (film prepared under dry conditions) to ≈1.9 (film prepared under humid conditions) because of the interior porous structure and fluorine‐containing framework. Both a low‐k and superhydrophobicity are very important parameters for PI films in microelectronic and insulating applications.  相似文献   

2.
A new diamine, 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′‐diiodo‐4,4′‐dinitrodiphenyl ether with 3,4,5‐trifluorophenylboronic acid to produce 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐dinitrodiphenyl ether (FPNPE), followed by palladium‐catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all‐aromatic poly(ether‐imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 °C were measured through the extrapolation of the concentrations used to zero. Mn and Mw of these polymers were about 10 000 and 25 000 g mol?1, respectively. The polymers showed a good film‐forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X‐ray diffraction measurements showed that the fluoro‐containing polymers have a nearly amorphous nature. The resulting polymers had Tg values higher than 340 °C and were thermally stable, with 10% weight loss temperatures being recorded above 550 °C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials. Copyright © 2011 Society of Chemical Industry  相似文献   

3.
High refractive index homogeneous hybrid materials were successfully prepared. The polymer matrix was the copolymer of methyl methacrylate, sulfur‐containing monomer 2,2′‐mercaptoethylsulfide dimethacrylate (MESDMA), and nanotitania was prepared by in situ solgel process of titanium n‐butoxide. The transmission electron microscope (TEM) study suggested that the hybrid was homogeneous without inorganic agglomerate, and the inorganic particles were 4–7 nm. The refractive index was ~ 1.75 when the inorganic content of the hybrid film reached to 70 wt %, and the transmittance maintained up to 85%. The sulfur‐containing monomer was used to improve the refractive index, also, it was a crosslinking reagent, which improved the film‐forming ability of the hybrid. After copolymerized with MESDMA, the film‐forming ability of the hybrid was better than the one without MESDMA. Even if the inorganic content exceeded 75 wt %, the films kept integrity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

4.
Surface segregation in polymer blend systems between 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐diaminodiphenyl ether (s‐BPDA/ODA) polyimide and block copolymer based on polysiloxane‐block‐polyimide (SPI) has been investigated. These polyimide blends, having various compositions of the SPI, were processed by a solution casting method. The glass substrate used in the film‐casting process shows significant effect on the migration of surface segregated species to enrich the air‐exposed surface, whereas the more polar s‐BPDA/ODA tends to remain close to the polar glass substrate. X‐ray photoelectron spectroscopy reveals that even at low SPI concentration, the siloxane moieties in the block copolymer tend to segregate into the air side surface. Contact angle measurement evidently indicates an enrichment of the hydrophobic siloxane fraction on the blend film surface. The average water contact angle of glass side surface is 77°C whereas that of the air side is about 102°C in every blend ratio. This behavior confirms the surface segregation phase separation in these polymer blends. Finally, the surface morphology observed by atomic force microscopy also suggests segregation type of phase separation in these blend systems. POLYM. ENG. SCI., 47:489–498, 2007. © 2007 Society of Plastics Engineers.  相似文献   

5.
A new ultraviolet (UV)-curable acrylic monomer, 4,4'-hexafluoroisopropylidene-diphenoldihydroxyethylether diacrylate, was synthesized: it was cured as a film and its properties compared with those of its fully hydrogenated homologue. The introduction of two CF3groups into the monomer did not change its reactivity in the UV-curing reaction, but increased the glass transition temperature (Tg) of the cured polymeric film, decreased its refractive index (n), and lowered its surface tension. The fluorinated and the hydrogenated monomers were completely miscible and give homogeneous films: the Tg and n values were found linearly dependent on the fluorinated monomer content. The surface properties were deeply influenced by the presence of fluorine; a surface enrichment of the fluorinated monomer was evidenced by X-ray photoelectron spectroscopy analyses on the surfaces of the films obtained from mixtures of the two monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 979–983, 1997  相似文献   

