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1.
Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol−1) led to an 80% increase in the fracture toughness (KIC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry 相似文献
2.
Aromatic polyesters, prepared by the reaction of phthalic or isophthalic acids and α,ω-alkanediols, were used to reduce the brittleness of bisphenol-A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. These polyesters were effective as modifiers for toughening of the epoxy resin system. The most suitable composition for modification of the epoxy resins was inclusion of 20 wt % of poly(ethylene phthalate) (MW 7200), which resulted in a 150% increase in the fracture toughness (KIC) of the cured resin at no expense of its mechanical properties. The effectiveness of poly(alkylene phthalate)s as modifiers decreased with increasing the chain length of alkylene units. The toughening mechanism was discussed based on the morphological and dynamic mechanical behaviors of the modified epoxy resin system. 相似文献
3.
Takao Iijima Satoru Miura Masanori Fujimaki Takasi Taguchi Wakichi Fukuda Masao Tomoi 《应用聚合物科学杂志》1996,61(1):163-175
Aromatic polyesters, prepared by the reaction of aromatic dicarboxylic acids and 1,4-butanediol, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulfone. These polyesters contained poly(butylene phthalate)s (PBP), poly(butylene phthalate-co-butylene isophthalate)s, poly(butylene phthalate-co-butylene terephthalate)s, and poly(butylene phthalate-co-butylene 2,6-naphthalene dicarboxylate)s. All aromatic polyesters used in this study were soluble in the epoxy resin without solvents and were found to be effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PBP (MW 16,300) led to a 120% increase in the fracture toughness (KIC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 1996 John Wiley & Sons, Inc. 相似文献
4.
Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (KIC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363 相似文献
5.
Viju Susan Mathew Soney C. George Jyotishkumar Parameswaranpillai Sabu Thomas 《应用聚合物科学杂志》2014,131(4)
Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906. 相似文献
6.
A random acrylate copolymer with epoxy‐amphiphilic structure as an efficient toughener for an epoxy/anhydride system
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Fangqiao Zhao Xiaoma Fei Wei Wei Weitao Ye Jing Luo Yaxin Chen Ye Zhu Xiaoya Liu 《应用聚合物科学杂志》2017,134(26)
Toughening of epoxy resin by block copolymers containing an epoxy‐philic block and an epoxy‐phobic block is usually costly because of their complex preparation procedure. In this work, a novel, random epoxy‐amphiphilic copolymer (PHGEL), which combines an “epoxy‐philic” component and an “epoxy‐phobic” component, has been synthesized and evaluated as a potential toughening agent for a diglycidyl ether of bisphenol A–based epoxy thermoset (EP). The curing behavior of the EP/PHGEL system has been investigated, and the results show that the hydroxyl group on the PHGEL chain can slightly activate the curing reaction. The mechanical testing shows that the toughness of the epoxy resin is improved by 294% when 4 wt % of PHGEL is added. Simultaneously, the tensile strength, elongation at break, and glass‐transition temperature are also improved. In addition, the thermogravimetric analysis shows that PHGEL has no obvious effect on the thermal stability of the epoxy thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44863. 相似文献
7.
A thermoplastic modification method was studied for the purpose of improving the toughness and heat resistance and decreasing the curing temperature of the cured epoxy/4, 4′‐diaminodiphenyl sulfone resin system. A polyimide precursor‐polyamic acid (PAA) was used as the modifier which can react with epoxy. The effects of PAA on curing temperature, thermal stability and mechanical properties were investigated. The initial curing temperature (Ti) of the resin with 5 wt % PAA decreased about 50°C. The onset temperature of thermal decomposition and 10 wt %‐weight‐loss temperature for the resin system containing 2 wt % PAA increased about 60°C and 15°C respectively. Besides, the value of impact toughness and plain strain fracture toughness for the modified epoxy resin increased ~ 190% and 55%, respectively. Those changes were attributed to the outstanding thermal and mechanical properties of polyimide, and more importantly to formation of semi‐interpenetrating polymer networks composed by the epoxy network and linear PAA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
8.
A copolymer comprising poly(oxymethylene) (POM, polyacetal) was used to improve the fracture toughness of a resin based on diglycidyl ether of bisphenol A (DGEBA) cured with 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenyl methane. POM was a less effective modifier for epoxies and a third component was used as a toughener or a compatibilizer for POM. The third component includes polypropylene glycol-type urethane prepolymer (PU) and aromatic polyesters. The hybrid modifiers composed of POM and PU were more effective as modifiers for toughening epoxies than POM alone. In the ternary DGEBA/POM/PU (90/10/10wt ratio) blend, the fracture toughness, KIC, for the modified resin increased 50% with retention of flexural properties and a slight decrease in glass transition temperature (Tg) compared with those of the unmodified epoxy resin. The aromatic polyesters include poly(ethylene phthalate) (PEP), the related copolyesters and poly(butylene phthalate). PEP was most effective of them as a third component in the hybrid modifier. In the ternary DGEBA/POM/PEP (85/15/10) blend, KIC for the modified resin increased 70% with medium loss of flexural strength and retention of Tg. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviour of the modified epoxy resin systems. ©1997 SCI 相似文献
9.
Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (Kc) and energy (Gc) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (Tg) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and Tg. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392 相似文献
10.
Russell J Varley 《Polymer International》2004,53(1):78-84
This study has evaluated three low‐viscosity epoxy additives as potential tougheners for two epoxy resin systems. The systems used were a lower‐reactive resin based upon the diglycidyl ether of bisphenol A (DGEBA) and the amine hardener diethyltoluene diamine, while the second epoxy resin was based upon tetraglycidyl methylene dianiline (TGDDM) and a cycloaliphatic diamine hardener. The additives evaluated as potential tougheners were an epoxy‐terminated aliphatic polyester hyperbranched polymer, a carboxy‐terminated butadiene rubber and an aminopropyl‐terminated siloxane. This work has shown that epoxy‐terminated hyperbranched polyesters can be used effectively to toughen the lower cross‐linked epoxy resins, i.e. the DGEBA‐based systems, with the main advantage being that they have minimal effect upon processing parameters such as viscosity and the gel time, while improving the fracture properties by about 54 % at a level of 15 wt% of additive and little effect upon the Tg. This result was attributed to the phase‐separation process producing a multi‐phase particulate morphology able to initiate particle cavitation with little residual epoxy resin dissolved in the continuous epoxy matrix remaining after cure. The rubber additive was found to impart similar levels of toughness improvement but was achieved with a 10–20 °C decrease in the Tg and a 30 % increase in initial viscosity. The siloxane additive was found not to improve toughness at all for the DGEBA‐based resin system due to the poor dispersion within the epoxy matrix. The TGDDM‐based resin systems were found not to be toughened by any of the additives due to the lack of plastic deformation of the highly cross‐linked epoxy network Copyright © 2003 Society of Chemical Industry 相似文献
11.
Xavier Fernández-Francos David Foix Àngels Serra Josep M. Salla Xavier Ramis 《Reactive and Functional Polymers》2010,70(10):798-806
The cationic polymerization of DGEBA with two hyperbranched polymers (HBPs) with epoxy or vinyl end groups, using ytterbium triflate as initiator, has been studied. These HBPs have been obtained from commercial Boltorn H30 of which terminal hydroxyl groups have been replaced with long aliphatic ester chains having vinyl or epoxy end groups. Differences between the HBPs added as modifiers are observed with respect to the curing kinetics, network development, properties and morphology of the cured materials. While terminal epoxy groups ease the solubility of the HBP in DGEBA and allows its covalent incorporation into the network structure, the HBP with vinyl terminal groups is only miscible at high temperature and phase-separates during curing. As a consequence, morphology and thermal–mechanical properties are strongly dependent on the HBP employed. 相似文献
12.
Kandasamy Natarajan Rao Prakash Kumar P
V Reddy N
M Nanje Gowda R
M
V
G
K Rao 《Polymer International》2000,49(11):1321-1323
The effect of polybenzimidazole (PBI) on a silica‐filled epoxy resin matrix has been investigated. Polybenzimidazole (PBI) was incorporated into a difunctional epoxy resin matrix to the extent of 10 %, before being cured with an anhydride hardener. The effects of PBI on the curing reaction and glass transition temperature (Tg) and on the toughness of the cured epoxy matrix have been studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and a universal testing machine (Instron). The results indicate that the PBI modifier enhanced not only the glass transition temperature of the difunctional epoxy matrix but also its toughness, by its catalytic action. Further investigations have been carried out on the fractured specimens, using scanning electron microscopy (SEM) to support the enhanced toughness property of the epoxy matrix. © 2000 Society of Chemical Industry 相似文献
13.
This paper reports on the cationic electron‐beam curing of a high‐functionality SU8 epoxy resin, which is extensively used as a UV‐curing negative photoresist for micro‐electronics machine systems (MEMS) applications. Results show that elevated post‐curing treatment significantly increased both the conversion and the glass transition. The degree of conversion and the glass transition temperature were measured by using Fourier‐transform infrared (FTIR) spectroscopy and modulated differential scanning calorimetry (MDSC®), respectively. The glass transition temperature (Tg), which has been observed to be dependent on the degree of conversion, reaches a maximum of 162 °C at 50 Mrad and post‐curing at 90 °C. The degradation pattern of the cured resin does not show much variation for exposure at 5 Mrad, but does show significant variation for 50 Mrad exposure at various post‐curing temperatures. A degree of conversion of more than 0.8 was achieved at a dosage of 30 Mrad with post curing at 80 °C, for the epoxy resin with an average functionality of 8 a feature simply not achievable when using UV‐curing. Copyright © 2004 Society of Chemical Industry 相似文献
14.
