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1.
It has been proved in our previous study that during the melt‐blending of an epoxy oligomer based on the diglycidyl ether of bisphenol‐A (DGEBA) with polycarbonate (PC) at 200°C, the secondary hydroxyl groups in the DGEBA react with the carbonate groups in PC through transesterification, resulting in degraded PC chains with phenolic end groups and also in PC/DGEBA copolymers. Yet, in the same study, it was found that the prereactions between DGEBA and PC can be minimized or eliminated if a solution‐blending process was used. Therefore, it was expected that, after being cured with a curing agent, different epoxy‐network structures should result as a consequence of the two different premixing processes of DGEBA and PC. In addition, we also expect that in the melt‐blending process, the fracture toughness of epoxies should be increased due to the incorporation of ductile PC chains into the epoxy network. In this study, therefore, we attempted to examine and compare the structures and properties of PC‐modified epoxies through these two different blending processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2510–2521, 1999  相似文献   

2.
BACKGROUND: Reactive thermoplastics have received increasing attention in the field of epoxy resin toughening. This paper presents the first report of using a novel polyaryletherketone bearing one pendant carboxyl group per repeat unit to cure the diglycidyl ether of bisphenol‐A epoxy resin (DGEBA). The curing reactions of DGEBA/PEK‐L mixtures of various molar ratios and with different catalysts were investigated by means of dynamic differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy methods. RESULTS: FTIR results for the DGEBA/PEK‐L system before curing and after curing at 135 °C for different times demonstrated that the carboxyl groups of PEK‐L were indeed involved in the curing reaction to form a crosslinked network, as evidenced by the marked decreased peak intensities of the carboxyl group at 1705 cm?1 and the epoxy group at 915 cm?1 as well as the newly emerged strong absorptions of ester bonds at 1721 cm?1 and hydroxyl groups at 3447 cm?1. Curing kinetic analysis showed that the value of the activation energy (Ea) was the highest at the beginning of curing, followed by a decrease with increasing conversion (α), which was attributed to the autocatalytic effect of hydroxyls generated in the curing reaction. CONCLUSION: The pendant carboxyl groups in PEK‐L can react with epoxy groups of DGEBA during thermal curing, and covalently participate in the crosslinking network. PEK‐L is thus expected to significantly improve the fracture toughness of DGEBA epoxy resin. Copyright © 2009 Society of Chemical Industry  相似文献   

3.
A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between GIC and plateau modulus (above the resin Tg), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999  相似文献   

4.
Epoxy resins based on 4,4′-dihydroxydiphenylsulfone (DGEBS) and diglycidyl ether of bisphenol A (DGEBA) were prepared by alkaline condensation of 4,4′-dihydroxydiphenylsulfone (bisphenol S) with epichlorohydrin and by recrystallization of liquid, commercial bisphenol A-type epoxy resin, respectively. Curing kinetics of the two epoxy compounds with 4,4′-diaminodiphenylmethane (DDM) and with 4,4′-diaminodiphenylsulfone (DDS) as well as Tg values of the cured materials were determined by the DSC method. It was found that the ? SO2? group both in the epoxy resin and in the harener increases Tg values of the cured materials. DGEBS reacts with the used hardeners faster than does DGEBA and the curing reaction of DGEBS begins at lower temperature than does the curing reaction of DGEBA when the same amine is used. © 1994 John Wiley & Sons, Inc.  相似文献   

5.
Amino‐functionalized multiwalled carbon nanotubes (MWCNT‐NH2s) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with amine‐terminated butadiene–acrylonitrile (ATBN). The curing kinetics, glass‐transition temperature (Tg), thermal stability, mechanical properties, and morphology of DGEBA/ATBN/MWCNT‐NH2 nanocomposites were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis, a universal test machine, and scanning electron microscopy. DSC dynamic kinetic studies showed that the addition of MWCNT‐NH2s accelerated the curing reaction of the ATBN‐toughened epoxy resin. DSC results revealed that the Tg of the rubber‐toughened epoxy nanocomposites decreased nearly 10°C with 2 wt % MWCNT‐NH2s. The thermogravimetric results show that the addition of MWCNT‐NH2s enhanced the thermal stability of the ATBN‐toughened epoxy resin. The tensile strength, flexural strength, and flexural modulus of the DGEBA/ATBN/MWCNT‐NH2 nanocomposites increased increasing MWCNT‐NH2 contents, whereas the addition of the MWCNT‐NH2s slightly decreased the elongation at break of the rubber‐toughened epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40472.  相似文献   

