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1.
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   

2.
The poly(sily ether) with pendant chloromethyl groups (PSE) was synthesized by the polyaddition of dichloromethylsilane (DCM) and diglycidylether of bisphenol A (DGEBA) with tetrabutylammonium chloride (TBAC) as a catalyst. This polymer was miscible with diglycidyl ether of bisphenol A (DGEBA), the precursor of epoxy resin. The miscibility is considered to be due mainly to entropy contribution because the molecular weight of DGEBA is quite low. The blends of epoxy resin with PSE were prepared through in situ curing reaction of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐diaminodiphenylmethane (DDM) in the presence of PSE. The DDM‐cured epoxy resin/PSE blends with PSE content up to 40 wt % were obtained. The reaction started from the initial homogeneous ternary mixture of DGEBA/DDM/PSE. With curing proceeding, phase separation induced by polymerization occurred. PSE was immiscible with the 4,4′‐diaminodiphenylmethane‐cured epoxy resin (ER) because the blends exhibited two separate glass transition temperatures (Tgs) as revealed by the means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). SEM showed that all the ER/PSE blends are heterogeneous. Depending on blend composition, the blends can display PSE‐ or epoxy‐dispersed morphologies, respectively. The mechanical test showed that the DDM‐cured ER/PSE blend containing 25 wt % PSE displayed a substantial improvement in Izod impact strength, i.e., epoxy resin was significantly toughened. The improvement in impact toughness corresponded to the formation of PSE‐dispersed phase structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 505–512, 2003  相似文献   

3.
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   

4.
The curing reaction of bisphenol S epoxy resin (BPSER) with 4,4′‐diaminodiphenylmethane (DDM) was studied by means of torsional braid analysis (TBA) in the temperature range of 393–433 K. The glass transition temperature (Tg) of the BPSER/DDM system is determined, and the results show that the reaction rate increases with increasing the Tg in terms of the rate constant, but decreases with increasing conversion. 1 The Tg of BPSER/DDM is about 40 K higher than BPAER/DDM. The gelation and vitrification time were assigned by the isothermal TBA under 373 K; in addition, an FTIR spectrum was carried out to describe the change of the molecular structure. The thermal degradation kinetics of this system was investigated by thermogravimetric analysis (TGA). It illustrated that the thermal degradation of the BPSER/DDM has n‐order reaction kinetics. 2 © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 794–799, 2000  相似文献   

5.
Times to gelation and vitrification have been determined at different isothermal curing temperatures between 200 and 240°C for an epoxy/amine system containing both tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and a multifunctional Novolac glycidyl ether with 4,4′-diaminodiphenylsulphone (DDS). The mixture was rich in epoxy, with an amine/epoxide ratio of 0·64. Gelation occurred around 44% conversion. Vitrification was determined from data curves of glass transition temperature, Tg, versus curing time obtained from differential scanning calorimetry experiments. The minimum and maximum values Tg determined for this epoxy system were Tg0=12°C and Tgmax=242°C. Values of activation energy for the cure reaction were obtained from Tg versus time shift factors, aT, and gel time measurements. These values were, respectively, 76·2kJmol-1 and 61·0kJmol-1. The isothermal time–temperature–transformation (TTT) diagram for this system has been established. Vitrification and gelation curves cross at a cure temperature of 102°C, which corresponds to glass transition temperature of the gel. © of SCI.  相似文献   

6.
A high‐performance difunctional epoxy resin, 4‐(4‐hydroxyphenoxy)phenol diglycidyl ether (DHPOP), was synthesized by a two‐step method. The curing behavior of DHPOP was investigated by nonisothermal differential scanning calorimetry method and the curing kinetics results revealed that the introduction of ether linkage could improve the activity of epoxy groups, leading to a lower curing temperature and apparent activation energy compared with that of the commercial bisphenol‐A diglycidyl ether (DGEBA). A series of copolymers were then prepared by varying the mass ratio of DHPOP and DGEBA, which were cured with 4,4′‐diaminodiphenyl methane. The effect of DHPOP contents on thermal and mechanical properties and fracture morphology was studied. As expected, with the increase of DHPOP in the network, the impact strength and char yield were significantly enhanced, while the glass transition temperature (Tg) remained unchanged because of the increase of crosslink density. The excellent toughness endows the DHPOP with the promising potential for the application as high‐performance resin matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46458.  相似文献   