Curing behavior and thermal and mechanical properties enhancement of tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone using a liquid crystalline epoxy
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Hao Jiang Rumin Wang Shameel Farhan Dandan Zhang Shuirong Zheng 《Polymer International》2016,65(4):430-438
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
15.
Synthesis,characterization, and mechanical properties of a novel terphenyl liquid crystalline epoxy resin
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A novel terphenyl liquid crystalline (LC) epoxy resin was synthesized and characterized by 1H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), and polarizing optical microscopy. Depending on the curing temperature, the synthesized resin formed both smectic and nematic LC phases. A time‐temperature‐transformation diagram was constructed to optimize the curing process, which helped in the preparation of LC and isotropic system. The terphenyl epoxy resin obtained exhibited higher acid resistance than a comparable Schiff‐base epoxy resin, and also displayed excellent fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41296. 相似文献
16.
In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
17.
An organo‐modified Boehmite (o‐Boehmite) was used to prepare nanocomposite UV‐curing coatings, based on a cycloaliphatic epoxy resin (3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate). A hyperbranched polymer (HBP) based on highly branched polyester, was also added to the resin, with the aim to modify its reactivity, such as a possible route to increase the toughness of the resin. Different amounts of the nanofiller and the HBP, ranging from 5 up to 20 wt % of resin, were dispersed into the resin in the presence of triarylsulfonium hexafluoroantimonate, as a photoinitiator for the UV curing of the resin. The rheological behavior of the formulations produced was studied as function of the shear rate and of the content of each filler using a cone and plate rheometer. A general increase in viscosity was observed with increasing the volume fraction of each filler and a moderate pseudoplastic behavior was observed when o‐Boehmite filler was added. A non‐Newtonian behavior was observed with the incorporation of the HBP. The viscosity of the epoxy/boehmite resin mixtures was analyzed as function of the nanofiller volume fraction. In the case of epoxy/hyperbranched resin mixtures, the Cross equation was used to predict the viscosity of each formulation as a function of the shear rate and an appropriate relationship to predict the viscosity of each formulation as a function of the filler volume fraction, was determined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
18.
Alan C. Meeks 《Polymer International》1975,7(1):1-10
The tapered cantilever cleavage and the single-edge-notch tension fracture toughness tests have been shown to give similar results for several cured epoxy resin systems. Methods for the calculation of fracture energy and critical stress intensity factors are described and discussed. These tests have been used to study the influence of rubber modifiers (“Hycar” CTBN and “Blendex” 311) on the toughness of a conventional epoxy resin (“Epikote” 828) reacted with anhydride curing agents. The modifiers used increase fracture energies and stress intensity factors by factors of approximately 5 and 2 respectively. 相似文献
19.
A new spiro ortho carbonate, 3,9‐di(p‐methoxybenzyl)‐1,5,7,11‐tetra‐oxaspiro(5,5)undecane was prepared by the reaction of 2‐methoxybenzyl‐1,3‐propanediol with di(n‐butyl)tin oxide, following with carbon disulfide. Its cationic polymerization was carried out in dichloromethane using BF3‐OEt2 as catalyst. The [1H], [13C]NMR and IR data as well as elementary analysis of the polymers obtained indicated that it underwent double ring‐opening polymerization. The polymerization mechanism is discussed. The curing reaction of bisphenol A type epoxy resin in the presence of the monomer and a curing agent was investigated. DSC measurements were used to follow the curing process. In the case of boron trifluoride‐o‐phenylenediamine (BF3‐OPDA) as curing agent, two peaks were found on the DSC curves, one of which was attributed to the polymerization of the epoxy group, and the other to the copolymerization of the monomer with the isolated epoxy groups or homopolymerization. However, when BF3‐H2NEt was used as curing agent, only one peak was present. IR measurement of the modified epoxy resin with various weight ratios of epoxy resin/monomer was performed in the presence of BF3‐H2NEt as curing agent. The results demonstrate that the conversion of epoxy group increases as the content of monomer increases. The curing process and the structure of the epoxy resin network are discussed. © 2000 Society of Chemical Industry 相似文献
20.
A soy‐based resin was prepared by the process of transesterfication and epoxidation of regular food‐grade soybean oil. The soy‐based resin was used as a reactive diluent and also as a replacement of bisA epoxy resin in an anhydride‐cured polymer. The curing efficiency of soy epoxy resin was studied using differential scanning calorimetry. Physicochemical properties and fracture behavior of soy‐based resin polymers were studied using dynamic mechanical analysis and fracture toughness measurements, respectively. Toughness measurements were carried out using the compact tension geometry following the principles of linear elastic fracture mechanics. Tests showed that the addition of soy‐based epoxy resin to the base epon resin improved the toughness of the blend. Morphology of the fractured specimens has been analyzed by scanning electron microscopy. The soy‐based resins hold great potential for environmentally friendly, renewable resource based, and low cost materials for structural applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 相似文献