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1.

In the present study, TEIA bioresin was blended with the diglycidyl ether bisphenol A (DGEBA) epoxy resin in different ratios (i.e. 10, 20, 30, 40 mass%), cured with methylhexahydrophthalic anhydride curing agent in the presence of 2-methylimidazole catalyst. The optimized composition of DGEBA and TEIA bioresin blends system was employed as an adhesive strength. The adhesive strength of the TEIA-modified DGEBA epoxy resin blend system was increased from 4.14 to 6.31 MPa on an aluminium substrate compared to the DGEBA epoxy resin. The curing kinetics of non-isothermal, DGEBA epoxy resin and its bio-based blend systems were investigated employing differential scanning calorimetry. An increase in the peak temperature and reduction in a heat of curing as well as activation energy in DGEBA epoxy resin were observed with the addition of TEIA bioresin content. The activation energy (Ea) of the DGEBA resin and their bio-based blend system were obtained from Kissinger and Flynn–Wall–Ozawa methods.

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2.
High molecular weight bisphenol A or hydroquinone‐based poly(arylene ether phosphine oxide/sulfone) homopolymer or statistical copolymers were synthesized and characterized by thermal analysis, gel permeation chromatography, and intrinsic viscosity. Miscibility studies of blends of these copolymers with a (bisphenol A)‐epichlorohydrin based poly(hydroxy ether), termed phenoxy resin, were conducted by infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. All of the data are consistent with strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the phenoxy resin as the miscibility‐inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mol % of phosphine oxide units in the bisphenol A poly(arylene ether phosphine oxide/sulfone) copolymer. Single glass transition temperatures (Tg) from about 100 to 200°C were achieved. Replacement of bisphenol A by hydroquinone in the copolymer synthesis did not significantly affect blend miscibilities. Examination of the data within the framework of four existing blend Tg composition equations revealed Tg elevation attributable to phosphonyl/hydroxyl hydrogen bonding interactions. Because of the structural similarities of phenoxy, epoxy, and vinylester resins, the new poly(arylene ether phosphine oxide/sulfone) copolymers should find many applications as impact‐improving and interphase materials in thermoplastics and thermoset composite blend compositions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1849–1862, 1999  相似文献   

3.
The properties of diglycidyl ether of bisphenol-A epoxy resin toughened with poly(ether sulfone ether ketone) (PESEK) and poly(ether sulfone) (PES) polymers were investigated. PESEK was synthesised by the nucleophilic substitution reaction of 4,4’-difluorobenzophenone with dihydroxydiphenylsulfone using sulfolane as solvent and potassium carbonate as catalyst at 230 °C. The T g–composition behaviour of the homogeneous epoxy resin/PESEK blend was modelled using Fox, Gordon–Taylor and Kelley–Bueche equations. A single relaxation near the glass transition of epoxy resin was observed in all the blend systems. From dynamic mechanical analysis, the crosslink density of the blends was found to decrease with increase in the thermoplastic concentration. The storage modulus of the epoxy/PESEK blends was lower than that of neat resin, whilst it is higher for epoxy/PES blends up to glass transition temperature, thereafter it decreases. Scanning electron microscopic studies of the blends revealed a homogeneous morphology. The homogeneity of the blends was attributed to the similarity in chemical structure of the modifier and the cured epoxy network and due to the H-bonding interactions between the blend components. The fracture toughness of epoxy resin increased on blending with PESEK and PES. The increase in fracture toughness was due to the increase in ductility of the matrix. The thermal stability of the blends was comparable to that of neat epoxy resin.  相似文献   