6.
BACKROUND: Polyimide films coated on copper are a potential new substrate for fabricating printed circuit boards; however, adhesion between the copper and polyimide films is often poor. The relations between residual stress and adhesion strength according to the development of molecular orientation of polyimide films with different chemical backbone structure coated on copper were studied. RESULTS: The effect of chemical structures on properties including the residual stress and the adhesion strength were widely investigated for four different polyimides. Diamine 4,4′‐oxydianiline (ODA) and dianhydrides 1,2,4,5‐benzenetetracarboxylic dianhydride (PMDA), 4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) were used to synthesize polyimide. In an attempt to quantify the interaction of thermal mismatch with the polyimide films depending on various structures, residual stress experiments between polyimide film and Cu? Si wafer were carried out over a range of 25–400 °C using in situ thin film stress analysis. A universal test machine was used to conduct 180° peel test (ASTM D903‐98) of polyimide film from cooper foil. The residual stress on Cu? Si (100) wafer decreased in the order 6FDA‐ODA > BTDA‐ODA > ODPA‐ODA > PMDA‐ODA, and the interfacial adhesion strength decreased in the order BTDA‐ODA (5 N mm?2) > ODPA‐ODA > PMDA‐ODA > 6FDA‐ODA. The results may suggest that the morphological structure, degree of crystallinity of chain orientation and packing significantly relate to the residual stress and adhesion strength in polyimide films. Wide‐angle X‐ray diffraction was used for characterizing the molecular order and orientation and X‐ray photoelectron spectroscopy was used for the analysis of components on copper after polyimide films were detached to confirm the existence of copper oxide chemical bonding and to measure the binding energy of elements on the copper surface. CONCLUSION: In this research, it is demonstrated that BTDA‐ODA polyimide has a low residual stress to copper, good adhesion property, good thermal property and low dielectric constant. Therefore, BTDA‐ODA would be expected to be a promising candidate for a two‐layer copper‐clad laminate. Copyright © 2007 Society of Chemical Industry  相似文献   

7.
4,4′‐Diamino‐3,3′‐dimethyldiphenylmethane was used to prepare polyimides in an attempt to achieve good organo‐solubility and light color. Polyimides based on this diamine and three conventional aromatic dianhydrides were prepared by solution polycondensation followed by chemical imidization. They possess good solubility in aprotonic polar organic solvents such as N‐methyl 2‐pyrrolidone, N,N‐dimethyl acetamide, and m‐cresol. Polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is even soluble in common solvents such as tetrahydrofuran and chloroform. Polyimides exhibit high transmittance at wavelengths above 400 nm. The glass transition temperature of polyimide from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and pyromellitic dianhydride is 370°C, while that from 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane and diphenylether‐3,3′,4,4′‐tetracarboxylic acid dianhydride is about 260°C. The initial thermal decomposition temperatures of these polyimides are 520–540°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1299–1304, 1999  相似文献   

8.
A series of polyimide/titania (PI/TiO2) hybrid films have been successfully synthesized based on titanium tetrabutoxide (Ti(OEt)4), 3,3′,4,4′‐bezonphenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydianiline (ODA), and 1,3‐bis(aminopropyl) tetramethyldisiloxane (APrTMOS) by a sol–gel process. The atomic oxygen (AO) exposure tests were carried out using a ground‐based AO effects simulation facility. The chemical structure of PI/TiO2 films was characterized by Fourier transform‐infrared (FT‐IR) spectroscope before and after AO exposure. The glass transition temperature (Tg) and mechanical properties were examined by dynamic mechanical analysis (DMA) and universal mechanical testing machine, respectively. The tensile strength and elongation of the hybrid film decreased with the increase of TiO2 content, whereas the Tg increased with the increase of TiO2 content. The effects of TiO2 content on the morphology and structure evolvement of PI/TiO2 hybrid films were also investigated using field emission scanning electron microscopy (FE‐SEM) and X‐ray photoelectron spectroscope (XPS), respectively. The results indicated that a TiO2‐rich layer resulting from the Ti(OEt)4 formed on the PI film after AO exposure, which decreased the mass loss rate and obviously improved the AO resistance of PI films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
Ultralow refractive index films were prepared based on a base‐catalyzed sol–gel process using methyltriethoxysilane (MTES), tetraethylorthosilicate (TEOS) as co‐precursors, and hydroxypropyl‐beta‐cyclodextrin (HPCD) as porogen. After further modification by hexamethylisilazane (HMDS), the lowest refractive index of these silica coatings obtained from the hybrid sol was 1.05 and the static water contact angles of the coatings increased from 66.4° to 128.7°. The effect of weight ratio of HPCD to SiO2 on the refractive index and on the formation of coating films were systematically studied. The data showed that the films prepared with HPCD as porogen got a pore diameter around 4 nm. Compared with those templates such as poloxamer (F127), HPCD not only perform well in decreasing the refractive index of films, but also eliminate light scattering caused by mesopore of the film, will have potential value in the field of surfactant‐templated methods. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44686.  相似文献   

10.
Layered silicate/polyimide (PI) hybrid films were prepared from 4,4′‐oxydianiline, 3,3′,4,4′‐oxydiphthalic anhydride, and chemically modified montmorillonite via an in situ intercalation polymerization pathway. The X‐ray diffraction and transmission electron microscopy results indicated that the silicates were homogeneously dispersed as exfoliated layers in the PI hybrid film with 2% silicate. The mechanical properties and thermal stabilities of the PI hybrid films changed with the content of the layered silicates. The coefficient of thermal expansion and water uptake of the PI hybrid films decreased with increasing silicate contents because of the barrier effect of platelike silicate layers, which prevented the diffusion and penetration of water. The dielectric strength and electrical aging performance of the PI hybrid films could also be improved as the silicate layer highly dispersed in the films. For the hybrid PI film with 5% layered silicate, the time to failure during electrical aging exceeded 280 h, which was 2.5 times as long as that of pure PI film. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1176–1183, 2005  相似文献   