7.
The bisphenol‐containing 4,4′‐biphenylene moiety was prepared by the reaction of 4,4′‐bis(methoxymethyl) biphenyl with phenol in the presence of p‐toluenesulfonic acid. The bisphenol was end‐capped with the cyanate moiety by reacting with cyanogen chloride and triethylamine in dichloromethane. Their structures were confirmed by Fourier transform infrared spectroscopy, 1H‐NMR, and elemental analysis. Thermal behaviors of cured resin were studied by differential scanning calorimetry, dynamic mechanical analysis, and TGA. The flame retardancy of cured resin was evaluated by limiting oxygen index (LOI) and vertical burning test (UL‐94 test). Because of the incorporation of rigid 4,4′‐biphenylene moiety, the cyanate ester (CE) resin shows good thermal stability (Tg is 256°C, the 5% degradation temperature is 442°C, and char yield at 800°C is 64.4%). The LOI value of the CE resin is 42.5, and the UL‐94 rating reaches V‐0. Moreover, the CE resin shows excellent dielectric property (dielectric constant, 2.94 at 1 GHz and loss dissipation factor, 0.0037 at 1 GHz) and water resistance (1.08% immersed at boiling water for 100 h). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

8.
The study synthesized a trifluoromethyl (CF3) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (Tg) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (Td5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (Dk) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF3 groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

9.
Copolycondensations of IPA, TPA, bisphenol A (BPA), and several cimonomers were carried out to improve thermal properties, such as, the glass transition temperature (Tg) of the IPA/TPA (50/50)–BPA polyester. Among the comonomers examined, 4,4′‐Dihydroxydiphenylsulfone (BPS) and 4,4′‐Dicarboxydiphenylsulfone (DCDPS) having a strongly dipolar sulfonyl group in the chain were significantly effective. The favorable effect upon the Tgs was studied by varying the amounts of BPS and DCDPS incorporated into the copolymers. In the copolycondensation with BPS, two‐stage copolycondensation of BPA first and then BPS, the reverse order of reaction, and their spontaneous addition were examined to investigate the effect of distribution of the BPS unit segments in the copolymer upon the Tgs of the resulted copolymers. The distribution was briefly studied from distribution of the IPA/TPA‐BPA oligomers in the initial reaction using GPC. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 875–879, 2000  相似文献   

10.
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   

11.
Reaction intermediates in the reaction of 4,4′-thiodiphenol (TDP) and Epikote 828 (E 828) for the formation of the diglycidyl ether of bisphenol A (DGEBA) epoxy copolymers (ETP) were determined by using a combination of two methods, viz. gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization/time-of-flight (MALDI–TOF) spectrometer. This combination provides the measurement of true molecular weight and distribution, which in turn, enables the structural identification of intermediates and determination of their respective contents. The content of ideal component, the E 828-(TDP-E 828)n, n = 1 in ETP copolymer, was found to be 2.3, 13.0, and 34.4% for ratios of 1/1, 1/2, and 1/3 of TDP and E 828, respectively. The ETP epoxy copolymers also exhibited thermal improvement over E 828 and other DGEBA resins of the E 1000 series, as indicated by their higher glass transition temperature (Tg) in differential scanning calorimeter (DSC) and better thermostability in thermogravimetric analysis (TGA) measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1621–1631, 1998  相似文献   

12.
The cure behavior of diglycidyl ether of bisphenol A (DGEBA) type of epoxy resins with three aromatic diamines, 4,4′-diaminodiphenyl methane (DDM), 4,4′-diaminodiphenyl sulfone (44DDS), and 3,3′-diaminodiphenyl sulfone (33DDS) was studied by torsional braid analysis. For each curing agent the stoichiometry of the resin mixtures was varied from a two to one excess of amino hydrogens per epoxy group to a two to one excess of epoxy groups per amino hydrogen. Isothermal cures of the resin mixtures were carried out from 70 to 210°C (range depending on epoxy—amine mixture), followed by a temperature scan to determine the glass transition temperature (Tg). The times to the isothermal liquid-to-rubber transition were shortest for the DDM mixtures and longest for the 44DDS mixtures. The liquid-to-rubber transition times were also shortest for the amine excess mixtures when stoichiometry was varied. A relatively rapid reaction to the liquid-to-rubber transition was observed for the epoxy excess mixtures, followed by an exceedingly slow reaction process at cure temperatures well above the Tg. This slow process was only observed for epoxy excess mixtures and eventually led to significant increases in Tg. Using time—temperature shifts of the glass transition temperature vs. logarithm of time, activation energies approximately 50% higher were derived for this process compared to those derived from the liquid-to-rubber transition. The rate of this reaction was virtually independent of curing agent and was attributed to etherification taking place in the epoxy excess mixtures. © 1994 John Wiley & Sons, Inc.  相似文献   

