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1.
The kinetics of the cure reaction for a system of bisphenol‐S epoxy resin (BPSER), with 4,4′‐diaminodiphenyl sulfone (DDS) as a curing agent was investigated with a differential scanning calorimeter (DSC). Autocatalytic behaviour was observed in the first stages of the cure which can well be described by the model proposed by Kamal, using two rate constants, k1 and k2, and two reaction orders, m and n. The overall reaction order, m + n, is in the range 2∼2.5, and the activation energy for k1 and k2 was 86.26 and 65.13 kJ mol−1, respectively. In the later stages, a crosslinked network was formed and diffusion control was incorporated to describe the cure. The glass transition temperature (Tg) of the BPSER/DDS samples partially cured isothermally was determined by means of torsional braid analysis (TBA) and the results showed that the reaction rate increased with increasing Tg, in terms of rate constant, but decreased with increasing conversion. It was also found that the  SO2 group both in the epoxy resin and in the hardener increases the Tg values of the cured materials compared with that of BPAER. The thermal degradation kinetics of this system was investigated by thermogravimetric analysis (TGA). It illustrated that the thermal degradation of BPSER/DDS has nth order reaction kinetics. © 2000 Society of Chemical Industry  相似文献   

2.
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   

3.
The curing kinetics of bisphenol‐F epoxy resin (BPFER) and curing agent phthalic anhydride, with N,N‐dimethylbenzylamine as an accelerator, were studied by differential scanning calorimetry (DSC). Analysis of DSC data indicated autocatalytic behaviour in the first stages of the cure for the system, and that this, could be well described by the model proposed by Kamal, which includes two rate constants, k1 and k2, and two reaction orders, m and n. The curing reaction in the later stages was practically diffusion‐controlled. To consider the diffusion effect more precisely, a diffusion factor, ??(α), was introduced into Kamal's equation. The glass transition temperatures (Tgs) of the BPFER/phthalic anhydride samples were determined by means of torsional braid analysis. The thermal degradation kinetics of cured BPFER were investigated by thermogravimetric analysis. © 2002 Society of Chemical Industry  相似文献   

4.
    
Two novel liquid crystalline epoxy resins (LCER) based on bisphenol‐S mesogen, 4,4′‐Bis‐(2,3‐epoxypropyloxy)‐sulfonyl bis(1,4‐phenylene) (p‐BEPSBP) and sulfonyl bis(4,1‐phenylene) bis[4‐(2,3‐epoxypropyloxy)benzoate] (p‐SBPEPB), were synthesized. Their liquid crystalline behavior and structure were characterized by Fourier transmittance infrared ray (FTIR), differential scanning calorimetry (DSC), 1HNMR, polarized optical microscopy (POM) and X‐ray diffraction (XRD). The results show that p‐BEPSBP is a kind of thermotropic liquid crystal and has a smectic mesophase with a melting point (Tm) at 165°C; the p‐SBPEPB is a kind of nematic mesophase with the temperature range of 155–302°C from the Tm to the clearing point Ti. The curing behaviors and texture of the liquid crystalline epoxy resins with 4,4′‐diaminodiphenyl ether (DDE) were also studied by DSC and some kinetic parameters were evaluated according to the Ozawa's method. The dynamic mechanical properties of curing products were also investigated by torsional braid analysis (TBA), and the results suggest that the dynamic mechanical loss peak temperature (Tp) of p‐BEPSBP/DDE and p‐SBPEPB/DDE is 120 and 130°C, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

5.
The curing kinetics of bisphenol-F epoxy resin (BPFER)/4,4′-diaminodiphenyl sulfone (DDS) system were studied by isothermal experiments using a differential scanning calorimeter (DSC). Autocatalytic behavior was shown in the first stages of the cure for the system, which could be well described by the model proposed by Kamal that includes two rate constants, k 1 and k 2, and two reaction orders, m and n. The curing reaction at the later stages was practically diffusion-controlled due to the onset of gelation and vitrification. To consider the diffusion effect more precisely, diffusion factor, f(α), was introduced into Kamal's equation. Thus, the curing kinetics could be predicted well over the whole range of conversion covering both pre- and postvitrification stages. The glass transition temperatures (Tgs) of the BPFER/DDS system isothermally cured partially were determined by means of torsional braid analysis (TBA), and the results showed that Tgs increased with conversion up to a constant value. The highest Tg was 406.2 K. The thermal degradation kinetics of cured BPFER were investigated by thermogravimetric analysis (TGA), revealing two decomposition steps.  相似文献   

6.
The kinetics of the cure reaction for a system of bisphenol-S epoxy resin (BPSER), with 4,4′-diaminodiphenylmethane (DDM) as a curing agent, were studied by means of differential scanning calorimetry (DSC). Analysis of DSC data indicated that an autocatalytic behavior showed in the first stages of the cure, with the model proposed by Kamal, which includes two rate constants, k1 and k2, and two reaction orders, m and n. Rate constants k1 and k2 were observed to be greater when curing temperature increased. The over-all reaction order, m + n, is in the range of 2.5 ∼ 3. The activation energies for k1 and k2 were 55 kJ/mol and 57 kJ/mol, respectively. Diffusion control is incorporated to describe the cure in the latter stages. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1799–1803, 1999  相似文献   

7.
    
