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1.
Blends of poly(ethylene terephthalate) and poly(ethylene‐2,6‐naphthalate) (70 : 30 w/w) were prepared via a melt‐mixing process at 280°C with various mixing times. The melt‐mixed blends were analyzed by magnetic resonance spectroscopy, differential scanning calorimetry, dynamic mechanical measurements, transmission electron microscopy, and tensile tests. The results indicate that the blends mixed for short times had lower extents of transesterification and were miscible to a limited extent. The blends initially show two glass transitions, which approached more closely and merged gradually with increasing mixing time. A mechanical model was used to help understand the glass‐transition behavior. With increasing mixing time, the phase structure of the blends improved, and this led to an increase in the tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
2.
Jyh‐Ping Dong Jyh‐Gau Huang Fuh‐Huah Lee Jiunn‐Wei Roan Yan‐Jyi Huang 《应用聚合物科学杂志》2004,91(5):3388-3397
The effects of three series of self‐synthesized poly(methyl methacrylate) (PMMA)‐based low‐profile additives (LPAs), including PMMA, poly(methyl methacrylate‐co‐butyl acrylate), and poly(methyl methacrylate‐co‐butyl acrylate‐co‐maleic anhydride) with different chemical structures and MWs on the volume shrinkage characteristics and internal pigmentability for low‐shrink unsaturated polyester (UP) resins during curing were investigated by an integrated approach of static phase characteristics of the ternary styrene (ST)/UP/LPA system, reaction kinetics, cured‐sample morphology, microvoid formation, and property measurements. The relative volume fraction of microvoids generated during the cure was controlled by the stiffness of the UP resin used, the compatibility of the uncured ST/UP/LPA systems, and the glass‐transition temperature of the LPAs used. On the basis of the Takayanagi mechanical model, the LPA mechanism on volume shrinkage control, which accounted for phase separation and microvoid formation, and factors leading to both a good volume shrinkage control and acceptable internal pigmentability for the molded parts are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3388–3397, 2004 相似文献
3.
Shao‐Jung Wu 《应用聚合物科学杂志》2006,102(2):1139-1145
The cure reaction and phase separation mechanism of a cyanate ester‐cured epoxy and its blends with polyphenylene oxide (PPO) were studied. An autocatalytic mechanism was observed for the epoxy and its blends. The reaction rate of the blends was higher than that of the neat epoxy at initial stage; however, the reached conversion decreased with PPO content. FTIR analysis revealed that the cyanate functional group reactions were accelerated by adding PPO and indicated that several coreactions have occurred. This was caused by the reaction of cyanate ester with the PPO reactive chain ends. But at a later stage of cure, the reaction could not progress further due to diffusional limitation of PPO. To understand the relationship between the cure kinetics and phase separation of the blends, the morphology of the blends during cure was examined. When the homogeneous epoxy/PPO blends with low PPO content (10 phr) were cured isothermally, the blends were separated by nucleation and growth (NG) mechanism to form the PPO particle structure. But at high PPO content (30 phr), the phase separation took place via spinodal decomposition (SD). SD is favored near critical concentration and high cure rate system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1139–1145, 2006 相似文献
4.
Unsaturated polyester resins are the most widely used thermoset resins in the composite industry. In this study, three well‐defined unsaturated polyester resins were used. These resins have similar number‐average molecular weights, and they have different numbers of C?C bonds per molecule. The reaction kinetics of unsaturated polyester resins was studied using a differential scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer. The glass transition temperature of the isothermally cured resin was also measured. Trapped radicals were observed in the cured polyester resin from electron spin resonance (ESR) spectroscopy. Considering the diffusion‐limitation effect, a simple kinetic model was developed to simulate the reaction rate and conversion profiles of polyester vinylene and styrene vinyl groups, as well as the total reaction rate and conversion. Experimental results from DSC and FTIR measurements compare favorably with the model prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 211–227, 2002; DOI 10.1002/app.10317 相似文献
5.
A strong fluorescence emission was observed during cure of an unsaturated polyester resin containing about 30% styrene by weight. As the cure proceeded, the emission intensity at 306 nm increased. Model compound studies confirmed that the unsaturated polyester component exhibited negligible fluorescence when excited at 250 nm where styrene has strong absorption. Based on the studies of styrene/polystyrene mixtures, the fluorescence emission at 306 nm was attributed to a reduced inner‐filter effect of styrene monomer. Fluorescence intensity changes following cure at 75°C were correlated to the extent of styrene conversion determined by FT‐IR spectroscopy, demonstrating that the fluorescence measurement is more sensitive to styrene conversion in the later stages of cure than conventional IR measurements. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2446–2450, 2004 相似文献
6.