11.
A series of novel aromatic polyimides were synthesized from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic tetracarboxylic dianhydrides through a conventional two‐step procedure. Most of the polyimides exhibited reasonable solubility in organic solvents and could afford robust films via solution casting. The polyimides exhibited high thermal stability, with glass transition temperatures in the range 227–273 °C and 10% weight‐loss temperatures in excess of 550 °C. All the polyimide films showed ambipolar redox and multi‐electrochromic behaviors. They exhibited two reversible oxidation redox couples at 0.94–0.98 and 1.09–1.12 V versus Ag/AgCl in acetonitrile solution. A coupling reaction between the radical cations of the pendent triphenylamine units occurred during the oxidative process forming a tetraphenylbenzidine structure which resulted in an additional redox state and color change. © 2014 Society of Chemical Industry  相似文献   

12.
Two new aromatic diamines, 2,2′‐dibromo‐4,4′‐oxydianiline (DB‐ODA 4 ) and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianiline (TB‐ODA 5 ), have been synthesized by oxidation, bromination, and reduction of 4,4′‐oxydianiline (4,4′‐ODA). Novel polyimides 6a–f and 7a–f were prepared by reacting DB‐ODA ( 4 ) and TB‐ODA ( 5 ) with several dianhydrides by one‐step method, respectively. The inherent viscosities of these polyimides ranged from 0.31 to 0.99 dL/g (0.5 g/dL, in NMP at 30°C). These polyimides showed enhanced solubilities compared to those derived from 4,4′‐oxydianiline and corresponding dianhydrides. Especially, polyimides 7a , derived from rigid PMDA and TB‐ODA ( 5 ) can also be soluble in THF, DMF, DMAc, DMSO, and NMP. These polyimides also exhibited good thermal stability. Their glass transition temperatures measured by thermal mechanical analysis (TMA) ranged from 251 to 328°C. When the same dianhydrides were used, polyimides 7 containing four bromide substituents had higher glass transition temperatures than polyimides 6 containing two bromide substituents. The effects of incorporating more polarizable bromides on the refractive indices of polyimides were also investigated. The average refractive indices (nav) measured at 633 nm were from 1.6088 to 1.7072, and the in‐plane/out‐of‐plane birefringences (Δn) were from 0.0098 to 0.0445. It was found that the refractive indices are slightly higher when polyimides contain more bromides. However, this effect is not very obvious. It might be due to loose chain packing resulted from bromide substituents at the 2,2′ and 2,2′,6,6′ positions of the oxydiphenylene moieties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

13.
A series of new, organosoluble, and light‐colored poly(amide imide imide)s were synthesized from tetraimide dicarboxylic acid ( I ) and various aromatic diamines by direct polycondensation with triphenyl phosphite and pyridine as condensing agents. I was prepared by the azeotropic condensation of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, m‐aminobenzoic acid, and 4,4′‐oxydianiline at a 2/2/1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP)/toluene. The thin films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 400 nm (365–394 nm) and color coordinate b* values between 13.10 and 36.07; these polymers were lighter in color than the analogous poly(amide imide)s and isomeric polymers. All of the polymers were readily soluble in a variety of organic solvents, including NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even less polar dioxane and tetrahydrofuran. The cast films exhibited tensile strengths of 90–104 MPa, elongations at break of 7–22%, and initial moduli of 1.9–2.4 GPa. The glass‐transition temperatures of the polymers were recorded at 274–319°C. They had 10% weight losses at temperatures beyond 520°C and left more than a 50% residue even at 800°C in nitrogen. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 669–679, 2003  相似文献   

14.
A new synthesis route for elastic polyurethane‐imides (EPUIs) has been established by a method involving the use of urea. Various EPUIs were synthesized from polyurethane‐urea, which was prepared from 4,4′‐diphenylmethane diisocyanate (MDI), polyoxytetramethylene glycol (PTMG) and 4,4′‐diphenylmethanediamine (MDA), and pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP). Flexible films were cast from these solutions that had different inherent viscosities. Imidization of the EPUI films was completed at 200°C for 4 h in vacuo. The EPUIs were determined by FTIR, 1H NMR, and 13C NMR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