The extent of conversion of epoxy groups cured with diaminodiphenyl methane, a diamine, at 100°C was approximately 100%, and the glass‐transition temperature (T) was found to be an increasing function of cure time with very large increases with extended postcure treatments at 180°C. However, this considerable increase in the Tg with postcure at 180°C was not due to the reactions of epoxy and amine groups. The specific volume reduced with the Tg to a minimum at 103° for the cured samples but showed a very slight increase with the Tg for the postcured samples. It was also found that the glassy modulus (Eg) was a linear decreasing function of the Tg. There were two separate relationships between the Eg and the rubbery modulus that depended on the cure conditions and suggested that the “structure” formed due to cure at a temperature of 100°C was different than that at postcure, which was 180°C. The most sensitive structural parameter for these cured epoxy resins was their T. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1265–1276, 2001  相似文献   

8.
Spectral analysis of the infrared radiation emitted from thin films of resin transferred from the surface of high performance aerospace carbon fibreepoxy composite prepregs and heated to the cure temperature allows the cure chemistry and kinetics to be monitored in real time. Quantitative spectra with excellent signal-to-noise ratio are obtained by heating a thin resin film on a platinum hotplate fitted to the external optics of a Fourier transform infrared (FTIR) spectrometer and referencing the resulting emission (with the platinum emission subtracted) to a graphite black body at the same temperature. The resulting spectra are identical to absorption spectra and the quantitative features of the analysis are demonstrated by the appearance of isosbestic points during the curing reactions, so indicating that concentration profiles of the reacting species may be obtained. From the initial rate of amine and epoxy consumption, activation energies of 75kJ mol−1 were obtained for both functional groups in the uncatalysed resin 4,4′-tetraglycidyl diamino diphenyl methane (TGDDM) with 27% 4,4′-diaminodiphenylsulfone (DDS), while values of 74 and 89kJ mol−1 were obtained for amine and epoxy consumption from the TGDDM/DDS prepreg catalysed with boron trifluoride monoethylamine (Hercules 3501–6), consistent with homopolymerization occurring in the prepreg as well as amine–epoxy addition. Analysis of the FTIR emission at 177°C of resin from prepreg aged up to 90h at 23°C and 55% relative humidity shows a lowering of epoxy and amine concentration and a higher rate of cure, consistent with the formation of catalytic species. This technique may be used to monitor changes in surface properties such as tack and resin transfer, in addition to changes in the cure profile of the aged epoxy propreg.  相似文献   

9.
An analytical procedure has been developed for modelling the kinetics of the cure process of a commercial epoxy resin for resin transfer moulding (RTM) applications, using differential scanning calorimetry (DSC) in the isothermal and dynamic modes to obtain the experimental database. The overall reaction rate of the epoxide groups with amines was determined and fitted by an autocatalytic kinetic model. An improvement of the model to allow for diffusion limitation effects results in a good agreement between experimentally determined and predicted reaction rates. A non-linear least squares regression analysis method based on Marquardt's algorithm was used to fit the DSC reaction rate data with an appropriate model and to evaluate the activation energies and the reaction orders for this particular resin system. The Di Benedetto equation was utilised to establish the relationship between conversion and glass transition temperature (Tg), required to develop the diffusion-dominated part of the model.  相似文献   

10.
研究了邻甲酚醛环氧树脂(o CFER)与邻苯二甲酸酐固化物的热分解动力学,用动态力学谱仪测定了玻璃化温度(Tg)。讨论了固化剂用量、固化时间等因素对玻璃化转变温度(Tg)的影响。结果表明,固化体系的玻璃化温度随反应程度的增加而升高,当达到一定程度后,趋于一定值。利用热重分析仪(TGA)研究了完全固化产物的热分解动力学,说明热分解反应分2步进行。  相似文献   

11.
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   

12.
    