Summary: Biobased neat epoxy materials containing epoxidized linseed oil (ELO) were processed with an anhydride curing agent. A defined amount of the diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO. The selection of the DGEBF, ELO, and an anhydride curing agent resulted in an excellent combination, to provide a new biobased epoxy material showing high elastic modulus, high glass transition temperature, and high heat distortion temperature (HDT) with larger amounts of ELO. The Izod impact strength was almost constant while changing the amount of ELO. This is a promising result for future industrial applications in different engineering industries.
The effect of changing ELO concentration of the anhydride‐cured neat epoxy on the storage modulus. 相似文献
7.
Summary: Biobased neat epoxy materials containing epoxidized linseed oil (ELO) were processed with an amine curing agent. A defined amount of diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO. The thermophysical properties of the amine‐cured biobased neat epoxy were measured by dynamic mechanical analysis (DMA). The Izod impact strength increased with an increase in the amount of ELO added. The change in the Izod impact strength was correlated with the thermophysical properties measured by DMA.
Relation between the Izod impact strength and loss factor for amine‐ and anhydride‐cured ELO‐containing epoxy resins. 相似文献
8.
In this work, the viscoelastic properties of Cytec FM73 structural film adhesive were characterized. Several resin plates were cured using various process cycles to achieve a range of final cure states. Specimens cut from these plates were tested using a dynamic mechanical analyzer (DMA) and the glass‐transition temperature at each degree of cure was determined. Stress relaxation tests at different temperatures were then performed using DMA in stress relaxation mode and time‐temperature superposition was used to generate master stress relaxation curves and associated shift functions for each degree of cure. Several different constitutive models were examined for their ability to describe relaxation modulus development during cure. A simple three‐parameter model consisting of a stretched exponential with cure‐dependent terms was found to provide the best results. The results indicate that of the parameters used in the model, relaxation time strongly depends on cure state. The empirical DiBenedetto equation was used to obtain an expression for glass‐transition temperature as a function of degree of cure. This expression was in turn used to derive a new relation to describe stress relaxation time as a function of degree of cure. The shift function was modeled using a simplified form of the Vogel equation with cure‐dependent coefficients. Good correlation between measured relaxation modulus and model predictions was observed. © 2003 Wiley Periodicals, J Appl Polym Sci 91: 2548–2557, 2004 相似文献
9.
The Tg‐conversion relationship, during the thermal curing of different stoichiometric formulations of 1,1′‐(methylene‐di‐4,1‐phenylene) bismaleimide (BMI), modified with o,o′‐diallyl bisphenol A (DABA), was investigated. The DiBenedetto equation was used to model this relationship for the formulation of DABA‐1 (BMI : DABA, 1 : 1). Based on this model, the Tg‐conversion relationship of formulation DABA‐0.5 (BMI : DABA, 1 : 0.5) was modeled. The high consistency between the model curve and experimental data showed that the change of Tg, attributed to copolymerization between BMI and DABA in DABA‐0.5, in the low‐conversion regime, was the same as that in DABA‐1. This also verifies that, for the formulation DABA‐0.5, copolymerization and homopolymerization do not overlap with each other. The reactions progressed sequentially and homopolymerization occurred after completion of copolymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3244–3247, 2004 相似文献
10.
Pedro Cañamero‐Martínez José Luis de la Fuente Marta Fernández‐García 《应用聚合物科学杂志》2011,120(4):2166-2172
The curing reaction of a well‐defined glycidyl methacrylate‐co‐butyl acrylate statistical copolymer, prepared by atom transfer radical polymerization, and a commercial linear diamine (Jeffamine D‐230) was studied with the objectives of constructing and discussing a time–temperature–transformation isothermal curing for this system. Thermal and rheological analyses were used to obtain the gelation and vitrification times. Differential scanning calorimetry data showed a one‐to‐one relationship between the glass‐transition temperature (Tg) and fractional conversion independent of the cure temperature. As a result, Tg was used as a measurement of conversion. We obtained a kinetically controlled master curve for isothermal curing temperatures from 50 to 100°C by shifting Tg versus the natural logarithm time data to a reference temperature of 80°C. We calculated the apparent activation energy by applying two different methods, gel time measurements versus shift factors, suggesting a good agreement between them. Isoconversion contours were calculated by the numerical integration of the kinetic model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
11.
Several kinetic models have been proposed to simulate thermosetting cure reactions. The most complex models, based on a mechanistic approach of cure reactions, are developed based on the concepts of free radical polymerization and the mechanism of reactions with diffusion. However, mechanistic models are usually quite impractical for engineering purposes because of the difficulty in obtaining the model parameters. An alternative to these mechanistic models are the phenomenological models, formulated in terms of the degree of cure and much easier to apply. Phenomenological models have been largely used to study thermal‐initiated cure reactions, although only few works used them to model the kinetics of ultraviolet‐initiated cure reaction. This work proposes a photo‐thermal‐kinetic model to study the behavior of unsaturated polyester resins during ultraviolet‐initiated cure reactions. The model considers samples with different amounts of initiator concentration and cure reactions performed under different ultraviolet light intensities. The model has been numerically solved using the finite element technique. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
12.