13.
A novel phosphorus‐containing dicyclopentadiene novolac (DCPD‐DOPO) curing agent for epoxy resins, was prepared from 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and n‐butylated dicyclopentadiene phenolic resin (DCPD‐E). The chemical structure of the obtained DCPD‐DOPO was characterized with FTIR, 1H NMR and 31P NMR, and its molecular weight was determined by gel permeation chromatography. The flame retardancy and thermal properties of diglycidyl ether bisphenol A (DGEBA) epoxy resin cured with DCPD‐DOPO or the mixture of DCPD‐DOPO and bisphenol A‐formaldehyde Novolac resin 720 (NPEH720) were studied by limiting oxygen index (LOI), UL 94 vertical test and cone calorimeter (CCT), and differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. It is found that the DCPD‐DOPO cured epoxy resin possess a LOI value of 31.6% and achieves the UL 94 V‐0 rating, while its glass transition temperature (Tg) is a bit lower (133 °C). The Tg of epoxy resin cured by the mixture of DCPD‐DOPO and NPEH720 increases to 137 °C or above, and the UL 94 V‐0 rating can still be maintained although the LOI decreases slightly. The CCT test results demonstrated that the peak heat release rate and total heat release of the epoxy resin cured by the mixture of DCPD‐DOPO and NPEH720 decrease significantly compared with the values of the epoxy resin cured by NPEH720. Moreover, the curing reaction kinetics of the epoxy resin cured by DCPD‐DOPO, NPEH720 or their mixture was studied by DSC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44599.  相似文献   

14.
A polymer with high aromaticity and/or cyclic ring structures chain backbone usually has high heat, thermal, and flame resistance. Two diglycidyl ethers of bisphenols were prepared from 4,4′ isopropylidenediphenol (DGEBA) and 9,9-bis(4-hydroxyphenyl) fluorene (DGEBF) for evaluation. Four boroxines—trimethoxyboroxine (TMB), triethoxyboroxine (TEB), triisopropoxyboroxine (TIPB) and triphenoxyboroxine (TPB)—were used as the curing agents. DGEBA and DGEBF cured with various boroxines indicate that the trend for their respective glass transition temperature (Tg's), degradation temperatures (Td's), and gel fractions are TMB-cured epoxy ≈ TEB-cured epoxy < TIPB cured epoxy < TPB cured epoxy. The DGEBF system usually has a higher Tg, Td, gel fraction, oxygen index (OI), and char yield than the related DGEBA system. DGEBF/DGEBA (80/20 mol ratio) shows a synergistic effect in regard to char formation. This effect exists not only in the copolymer system but also in blended homopolymers of the separately cured resins. A modified mechanism for the polymerization of phenyl glycidyl ether (PGE) with TMB has been proposed.  相似文献   

15.
The curing reaction of tetrabromo-bisphenol-A epoxy resin (TBBPAER) with 4,4′-diaminodiphenyl ether (DDE) was studied by isothermal differential scanning calorimetry (DSC) in the temperature range of 110–140°C. The results show that the isothermal cure reaction of TBBPAER–DDE in the kinetic control stage is autocatalytic in nature and does not follow simple nth-order kinetics. The autocatalytic behavior was well described by the Kamal equation. Kinetic parameters, including 2 rate constants, k1 and k2, and 2 reaction orders, m and n, were derived. The activation energies for these rate constants were 83.32 and 37.07 kJ/mol, respectively. The sum of the reaction orders is around 3. The glass transition temperatures (Tgs) were measured for the TBBPAER–DDE samples cured partially in isothermal temperature. With the degree of cure varies, different glass transition behaviors were observed. By monitoring the variation in these Tgs, it is illustrated that the network of the system is formed via different stages according to the sequence reactions of primary and second amines with epoxides. It is due to the presence of the 4 bromine atoms in the structure of TBBPAER that this curing process can be clearly observed in DSC curves. The thermal stability of this system studied by differential thermal analysis–thermogravimetric analysis illustrates that the TBBPAER–DDE material can automatically debrominate and takes the effect of flame retarding when the temperature reaches 238.5°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1991–2000, 1998  相似文献   