15.
Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ~ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
Graphite was functionalized electrochemically in a potassium fluoride solution and used to prepare polyimide (PI)/graphene nanohybrid films. The as‐made electrochemically fluorinated graphene (EFG) was used to prepare nanohybrid films with colorless PI, which was synthesized from 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride and bis(trifluoromethyl) benzidine by in situ polymerization. The surface functionalization of graphite was characterized by powder XRD, TEM with energy dispersive X‐ray spectroscopy elemental mapping, X‐ray photoelectron spectroscopy, Raman spectroscopy, and TGA. The microstructure of the films was characterized by Fourier transform IR spectroscopy, XRD and SEM. The film properties were measured using a universal testing machine, TGA, dynamic mechanical analysis, four‐point probe, UV–visible spectroscopy and water contact angle analysis. EFG improved the tensile strength and modulus of the nanohybrid films by 20% and 50%, respectively. The glass transition temperature and electrical conductivity of the nanohybrid films were 12 °C and nine orders of magnitude higher than those of the neat PI film, respectively. The nanohybrid film maintained 80% optical transmittance even after the addition of 0.1 wt% EFG. © 2019 Society of Chemical Industry  相似文献   

17.
In this research, a series of porous copolyimide (co‐PI) films containing trifluoromethyl group (CF3) were facilely prepared via a phase separation process. The co‐PI were synthesized by the reaction of benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride (BTDA) with two diamines of 4,4′‐diaminodiphenyl ether (ODA) and 3‐trifluoromethyl‐4,4'‐diaminodiphenyl ether (FODA) with various molar ratios. The flexible and tough porous co‐PI films with about 300 μm thickness and 8~10 μm average diameter could be obtained by solution casting conveniently. The thermal properties of the obtained porous co‐PI films were excellent with a glass transition temperature at 270 °C ~ 280 °C and only 5% weight loss in temperature from 530 °C to 560 °C under nitrogen atmosphere. In addition, the dielectric and hydrophobic properties of porous co‐PI films were remarkably improved owing to the presence of trifluoromethyl groups (CF3) in the polymer chains. Moreover, our synthesized porous co‐PI films also showed good mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44494.  相似文献   

18.
Poly(amide‐imide), PI, hybrid films are prepared by using sol–gel techniques. First, the poly(amide amic acid) with controlled block chain length of 5000 and 10,000 g/mol and uncontrolled chain length are synthesized by condensation reaction with 4,4′‐diaminodiphenyl ether (ODA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), trimellitic anhydride chloride (TMAC) and terminated with p‐aminopropyltrimethoxysilane (APrTMOS). And then the imidization reactions of poly (amide amic acid) are proceeded to obtain the poly (amide‐imide) hybrid film. Hybrid films with 5000 g/mol block chain length possess higher storage modulus, lower glass transition temperature and damping intensity comparing to films with 10,000 g/mol block chain length. The addition of TMAC to the poly(amide‐imide) hybrids is due to the increase of toughness and intermolecular hydrogen bonding, which is the average strength of intermolecular bonding and studied by the hydrogen‐bonded fraction (fbonded), frequency difference (Δν) and shiftment. Meanwhile, PI hybrid films containing more APrTMOS and TMAC content possess higher thermal and mechanical properties. On the other hand, hybrid films with 10,000 g/mol block chain length and more TMAC content have higher gas permeabilities than other films. The degradation temperatures of 5 wt % loss of all hybrid films are all higher than 540°C and increased as the increase of TMAC content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

19.
Thin films of an organo‐soluble polyimide based on 1,4‐(3,4‐dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2′‐dimethyl‐4,4′‐methylene dianiline (DMMDA) have been studied. A prism coupler was used to measure the refractive indices. The average refractive indices of thin films prepared by annealing at different temperatures and times were chosen to characterize the condensation states of thin films. Thin films annealed at 200 °C show irreversible changes in physical properties, eg solubility. FTIR spectroscopy showed that the chain structures of the above thin films remained unchanged. It is proposed that specific molecular interactions induce the irreversible changes revealed by fluorescence spectroscopy. © 2000 Society of Chemical Industry  相似文献   

20.
A novel aromatic diamine, 3,3′‐diisopropyl‐4,4′‐diaminophenyl‐4″‐methyltoluene with a 4‐methylphenyl pendant group and isopropyl side groups, was designed and synthesized in this study. Then it was polymerized with various aromatic dianhydrides including pyromellitic dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride via a one‐pot high temperature polycondensation procedure to produce a series of aromatic polyimides. These polyimides exhibited excellent solubility even in common organic solvents, such as chloroform and tetrahydrofuran. The flexible and tough films can be conveniently obtained by solution casting. The films were nearly colorless and exhibited high optical transparency, with the UV cutoff wavelength in the range 302–365 nm and the wavelength of 80% transparency in the range 385–461 nm. Moreover, they showed low dielectric constants (2.73–3.23 at 1 MHz) and low moisture absorption (0.13%–0.46%). Furthermore, they also possessed good thermal and thermo‐oxidative stability with 10% weight loss temperatures (T10%) in the range 489–507 °C in a nitrogen atmosphere. The glass transition temperatures of all polyimides are in the range 262–308 °C. Copyright © 2012 Society of Chemical Industry  相似文献   

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