Summary: Blends of the commercial liquid‐crystalline polyester Rodrun LC‐3000 (60–90 wt.‐%) with a bisphenol A‐diglycidyl ether based diepoxide (DOW D.E.R.330) and an aromatic diamine (MCDEA) prepared in a twin‐screw extruder have been compression‐moulded and cured either isothermally at 260 °C or in a temperature ramp between 160 and 230 °C. The blends were investigated with SEM and thermal analysis (DSC, DMTA). Blends with 80% Rodrun and less cured at 260 °C and the blend containing 60% Rodrun cured in a temperature ramp showed macro‐phase separation followed by reaction‐induced micro‐phase separation (RIPS) both in the Rodrun‐rich and in the epoxy‐rich macro‐separated phases. Blends containing 90, 80 and 70% Rodrun moulded at 160 °C and cured in the temperature ramp showed only RIPS and a morphology rather similar to that of the uncured blends that was most likely co‐continuous; the blend with 90% Rodrun cured at 260 °C showed RIPS and a dispersed epoxy phase in a Rodrun matrix. Phase composition has been determined by extraction of the soluble fraction and chemical analysis.
SEM showing the reaction induced micro‐phase separation for sample REA90/10i. 相似文献
13.
Pongdhorn Sae‐Oui Chakrit Sirisinha Kannika Hatthapanit Nilobon Phewthongin 《应用聚合物科学杂志》2008,110(5):2763-2769
The effect of magnesium carbonate (MgCO3) loading on the compound properties of polychloroprene (CR), natural rubber (NR), and their blends was investigated. The studied properties included Mooney viscosity, cure characteristics, and degree of filler–filler interaction. In addition to MgCO3 loading, the effect of the blend ratio on such properties was simultaneously determined. The results reveal that, regardless of the rubber type and blend ratio, increasing MgCO3 loading resulted in not only an increase in the compound viscosity, but also in the enhancements of the cure rate and state of cure. However, the effect of MgCO3 loading on the overcured behavior was strongly dependent on the rubber type and blend ratio. For CR, the presence of MgCO3 accelerated postcuring, whereas the opposite results were found for NR, in which the reversion rate was promoted. For CR/NR blends, a plateau behavior was obtained at a 50/50 blend ratio, where the degrees of postcuring and reversion were counterbalanced. The results also reveal that when MgCO3 was loaded at low concentrations (≤20 phr), the degree of filler–filler interaction was very low and had no significant effect on the compound properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
14.
An innovative method to control shrinkage in polymer blends, by using N,N‐dimethyl‐p‐toluidine to produce phase separation in an acrylic system, was applied to synthesize polymer blends from polymethyl methacrylate (PMMA) and polytriethylene glycol dimethacrylate (PTEGDMA). The morphology of several compositions, as analyzed by scanning electron microscopy, reveals microdomains as a function of the specific composition, in contrast to conventional MMA–TEGDMA copolymers synthesized by thermal decomposition of benzoyl peroxide, used here as reference materials. Micro‐Raman and DSC analyses were also carried out to support the electron microscopy results as well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1254–1260, 2004 相似文献
15.
The thermal and hydro‐thermal aging of a hot‐cured epoxy system (diglycidylether of bisphenol A (DGEBA) + dicyandiamide (DDA)) in the glassy state is revisited using DSC and IR attenuated total reflection spectroscopy. Because of the diffusion of DDA from the solid particles into the liquid DGEBA matrix, curing produces a highly crosslinked amorphous matrix that contains low crosslinked amorphous regions. After full curing, the network possesses a relatively low molecular mobility and no residual reactive groups. Thermal and hydro‐thermal loading is performed at 60°C, well below the principal glass transition temperature (Tg1 = 171°C). Both aging regimes cause significant chemical and structural changes to the glassy epoxy. It undergoes a phase separation of relatively mobile segments inside the low mobile matrix, providing a second glass transition that shifts from Tg2 = 86–114°C within 108 days of aging. This phase separation is reversible on heating into the viscoelastic state. Hydro‐thermal aging leads to a reversible and a nonreversible plasticizing effect as well. On thermal aging, no chemical changes are observed but hydro‐thermal aging causes significant chemical modifications in the epoxy system. These modifications are identified as a partial degradation of crosslinks produced by the cyano groups of the DDA and correspond to the nonreversible plasticitation. These changes in the cured epoxy should exert an influence on the mechanical properties of an adhesive bond. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006 相似文献
16.