4.
Hydroxyl‐terminated poly(ether ether ketone) with pendent tert‐butyl groups (PEEKTOH) was synthesized by the nucleophilic substitution reaction of 4,4′‐difluorobenzophenone with tert‐butyl hydroquinone with potassium carbonate as a catalyst and N‐methyl‐2‐pyrrolidone as a solvent. Diglycidyl ether of bisphenol A epoxy resin was toughened with PEEKTOHs having different molecular weights. The melt‐mixed binary blends were homogeneous and showed a single composition‐dependent glass‐transition temperature (Tg). Kelley–Bueche and Gordon–Taylor equations gave good correlation with the experimental Tg. Scanning electron microscopy studies of the cured blends revealed a two‐phase morphology. A sea‐island morphology in which the thermoplastic was dispersed in a continuous matrix of epoxy resin was observed. Phase separation occurred by a nucleation and growth mechanism. The dynamic mechanical spectrum of the blends gave two peaks corresponding to epoxy‐rich and thermoplastic‐rich phases. The Tg of the epoxy‐rich phase was lower than that of the unmodified epoxy resin, indicating the presence of dissolved PEEKTOH in the epoxy matrix. There was an increase in the tensile strength with the addition of PEEKTOH. The fracture toughness increased by 135% with the addition of high‐molecular‐weight PEEKTOH. The improvement in the fracture toughness was dependent on the molecular weight and concentration of the oligomers present in the blend. Fracture mechanisms such as crack path deflection, ductile tearing of the thermoplastic, and local plastic deformation of the matrix occurred in the blends. The thermal stability of the blends was not affected by blending with PEEKTOH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 541–556, 2006  相似文献   

5.
We synthesized novel aromatic epoxy, 4,4′‐bis(4‐oxyphenoxy)benzophenone diglycidyl ether (DGEEK), by a three step reaction sequence and then it was blended with 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexanecarboxylate (CAE). The DGEEK structure was confirmed by FT‐IR and 1H‐NMR measurement. Also, we investigated thermal properties of DGEEK/CAE blend epoxy by differential scanning calorimeter (DSC) and thermogravimetry analyzer (TGA). The glass transition temperature increased but initial decomposition temperature of cured epoxy decreased through the increasing amounts of ether–ether–ketone group of the epoxy network structure. By increasing the DGEEK mole fraction in the DGEEK/CAE blend epoxy matrix, the curing peak temperature decreased and the curing activation energy for DGEEK/CAE blend epoxy systems showed a considerable decrease. Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

6.
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   

7.
In this work we present the results from studies on novel poly(arylene ether ketone)s, including gas permeability, wide-angle x-ray diffraction (WAXD), and dynamic mechanical analysis (DMA). Poly(arylene ether ketone)s containing 2,2′- and 3,3′-dibenzoylbiphenyl (DBBP) moieties were characterized to study the effect of biphenyl substitution on gas transport properties. Gas permeabilities of naphthalene-containing poly(arylene ether ketone)s were also measured. Higher permeabilities were observed for polymers prepared with 6F-BPA, compared to 9,9-bis(4-hydroxyphenyl)fluorene (HPF). The naphthalene-containing polymers exhibited higher permeabilities than the DBBP polymers, except for a polymer having the 2,2′-DBBP and tetramethylbiphenyl moieties. Based on our work, and results reported in the literature, the 3,3′-DBBP polymers showed the lowest permeabilities for DBBP-containing poly-(arylene ether ketone)s. The low permeabilities are due to more efficiently packed chains brought on by greater flexibility of the backbone, compared to the other polymers studied. DMA studies confirmed the higher barriers to rotation which are believed to be responsible for 2,2′-DBBP polymers having similar selectivities compared to 3,3′-DBBP polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 425–431, 1998  相似文献   

8.
A series of macrocyclic arylene ether ketone oligomers from 4,4′-difluorobenzophenone, 2,4′-difluorobenzophenone and 1,3-bis(4′-fluorobenzoyl)benzene were prepared via aromatic nucleophilic substitution according to the pseudo-high dilution principle. Small-size aromatic macrocycles were isolated by silica gel column chromatography with cyclohexane/ethyl acetate as eluent. The chemical structures of these small-size macrocycles were characterized by matrix-assisted laser desorption ionization–time-of-flight–mass spectrometry (MALDI–TOF–MS), IR, 19F-,1H-, and 13C-NMR, and GPC techniques. Molecular chain length and steric hindrance of monomers affected the product compositions. The NMR results show that there are different chemical shifts in the different ring-size macrocyclic poly arylene ether ketones in spite of having the same repeating unit. The crystallizability and thermal properties of small-size arylene ether ketone macrocycles were also investigated by DSC, WAXD, TGA, and the results suggest that the crystallization and thermal properties are related to their intrinsic chemical structures. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1957–1967, 1999  相似文献   