Among various biomass‐based components, both lignin and glycerol are important, since they are abundantly produced as by‐products in industrial processes. Accordingly, in the present study, new types of crosslinked epoxy resins were synthesized from lignin and glycerol. Polymers derived from two types of lignin‐based crosslinked epoxy resins were prepared through two‐step reactions, ester‐carboxylic acid derivative preparation followed by crosslinked epoxy resin preparation, in order to establish a crosslinked epoxy resin system in which glycerol units were included. The resins obtained were labeled as follows: series 1, lignosulfonate‐glycerol polyacid (Ser1LSGLYPA); and series 2, glycerol diglycidyl ether (Ser2GLYDGE). The functional groups of the resins were analyzed using Fourier transform infrared spectrometry. The thermal properties of the resins were analyzed using differential scanning calorimetry and thermogravimetry. The glass transition temperature of the crosslinked epoxy resins increased with increasing LSGLYPA and GLYDGE contents for Ser1LSGLYPA and Ser2GLYDGE, respectively. The thermal degradation temperature for Ser1LSGLYPA and Ser2GLYDGE did not show significant change, suggesting that the crosslinked epoxy resins were thermally stable. The mass residue at 500 °C was not affected by the changes of LSGLYPA and GLYDGE contents. Copyright © 2009 Society of Chemical Industry  相似文献   

13.
    
A series of novel composites based on different ratios of epoxidised cresol novolac (ECN) and 4,4′‐diglycidyl(3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP) have been prepared with the curing agent 4,4′‐methylenediamine (DDM) and 4,4′‐diaminodiphenylsulfone (DDS), respectively. The investigation of cure kinetics was performed by differential scanning calorimetry using an isoconversional method. The high thermal stabilities of the cured samples were also studied by thermogravimetric analysis. In addition, no phase separation was observed for cured ECN/DDM and ECN/DDS blending with different amounts of TMBP by dynamic mechanical analysis and scanning electron microscopy. Moreover, the cured systems also exhibited excellent impact properties and low moisture absorption. All the results indicate that the ECN/TMBP/DDM and ECN/TMBP/DDS systems are promising materials in electronic packaging. Copyright © 2011 Society of Chemical Industry  相似文献   

14.
    
The objective of this investigation is to characterize various room temperature (RT)‐curable epoxies for vacuum‐assisted resin transfer molding (VARTM) of large structure manufacturing. Six epoxy candidate resins: X‐40, 780‐33, 780‐35, 8601/8602, 8602, 8603, and two vinyl ester resins (VE), 411‐350 and 411‐510A, are physically and thermochemically characterized. All the resins are cured at RT with extended period of time. The degree of cure for 24‐h RT‐cured samples ranges from 70 to 85% for epoxies and is comparable with the baseline VE systems (75%). After 1 year at RT, the degree of cure increases from 90 to 98%. Most of the epoxies show a single transition in dynamic mechanical analysis and differential scanning calorimetry. However, two heterogeneous transitions are observed for the VE systems. The glass transition temperature increases monotonically with exposure time, except X‐40, that rapidly achieves a plateau and remains constant. The degree of cure for the majority of the systems increases logarithmically with RT curing time with excellent fitting (R2 varies from 0.92 to 1). Consistent with the increase in degree of cure, the storage modulus increases and (tan δ)max decreases with time of exposure. A negative correlation between the curing temperature range and the total heat of reaction is observed among the epoxy systems. However, the VE systems show the reverse trend. RT curing epoxy resin (X‐40) shows promising overall result to VE system and can be a viable alternative to VE for VARTM processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

15.
    
Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized vegetable oils (EVOs) (epoxidized soybean oil and epoxidized castor oil) with a thermally latent initiator. The effects of EVO content on the thermomechanical properties of the EVO‐modified DGEBA epoxy resins were investigated using several techniques. Differential scanning calorimetry indicated that the cure reaction of the DGEBA/EVO systems proceeded via two different reaction mechanisms. Single and composition‐dependent glass transition temperature (Tg) mechanisms were observed for the systems after curing. The experimental values of Tg could be explained by the Gordon–Taylor equation [Gordon M and Taylor JS, J Appl Chem 2 :493 (1952)]. The thermal stability of the systems decreased as the EVO content increased, due to the lower crosslinking density of the DGEBA/EVO systems. The coefficient of thermal expansion of the systems was found to increase linearly with increasing EVO content. This could be attributed to the fact that the degrees of freedom available for motions of the segments of the macromolecules in the network structure were enhanced by the addition of EVO. Copyright © 2008 Society of Chemical Industry  相似文献   

16.
    