6.
A novolac epoxy resin based on 4,4′‐dihydroxybenzophenone (BZPNE) was synthesized via epoxidation of 4,4′‐dihydroxybenzophenone novolac resin (BZPN). BZPN was obtained by strong mineral acid catalyzed reaction of 4,4′‐dihydroxybenzophenone (BZP) and paraformaldehyde. The formation of BZPNE and BZPN was confirmed by Fourier transform infrared spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy, gel permeation chromatography, and epoxy equivalent weight. Different blends of BZPNE with diglycidyl ether of bisphenol‐A (DGEBA; EEW ~180) were cured using dicyandiamide were characterized by thermogravimetric analysis, thermomechanical analysis, dynamic mechanical analysis, and interfacial property between aluminum adherends at ambient and elevated temperature. Thermal properties were found to improve on increasing quantity of BZPNE in DGEBA as it is evidenced from glass transition temperature (Tg). Likewise, no deterioration in interfacial properties was observed with the highest quantity of BZPNE (30%) in DGEBA blend, when tested at 150 °C. Cure kinetics of compositions were studied by nonisothermal differential scanning calorimetry and Kissinger method was used to compute the kinetic parameters such as frequency factor (A), activation energy (Ea) followed by the dependency of rate constant (k) on temperature of different blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46164.  相似文献   

7.
The kinetics of the cure reaction for a system of bisphenol‐A epoxy resin (DGEBA), with 4, 4′‐diaminoazobenzene (DAAB), reinforced with nanosilica (NS), and nanoclay (NC) by means of isothermal technique of differential scanning calorimetry were studied. The Kamal autocatalytic‐like kinetic model was used to estimate the reaction orders (m, n), rate constants (k1, k2), and also active energies (Ea) and pre‐exponential factors (A) of the curing reaction. However, the existence of NS and NC with hydroxyl groups in the structure improves the cure reaction and influence the rate of reaction and therefore kinetics parameters. The Ea of cure reaction of DGEBA/DAAB system showed a decrease when nanoparticles were present and therefore the rate of the reaction was increased. Using the rate constants from the kinetic analysis and transition state theory, thermodynamic parameters such as enthalpy (ΔH#), entropy (ΔS#), and Gibbs free energy (ΔG#) changes were also calculated. The thermodynamic functions were shown to be very sensitive parameters for evaluation of the cure reaction. POLYM. COMPOS., 31:1442–1448, 2010. © 2009 Society of Plastics Engineers  相似文献   

8.
A novel, halogen‐free, phosphorus–nitrogen containing flame retardant 2[4‐(2,4,6‐Tris{4‐[(5,5‐dimethyl‐2‐oxo‐2λ5‐[1,3,2]dioxaphosphinan‐2‐yl)hydroxymethyl]phenoxy}‐(1,3,5)‐triazine (TNTP) was successfully synthesized in a three‐step process, and characterized by FTIR, NMR spectroscopy, mass spectra, and elemental analysis. A series of modified DGEBA epoxy resin with different loadings of TNTP were prepared and cured by 4,4‐diaminodiphenylsulfone (DDS). Thermal gravimetric analysis and vertical burning test (UL‐94) were used to evaluate the flame retardancy of TNTP on DGEBA epoxy resin. The results showed that TNTP had a great impact on flame retardancy. All modified thermosets by using TNTP exhibited higher Tg than pure DGEBA/DDS. The loading of TNTP at only 5.0 wt % could result in satisfied flame retardancy (UL‐94, V‐0) together with high char residue (27.3%) at 700°C. The addition of TNTP could dramatically enhance the flame retardancy of DGEBA epoxy resins, which was further confirmed by the analysis of the char residues by scanning electron microscopy and FTIR. Furthermore, no obviously negative effect was found on the Izod impact strength and flexural property of DGEBA epoxy resins when TNTP loading limited in 5.0 wt %. DGEBA/DDS containing 2.5 wt % TNTP could enhance Izod impact strength from 10.47 to 10.94 kJ m?2, and showed no appreciable effect on the flexural property (85.20 MPa) comparing with pure DGEBA/DDS (87.03 MPa). Results indicated that TNTP as a phosphorus–nitrogen synergistic intumescent flame retardant could be used for DGEBA epoxy resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41079.  相似文献   