9.
The application of FT Raman spectroscopy in the study of a wide range of polymer systems is discussed. The following have been included to give the reader an insight into the variety of areas which can successfully be studied using this important technique: the problem of crystallinity; nylons; poly(aryl ether ketone) and poly(aryl ether ether ketone); poly(aryl ether ether sulphone) and poly(aryl ether sulphone); epoxy resin curing; copolymers; copolymers of tetrafluoroethylene and hexafluoropropylene; polythioethers; and gels.  相似文献   

10.
New synthetic methodology was developed as part of an effort to increase the processibility of high Tg polyimide homo and copolymers, suitable as matrix resins and structural adhesives. Molecular weight and end group control together with solution imidization techniques were successfully employed to convert a variety of poly(amic acid) intermediates to fully cyclized polyimides. The solution imidization was conducted in N-methylpyrrolidone (NMP) with o-dichlorobenzene used as the azeotroping agent at 165–190°C. This technique has produced products which are more soluble than polyimides prepared previously by bulk thermal cyclization of poly(amic acids) at temperature of 300°C. They are also more stable than “chemically” imidized materials. In addition, incorporation of the monofunctional reagent phthalic anhydride provides nonreactive phthalimide end groups and controlled molecular weight. This latter feature significantly further improved the melt and solution processibility of the resulting polyimides. In this study thermoplastic, fully cyclized polyimides of 10 000, 20 000, and 30 000 M̄n were prepared which displayed glass transition temperatures ranging from 260–353°C, with the highest Tg observed with phthalimide capped polyimide systems derived from 6F-dianhydride and p-phenylene diamine. Tough, transparent films were prepared from polymers of 20 000 and 30 000 g/mol by casting from NMP solution or by compression molding at 50–70°C above the glass transition temperature. For purposes of molecular weight assessment, t-butyl phthalic anhydride was used as the end blocker. This permitted 400 M-Hertz proton NMR to be used for assessing the concentration of end groups. Comparison of the 18 aliphatic protons at the end of the chain allowed M̄n values to be determined, which agreed well with theory. A series of poly(arylene ether ketone)/aromatic polyimide blends were investigated to determine the influence of structural variation and composition on miscibility. As an extension to the PEEKTM/UltemTM blend system, which has been reported to be miscible over all proportions, this study examined how structural variations in both the poly(arylene ether ether ketone) and the polyimide portions affect miscibility. In particular, replacement of the hydroquinone fraction in PEEKTM with bisphenol A or sulfonyl diphenol produced an amorphous polymer which was no longer miscible with UltemTM. Polyimide structures modified by employing 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4′-[1,4-phenylene-bis-(1-methyl ethylidene)] bisaniline (Bis P) diamine to obtain higher glass transition temperatures were also investigated. This system afforded homogeneous blends with PEEKTM when the (Bis P) diamine was utilized in the synthesis of the polyimide. Furthermore, up to 50 mole percent of hexafluoro-bis-dianhydride (6FDA) could be substituted for BTDA without loss of miscibility. However, when the more polar 3,3′-diaminodiphenylsulfone diamine was employed, immiscible blends resulted. An additional important variant has been to incorporate polyimide siloxane segmented copolymers into the PEEKTM blend system. The polyimide segment can be designed to be miscible whereas the siloxane portion is homogeneously dispersed into a second phase which, in fact, enriches the surface behavior quite dramatically in siloxane content. The latter could be of some importance in allowing for atomic oxygen resistance and possibly improved flame resistance behavior.  相似文献   

11.
Thermoset/thermoplastic blends were prepared with epoxy–aromatic diamine mixtures and poly(L-lactide) (PLLA), as semicrystalline thermoplastic, in concentrations ranging from 4 to 25 wt.%. In some cases, poly(L,D-lactide) (PDLLA), an amorphous thermoplastic, was used instead for comparative purposes. Diglycidyl ether of bisphenol-A (DGEBA) was employed as epoxy resin and 4,4′-diaminodiphenylmethane (DDM) as curing agent. Phase behavior and morphology were studied during curing at 140 °C. Initially, all blends were homogeneous; however, the curing reaction of the epoxy resin caused a liquid–liquid phase separation. A co-continuous morphology was formed at the beginning of the phase separation in all the considered blend compositions. Blends evolved to a particle/matrix structure or to a phase-inverted structure depending on the initial blend composition. At 140 °C, crystallization only occurred in blends with 16 and 25 wt.% PLLA. This crystallization originates changes in the surface of the epoxy-rich droplets developed with the phase separation.  相似文献   