Rui Guo Auke G. Talma Rabin N. Datta Wilma K. Dierkes Jacques W. M. Noordermeer 《大分子材料与工程》2009,294(5):330-335
The current study provides indications for improving the properties of dissimilar rubber blends. As solubility is a key factor for the distribution and a driving force for the migration of curatives in dissimilar rubber blends, it is of importance to have precise data of their solubilities. The solubilities of (insoluble) sulfur and the accelerators CBS, MBT and DCBS are measured at RT and at 60 °C, in lightly crosslinked SBR, NBR and EPDM. The experimental results correlate well with calculated solubility parameters, as determined using the method of Hoftijzer and van Krevelen.
17.
An unsaturated polyester–organophilic montmorillonite hybrid was prepared by dispersing polymerizable quaternary ammonium‐modified montmorillonite in an unsaturated polyester resin, followed by cross‐linking reaction. The purpose of this investigation was to discover the role of the polymerizable group of quaternary ammonium in improving interfacial interaction between the silicate layers and polymer chains and the mechanical properties of unsaturated polyester–montmorillonite hybrids. It is found that when the content of organophilic montmorillonite is between 2 and 5%, the tensile strength, impact strength, heat resistance, and swelling resistance of the hybrid are obviously enhanced and are better than that of the composites prepared with pristine or nonpolymerizable quaternary ammonium‐modified montmorillonite. Results of X‐ray diffraction and transmission electron microscopy show that unsaturated polyester and styrene in the resin can be intercalated into the interlayer space of organophilic montmorillonites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2038–2044, 2004 相似文献
18.
An amine cured epoxy is prepared in two different network states for hydrothermal aging. The “low‐crosslinked” network has a considerable amount of residual reactive groups and a relatively high‐molecular mobility. The low‐crosslinked matrix contains high‐crosslinked regions. In contrast, the “highly crosslinked” epoxy system has little reactive groups and a lower molecular mobility. Here, low‐crosslinked regions are found in a high‐crosslinked matrix. Hydrothermal loading for both networks is performed in demineralized water at temperatures below their glass transition. The water plasticizes both kinds of networks which remain in the glassy state, however. As a consequence, in the low‐crosslinked epoxy, the increased molecular mobility promotes an ongoing curing reaction leading to the consumption of epoxy groups until an almost complete network has formed. As a new aging process, phase separation occurs in the highly crosslinked epoxy. The new phase is more mobile than the matrix because it has its own glass transition at a lower temperature. In addition, thermooxidative degradation is observed for both network states. Certainly, these chemical and structural changes in the epoxy networks should influence the performance of an adhesive joint, a coating, or a fiber‐reinforced composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 369–377, 2004 相似文献
19.
The depolymerization of poly(ethylene terephthalate) via an aminolysis process was studied. An excess of ethanol amine in the presence of sodium acetate as a catalyst was used to produce bis(2‐hydroxyl ethylene) terephthalamide (BHETA). Unsaturated polyester (UP) resins were obtained by the reaction of BHETA with different long‐chain dibasic acids such as decanedioic acid, tetradecanoic acid, and octadecanoic acid in conjunction with maleic anhydride as a source of unsaturation. The chemical structure of the UP resins was confirmed by 1H‐NMR. The vinyl ester resins were used as crosslinking agents for UP. The curing behavior and mechanical properties of the UP resins with vinyl ester were evaluated at different temperatures ranging from 25 to 55°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
20.
The thermal aging of an amine‐cured epoxy in the glassy state is studied for two network states by using DSC and attenuated total reflection‐infrared (IR‐ATR). The “low‐crosslinked” network possesses a relatively high molecular mobility and a considerable amount of residual reactive groups. In the low crosslinked matrix, the presence of high crosslinked regions is revealed. In contrast, the “highly crosslinked” epoxy system has a reduced molecular mobility and only small reactive groups. The high crosslinked matrix contains low crosslinked regions. Thermal loading for both networks is performed below their glass transition. During thermal aging, an ongoing curing reaction takes place in the low‐crosslinked epoxy. Thermooxidative degradation and the disintegration of short‐range ordering are observed as well. The highly crosslinked epoxy system undergoes a phase separation of relatively mobile segments in the low mobile matrix, which is a reversible process on heating. Thermooxidative degradation is also detected for this kind of network. In summary, for the “low” and the “highly” crosslinked epoxy, significant chemical and structural changes take place during thermal aging even though the networks are vitrified. It is convincing that these changes in the cured epoxy should exert an influence on the mechanical properties of a bonded structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 361–368, 2004 相似文献