A series of epoxy networks were synthesized in which the molecular weight between crosslinks (Mc) and crosslink functionality were controlled independent of the network chain backbone composition. The glass transition temperature (Tg) of these networks was found to increase as Mc decreased. However, the rate at which Tg increased depended on crosslink functionality. The dependency of Mc on Tg is well described by two models, one based on the concept of network free volume while the other model is based on the principle of corresponding states. Initially, neither model could quantitatively predict the effect of crosslink functionality in our networks. However, our tests indicated that both the glass transition and the rubbery moduli of our networks were dependent on Mc and crosslink functionality, while the glassy state moduli were independent of these structural variables. The effect of crosslink functionality on the rubbery modulus of a network has been addressed by the front factor in rubber elasticity theory. Incorporation of this factor into the glass transition temperature models allowed for a quantitative prediction of Tg as a function of Mc and crosslink functionality. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 387–395, 1997  相似文献   

17.
    
Tetramethylbisphenol F epoxy resin (TMBPFE) was successfully synthesized based on tetramethylbisphenol F (TMBPF) and epichlorohydrin with tetrabutylammonium bromide as the catalyst. The structure of TMBPFE was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and elemental analysis. Then, a mixed system composed of TMBPFE and 4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy (TMBP) was prepared by a melting method, i.e. without any solvent. Both the TMBPFE and the mixed system were cured using 4,4′‐diaminodiphenyl methane (DDM) as the curing agent. The thermal properties of TMBPFE and the mixed system were studied using differential scanning calorimetry, dynamic mechanical analysis and thermogravimetric analysis (TGA). The results showed that the TMBP mixed in the TMBPFE matrix had little effect on the thermal properties of TMBPFE. However, the glass transition temperature improved markedly with increasing content of TMBP. Moreover, the TGA results showed that the degradation characteristics of TMBPFE resins did not seriously decrease when TMBP was incorporated into the TMBPFE matrix, although there are large steric hindrance biphenyl groups in TMBP. Both TMBPFE and the TMBPFE/TMBP system have potential applications in electrical and electronic fields. Copyright © 2011 Society of Chemical Industry  相似文献   

18.
    
A dicyanate ester, namely, 2,2‐bis‐(4‐cyanatophenyl)propane, and a bismaleimide, namely, 2,2‐bis[4‐(4‐maleimido phenoxy)phenyl]propane, possessing closely resembling backbone structures, were cured together to derive bismaleimide–triazine network polymers of varying compositions. The blend manifested a eutectic melting behavior at a 1 : 1 composition with a eutectic melting point of 15°C. The cure characterization of the blends was done by DSC and dynamic mechanical analyses (DMA). The near simultaneous cure of the blend could be transformed to a clear sequential one by catalyzing the dicyanate cure to lower temperature using dibutyl tin dilaurate. The two‐stage, independent cure of the components of the blend evidenced in DSC was confirmed by DMA. The cure profile of the bismaleimide component predicted from the kinetic data derived from nonisothermal DSC was found to be in league with the isothermal DMA behavior. Both techniques led to optimization of the cure schedule of the blends. The cured polymers were characterized by FTIR and TGA. The cured blends underwent decomposition in two stages, each corresponding to the polycyanurate and polybismaleimide. Enhancing the bismaleimide component did not alter the initial decomposition temperature, but led to reduced rate of thermal degradation at higher temperature. Interlinking of the two networks and enhancing crosslink density through coreaction of the blend with 4‐cyantophenylmaleimide unaffected the initial decomposition properties but was conducive for increasing the char residue significantly. Computation of activation parameters for the thermal decomposition of the polymers confirmed that the first step in the degradation of the blends is caused by the polycyanurate component. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3365–3375, 1999  相似文献   

19.
    
The modification of the curing behaviour and the phase separation process for an epoxy resin blended with a crystalline thermoplastic was investigated in the case of the diglycidylether of bisphenol‐A (DGEBA)/4,4′‐methylene bis(3‐chloro‐2,6‐diethylaniline) (MCDEA) blended with syndiotactic polystyrene (sPS) and cured at 220 °C. Phase separation taking place during curing of the blend was investigated by differential scanning calorimetry (DSC) and optical microscopy in order to get a better understanding of the complex interactions between cure kinetics of epoxy matrix and crystallisation of sPS, both influenced by blend composition. Results suggested that phase separation and crystallisation of sPS occurred at almost similar times, with phase separation just being ahead of crystallisation. DSC and near‐infrared measurements were used for the determination of the cure kinetics. Slow delays on the cure reactions were observed during the first minutes for the sPS‐containing blends compared with the neat DGEBA/MCDEA system but, after some time, the reaction rate became faster for the blends than for the neat matrix. Phase separation occurring in the mixtures may explain this particular phenomenon. Copyright © 2004 Society of Chemical Industry  相似文献   

20.
    
The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004  相似文献   

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