12.
The development of high-performance dielectric films with high energy density and temperature stability is extremely desired for modern electronics and power systems. Herein, a simple and low-cost approach is proposed to fabricate all-organic blend films prepared from poly (arylene ether urea) (PEEU) and polyimide (PI) via solution casting and thermal imidization process. The incorporation of PEEU in PI matrix significantly improved dielectric breakdown strength and dielectric constant of PI. More precisely, blend film with 15 wt% PEEU exhibited highest energy density 5.14 J/cm3 at 495.65 MV/m, with enhanced dielectric constant of 4.73 and very low dissipation factor of 0.299%. Furthermore, the dielectric properties of the PEEU/PI blend displayed wonderful temperature stability in the range of − 50–+ 250°C, and great frequency stability between 10 and 106 Hz. The blend film also exhibited excellent heat resistance and presented valuable potential in thin film capacitors for high voltage direct current system.  相似文献   

13.
A series of poly(arylene ether)s were successfully prepared by aromatic, nucleophilic substitution reactions with various perfluoroalkyl‐activated bisfluoromonomers with 4,4′‐bishydroxybiphenyl and 4,4′‐bishydroxyterphenyl. 4,4′‐Bishydroxyterphenyl was synthesized through the Grignard coupling reaction of magnesium salt of 4‐bromoanisole with dibromobenzene followed by demethylation with pyridine–hydrochloride. The products obtained by the displacement of fluorine atoms exhibited good inherent viscosity, up to 0.77 dL/g, and number‐average molecular weights up to 69,300. These poly(arylene ether)s showed very good thermal stability, up to 548 °C for 5% weight loss according to thermogravimetric analysis under synthetic air, and high glass‐transition temperatures, up to 259 °C according to differential scanning calorimetry, depending on the exact repeat unit structure. These polymers were soluble in a wide range of organic solvents, such as N‐methylpyrrolidone, dimethylformamide, tetrahydrofuran, toluene, and CHCl3, and were insoluble in dimethyl sulfoxide and acetone. Thin films of these poly(arylene ether)s showed good transparency and exhibited tensile strengths up to 132 MPa, moduli up to 3.34 GPa, and elongations at break up to 84%, depending on their exact repeating unit structures. These values are comparable to those of high‐performance thermoplastic materials such as poly(ether ether ketone) (PEEK) and Ultem poly(ether imide) (PEI). These poly(arylene ether)s exhibited low dielectric constants. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 55–69, 2002  相似文献   

14.
A new monomer 1,5‐bis(4‐fluorobenzoyl)‐2,6‐dimethoxynaphthalene (DMNF) was prepared and further polymerized to form naphthalene‐based poly(arylene ether ketone) copolymers containing methoxy groups (MNPAEKs). The side‐chain‐type sulfonated naphthalene‐based poly(arylene ether ketone) copolymers (SNPAEKs) were obtained by demethylation and sulfobutylation. Flexible and tough membranes with reasonably high mechanical strength were prepared. The SNPAEKs membrane showed anisotropic membrane swelling with larger swelling in thickness than in plane. Transmission electron microscopy (TEM) analysis revealed clear nanophase separated structure of SNPAEKs membranes, which composed of hydrophilic side chain and hydrophobic main‐chain domains. Proton conductivities of copolymers increased gradually with increase in temperature. The highest conductivity of 0.179 S/cm was obtained for SNPAEK‐80 (IEC = 1.82 mequiv/g) at 80 °C, which is higher than that of Nafion117 (0.146 S/cm). The SNPAEKs membranes exhibit the methanol permeability in the range of 3.42 × 10?8?4.49 × 10?7 cm2/s, which are much lower than that of Nafion117. They could be the promising materials as alternative to Nafion membrane for direct methanol fuel cells applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:5772–5783, 2009  相似文献   