9.
The DGEBA–MHHPA epoxy system has found increasing applications in microelectronics packaging, making crucial the ability to understand and model the cure kinetics mechanism accurately. The present article reports on work done to elucidate an appropriate model, modified from the empirical DiBenedetto's equation, to relate the glass‐transition temperature (Tg) to the degree of conversion for a DGEBA–MHHPA epoxy system. This model employs the ratio of segmental mobility for crosslinked and uncrosslinked polymers, λ, to fit the model curve to the data obtained. A higher ratio value was shown to indicate a more consistent rate of increase of Tg in relation to the degree of conversion, while a lower value indicated that the rate of Tg increase was disproportionately higher at higher degrees of conversion. The best fit value of λ determined by regression analysis for the DGEBA–MHHPA epoxy system was 0.64, which appeared to be higher than for those previously obtained for other epoxy systems, which ranged from 0.43–0.58. The highest Tg value obtained experimentally, Tg max, was 146°C, which is significantly below the derived theoretical maximum Tg value of 170. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 511–516, 2000  相似文献   

10.
A novel poly(ethylene terephthalate)–poly(caprolactone) block copolymer (PET–PCL) is synthesized in a reactive twin‐screw extrusion process. In the presence of stannous octoate, ring‐opening polymerization of ϵ‐caprolactone is initiated by the hydroxyl end groups of molten PET to form polycaprolactone blocks. A block copolymer with minimal transesterification is obtained in a twin‐screw extruder as a consequence of the fast distributive mixing of ϵ‐caprolactone into high melt viscosity PET and the short reaction time. The PET–PCL structure is characterized by IV, GPC, 1H‐NMR, and DSC. Fully drawn and partially relaxed fibers spun from PET–PCL are characterized by WAXD and SAXS. A substantial decrease in the oriented amorphous fraction appears to be the major structural change in the relaxed fiber that provides the fiber with the desired stress–strain characteristics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1858–1867, 1999  相似文献   

11.
Low generation amino‐group‐terminated poly(ester‐amine) dendrimers PEA1.0 (NH2)3 and PEA1.5 (NH2)8, and poly(amido‐amine) dendrimer PAMAM1.0 (NH2)4 were used as diglycidyl ether of bisphenol A (DGEBA) epoxy resin hardeners. Thermal behavior and curing kinetics of dendrimer/DGEBA systems were investigated by means of differential scanning calorimetry (DSC). Compared with ethylene diamine (EDA)/DGEBA system, the dendrimer/DGEBA systems gradually liberated heat in two stages during the curing process, and the total heat liberated was less. Apparent activation energy and curing reaction rate constants for dendrimer and EDA/DGEBA systems were estimated. Thermal stabilities and mechanical properties of cured thermosetting systems were examined as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3902–3906, 2006  相似文献   

12.
Mixtures of diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin with poly(4‐vinyl phenol) (PVPh) of various compositions were examined with a differential scanning calorimeter (DSC), using the curing agent 4,4′‐diaminodiphenylsulfone (DDS). The phase morphology of the cured epoxy blends and their curing mechanisms depended on the reactive additive, PVPh. Cured epoxy/PVPh blends exhibited network homogeneity based on a single glass transition temperature (Tg) over the whole composition range. Additionally, the morphology of these cured PVPh/epoxy blends exhibited a homogeneous network when observed by optical microscopy. Furthermore, the DDS‐cure of the epoxy blends with PVPh exhibited an autocatalytic mechanism. This was similar to the neat epoxy system, but the reaction rate of the epoxy/polymer blends exceeded that of neat epoxy. These results are mainly attributable to the chemical reactions between the epoxy and PVPh, and the regular reactions between DDS and epoxy. Polym. Eng. Sci. 45:1–10, 2005. © 2004 Society of Plastics Engineers.  相似文献   

13.
The anionic epoxy homopolymerization initiated by tertiary amines, imidazoles, and ammonium salts is a complex reaction exhibiting two undesired characteristics for practical applications: (a) slow reaction rates with long induction periods, and (b) short primary chains due to the high rate of chain transfer reactions. Therefore, these systems have not found an important place in commercial applications. In this study, it is shown that using 4‐(dimethylamino)pyridine (DMAP) as initiator of the polymerization of phenyl glycidyl ether (PGE) or diglycidyl ether of bisphenol A (DGEBA) enables to obtain high polymerization rates and longer primary chains than those generated using typical initiators. A critical molar ratio DMAP/epoxy groups was necessary to attain complete conversion. Networks resulting from the DMAP‐initiated homopolymerization of DGEBA exhibited a high crosslink density and corresponding high values of the glass transition temperature (Tg = 160°C) and of the rubbery elastic modulus (higher than 100 MPa). An intense brown color of reaction products, associated with an absorption band with a maximum at 360 nm, was ascribed to the presence of initiator fragments with conjugated double bonds in chain ends. These results might revalorize the anionic homopolymerization of epoxy monomers for commercial applications. POLYM. ENG. SCI. 46:351–359, 2006. © 2006 Society of Plastics Engineers  相似文献   