16.
The curing behavior of epoxy resins was analyzed based on a simple kinetic model. We simulated the curing kinetics and found that it fits the experimental data well for both diglycidylether of bisphenol A–4,4′‐methylene dianiline and diglycidylether of bisphenol A–carboxyl‐terminated butadiene acrylonitrile–4,4′‐methylene dianiline systems. The kinetic results showed the curing of epoxy resins involves different reactive process and reaction stages, and the value of activation energy is dependent on the degree of conversion. By analyzing the effect of vitrification, at low curing temperature, we found the curing reaction at the later stage was practically diffusion‐controlled for unmodified resin, and the rubber component did not markedly decrease Tg at the early stage of reaction as would be expected. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2401–2408, 1999  相似文献   

17.
A series of highly thermostable epoxy foams with diglycidyl ether of bisphenol‐A and bisphenol‐S epoxy resin (DGEBA/DGEBS), 4,4′‐diaminodiphenyl sulfone (DDS) as curing agent have been successfully prepared through a two‐step process. Dynamic and steady shear rheological measurements of the DGEBA/DGEBS/DDS reacting mixture are performed. The results indicate all samples present an extremely rapid increase in viscosities after a critical time. The gel time measured by the crossover of tan δ is independent of frequency. The influence of SiO2 content on morphology, thermal, and mechanical properties of epoxy foams has also been investigated. Due to the heterogeneous nucleation of SiO2, the pore morphology with a bimodal size distribution is observed when the content of SiO2 is above 5 wt %. Dynamic mechanical analysis (DMA) reveals that pure epoxy foam possesses a high glass transition temperature (206°C). The maximum of specific compressive strength can be up to 0.0253 MPa m3 kg?1 at around 1.0 wt % SiO2. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40068.  相似文献   

18.
A thermosetting resin system, based on tetraglycidyl‐4,4′‐diaminodiphenylmethane, has been developed via copolymerization with 4,4′‐diaminodiphenylsulfone in the presence of a newly synthesized liquid crystalline epoxy (LCE). The curing behavior of LCE‐containing resin system was evaluated using curing kinetics method and Fourier transform infrared spectroscopy. The effect of LCE on the thermal and mechanical properties of modified epoxy systems was studied. Thermogravimetric analysis indicated that the modified resin systems displayed a high T0.05 and char yield at lower concentrations of LCE (≤5 wt%), suggesting an improved thermal stability. As determined using dynamic mechanical analysis and differential scanning calorimetry, the glass transition value increased by 9.7% compared to that of the neat resin when the LCE content was 5 wt%. Meanwhile, the addition of 5 wt% of LCE maximized the toughness with a 175% increase in impact strength. The analysis of fracture surfaces revealed a possible effect of LCE as a toughener and showed no phase separation in the modified resin system, which was also confirmed by dynamic mechanical analysis. © 2016 Society of Chemical Industry  相似文献   

19.
A polymer having high aromaticity and/or cyclic ring structures in the chain backbone usually gives high heat resistance and flame resistance. Five glycidyl ether-type epoxy resins are prepared from bisphenol A (DGEBA), 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF), 3,6-dihydroxyspiro-[fluorene-9,9′-xanthane] (DGEFX), 10,10-bis(4-hydroxyphenyl) anthrone (DGEA), and 9,9,10,10-tetrakis(4-hydroxyphenyl)anthracene (TGETA) in order to study structure–thermal stability–flame resistance property relationships. In this study, trimethoxyboroxine (TMB) and diaminodiphenylsulfone (DDS) are employed as the curing agents. The char yield at 700°C under a nitrogen atmosphere and the glass transition temperature (Tg) for the uncured resins decrease according to the sequence TGETA > DGEFX > DGEA > DGEBF > DGEBA. The Tg values for these cured epoxy resins are DGEBA < DGEBF < DGEFX < DGEA. A Tg for the TGETA is not obtainable but would be expected to be the highest. The char yields at 700°C of these cured epoxy resins have the same trend as the uncured resins. DGEBF, DGEFX, DGEA, and TGETA added to the DGEBA system show increases in the char yield, Tg, and oxygen index with increasing concentration of these novel epoxy resins.  相似文献   

20.
A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (Tg), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.  相似文献   

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