15.
Sulfonated poly(phthalazinone ether ketone)s (SPPEK)s were synthesized by the modification of poly(phthalazinone ether ketone) (PPEK) with 98% concentrated sulfuric acid or 98% concentrated sulfuric acid and chlorosulfonic acid mixture at 80–100°C. The presence of sulfonic acid groups in SPPEKs was confirmed by Fourier transform infrared (FTIR) analysis and nuclear magnetic resonance (NMR), and the DSs were determined by Energy Dispersive X‐Ray (EDX). A blend membrane of No. 21 SPPEK and phosphotungstic acid (PWA) was prepared. The methanol permeabilities of SPPEK and blend membranes were about 20 times lower than that of Nafion117 at room temperature. The direct methanol fuel cell (DMFC) test of 2 M methanol solution and air breathing showed that the blend membrane had a better performance than that of the Nafion117. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

16.
利用低分子量环氧树脂(DGEBA)在固化后和与之共混的聚氯乙烯(PVC)之间产生的相分离,用丁酮抽提其中的PVC组分,制备了环氧树脂基多孔增透膜。测试结果表明,当mDOEBA/mPVC=30/70、膜厚为110nm时,增透膜的透过率最高,达96%以上。薄膜在水或甲苯中煮沸不发生收缩、脱落,表现良好的粘附力和机械强度。  相似文献   

17.
Novel acid–base blend membranes consisting of acidic sulfophenylated poly(ether ether ketone ketone) (Ph-SPEEKK) and various amounts of basic polysulfone tethered with 5-amino-benzotriazole (PSf-BTraz) have been prepared and characterized. The blend membranes show higher proton conductivity and lower liquid uptake and dimensional swelling compared to plain Ph-SPEEKK and sulfonated poly(ether ether ketone) (SPEEK) membranes. The Ph-SPEEKK/PSf-BTraz blend membranes with optimized basic polymer contents exhibit lower methanol crossover and higher performance with improved stability in direct methanol fuel cells (DMFC) at various methanol concentrations (1–10 M) than plain Ph-SPEEK and Nafion-115 membranes.  相似文献   

18.
Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4′-difluorobenzophenone and easily polymerized to high molecular weight linear poly-(ether ketone). The cyclic compound was characterized by FTIR, 1H- and 13C-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of the phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1753–1761, 1997  相似文献   

19.
Novel poly(arylene thioether)s were synthesised using the one pot polymerisation method from the bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane and activated difluoro aromatic compounds. Each of the polymers, obtained in good yields and with fairly high molecular weights, were characterised by IR, GPC and NMR analyses. In particular, the NMR characterisation was performed using 1H NMR, 13C NMR, DEPT, 2D COSY and 2D HSQC experiments. To study the effect on the thermal properties of replacing the ethereal oxygen atoms with sulfur atoms, we have synthesised the counterparts, the poly(arylene ether)s, with similar molecular weights. We observed that the substitution of the ethereal oxygen atoms with sulfur atoms results in a slightly lower thermal stability for the poly(thioether ketone)s, both under nitrogen and in air, and does not modify the Tg values. For the poly(thioether sulfone), on the other hand, the thermal stability is equal to that of the poly(ether sulfone), while the Tg is 10 °C lower. Furthermore, each sample is completely amorphous, with the exception of one of the poly(thioether ketone)s (sample 1b), which shows the capacity to crystallise, even if with a very slow crystallisation kinetics.  相似文献   

20.
New alternating copolymers comprising a chlorotrifluorinated backbone and imidazole‐terminated pendant ethylene oxide groups have been prepared with a view to their use as a component of proton‐conducting membranes in polymer electrolyte fuel cells. A vinyl ether containing an imidazole (Imi) function protected by a benzyl group (BVI) was first synthesized in a three‐step reaction. It was then copolymerized in solution with chlorotrifluoroethylene (CTFE) by conventional radical copolymerization leading to alternating poly(BVI‐alt‐CTFE) copolymers in good yields. Deprotection of the benzyl group under hydrogen produced a chlorotrifluorinated poly(Imi‐alt‐CTFE) copolymer. The polymer was subsequently used to form blend membranes with sulfonated poly(ether ether ketone) (sPEEK). The conductivity of blend membranes of poly (Imi‐alt‐CTFE) with sPEEK lies in the range of 4–10 mS cm?1 at 40–70 °C and, for blend membranes rich in poly(Imi‐alt‐CTFE), is little dependent on relative humidity between 30 and 100%. It is surmised that the polymer and membrane composition favor microstructural phase separation into chlorotrifluorinated polymer backbone domains and regions in which imidazole groups are clustered. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 223–231, 2010  相似文献   

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