14.
Liquid oxidized poly(1,2‐butadiene) (LOPB) with multi epoxy groups is synthesized to modify diglycidyl end‐caped poly(bisphenol A‐co‐epichlorohydrin) (DGEBA) cured by 4,4′‐diaminodiphenyl sulfone (DDS). FTIR spectra shows that DGEBA and LOPB can be effectively cured by DDS, and the epoxide rubber particles are evenly distributed in the composites till their addition up to 20 wt % of DGEBA as seen from the scanning electron microscope (SEM). Their decomposition temperatures (Td) increase with the increase in LOPB addition at around 10 wt % of DGEBA while the Td for the composite containing 20 wt % LOPB of DGEBA is lower than that of the neat epoxy. The addition of LOPB improves their storage moduli and especially these values at temperatures higher above 150 °C; all the composites exhibit higher glass transition temperature (Tg) than that of the neat epoxy, and the maximum Tg reaches up to 255 °C for the composite containing 15 wt % LOPB of DGEBA. The incorporation of LOPB effectively decreases their dielectric constants and the composite with 10 wt % LOPB of DGEBA possesses the lowest one. The synergic improvements in their various properties are attributed to the networks formation via covalent linkage between the two phases in these reactive blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44689.  相似文献   

15.
Epoxy resin–silica nanocomposites with spherical silica domains with 29.0 nm in diameter in an epoxy resin matrix were synthesized from Bisphenol‐A type epoxide monomer, 2,2‐bis(4‐glycidyloxyphenyl)propane (DGEBA), and perhydropolysilazane (PHPS, ? [Si2? NH]n? ). The volume fraction of silica domain in the composite varied from 5.4 to 37.8 vol % by varying the feed ratio of PHPS to the epoxide monomer. The reaction mechanism of epoxy group and PHPS was investigated by using glycidyl methacrylate as a model compound of the epoxy monomer by 1H‐nucular magnetic resonance and Fourier transform infrared spectrometry. Ammonia gas provided by the decomposition of PHPS with moisture converted PHPS to silica and cured the epoxy monomer. The curing of epoxy monomer preferably proceeded than the conversion of silica. The addition of 1,4‐diaminobutane drastically accelerated the rate of curing; white and hard epoxy resin–silica nanocomposites were obtained. The good thermal stability of the composite prepared with DGEBA/PHPS/1,4‐diaminobutane was observed by thermogravimetric analysis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

16.
Furfuryl alcohol and bio‐based epichlorohydrin were used to prepare a fully bio‐based reactive diluent, 2‐[(oxiran‐2‐ylmethoxy) methyl] furan (FOM). After spectral characterization, FOM was blended with epoxy resin, diglycidylether bisphenol A (DGEBA), at different ratios for reducing the viscosity. For a comparison, Cardura (one of the most common commercial reactive diluents), was separately incorporated to DGEBA. Amine‐curing process of the blends was recorded by FTIR and DSC. Similar trends of curing progression for DGEBA containing the reactive diluents were observed. Thermogravimetric analysis and dynamic mechanical thermal analysis, mechanical (hardness, adhesion, and stress–strain) and morphological properties were also investigated to study characteristics of the epoxy matrices formulated with FOM or Cardura. It was concluded that FOM could be considered as an efficient reactive diluent in formulations of polymer composites, structural adhesives and surface coatings based on epoxy resins. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44957.  相似文献   

17.
The fluorinated epoxy resin, 2,2‐bisphenol hexafluoropropane diglycidyl ether (DGEBHF) was synthesized through a two‐step procedure, and the chemical structure was confirmed by 1H n uclear magnetic resonance (NMR), 13C NMR, and Fourier transform infrared (FTIR) spectra. Moreover, DGEBHF was thermally cured with methyl hexahydrophthalic anhydride (MHHPA). The results clearly indicated that the cured DGEBHF/MHHPA exhibited higher glass transition temperature (Tg 147°C) and thermal decomposition temperature at 5% weight loss (T5 372°C) than those (Tg 131.2°C; T5 362°C) of diglycidyl ether of bisphenol A (DGEBA)/MHHPA. In addition, the incorporation of bis‐trifluoromethyl groups led to enhanced dielectric properties with lower dielectric constant (Dk 2.93) of DGEBHF/MHHPA compared with cured DGEBA resins (Dk 3.25). The cured fluorinated epoxy resin also gave lower water absorption measured in two methods relative to its nonfluorinated counterparts. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2801–2808, 2013  相似文献   

18.
Ethylene‐vinyl alcohol copolymers (EVOH) were prepared by the conventional saponification of poly(ethylene‐co‐vinyl acetate) using a solution of potassium hydroxide in ethanol. An organic fungicide, consisting of a 2‐benzimidazole carbamoyl (CBZ) group supported on EVOH (EVOH‐CBZ), was prepared by the transesterification reaction of methyl 2‐benzimidazole cabamate (carbendazim) with EVOH. The antifungal activity of the synthesized polymers was examined by the halo zone test against Aspergillus fumigatus and Penicillium pinophilum. The synthesized EVOH‐CBZ complex showed a strong antifungal activity. The bound CBZ units were susceptible to hydrolysis. CBZ bonded to an epoxy resin precursor, diglycidyl ether of bisphenol A (DGEBA‐CBZ), retained its antifungal activity, which was somewhat weaker in comparison with that of EVOH‐CBZ. When the DGEBA‐CBZ complex was crosslinked by isophoronediamine, the antifungal activity disappeared almost completely, indicating that it is necessary for the CBZ units to release from their polymer supports to have the antifungal effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 728–736, 2001  相似文献   

19.
A series of epoxy‐bridged polyorganosiloxanes have been synthesized by reacting multifunctional aminoalkoxysilanes with diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The reactions of trifunctional 3‐aminopropyltriethoxysilane (APTES), difunctional 3‐aminopropylmethyldiethoxysilane (APMDS), and monofunctional 3‐aminopropyldimethylethoxysilane (APDES) with DGEBA epoxy have been monitored and characterized by FTIR, 1H NMR, and 29Si NMR spectra in this study. The synthesized epoxy‐bridged polyorganosiloxanes precursors, with different terminated alkoxysilane groups, are thermally cured with or without the addition of curing catalysts. Organometallic dibutyltindilaurate, and alkaline tetrabutylammonium hydroxide have been used as curing catalysts to investigate the thermal curing behaviors and cured properties of epoxy‐bridged polyorganosiloxanes precursors. The maximum exothermal curing temperatures of epoxy‐bridged polyorganosiloxanes precursors are found to appear around the same region of 120°C in DSC analysis. The addition of catalysts to the epoxy/APTES precursor shows significant influence on the cured structure; however, the catalysts exhibit less influence on the cured structure of epoxy‐APMDS precursor and epoxy/APDES precursor. Curing catalysts also show significant enhancement in increasing the thermal decomposition temperature (Td50s) of cured network of trifunctional epoxy‐bridged polyorganosiloxane (epoxy/APTES). High Td50s of 518.8 and 613.6 in the cured hybrids of epoxy/APTES and epoxy/APMDS precursors are also observed, respectively. When trialkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes precursor are cured, with or without the addition of catalyst, no obvious Tg transition can be found in the TMA analysis of cured network. The cured network of trialkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes also exhibits the lowest coefficient of thermal expansion (CTE) among the three kinds of alkoxysilane‐terminated epoxy‐bridged polyorganosiloxanes investigated. The organic–inorganic hybrid, from epoxy‐bridged polyorganosiloxanes after the thermal curing process, shows better thermal stability than the cured resin network of pure epoxy‐diaminopropane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3491–3499, 2006  相似文献   

20.
In this study, bisphenol A epoxy resin (DGEBA) was chemically modified by 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and the molecular structure of the modified epoxy resin was characterized by Fourier transform infrared spectra. The effects of DOPO on liquid oxygen compatibility of DGEBA were calculated using mechanical impact method. The results indicated that epoxy resin (EP‐P1)/4,4‐diaminobisphenol sulfone (DDS) was compatible with liquid oxygen. When compared with EP/DDS, differential scanning calorimetry and thermogravimetry analyses showed that EP‐P1/DDS and EP‐P2/DDS had much higher glass transition temperatures and char yield. X‐ray photoelectron spectroscopic analysis suggested that phosphorus atoms on the surface of EP‐P1/DDS and EP‐P2/DDS could act in the solid phase to restrain the incompatible reaction, which was in accordance with the flame‐retardant mechanism of phosphorus‐containing compounds. The compatibility mechanism of EP‐P1/DDS was further proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40848.  相似文献   

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