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1.
Binary blends composed of 4,4′‐bis(3,4‐dicyanophenoxy)biphenyl (biphenyl PN) and diglycidyl ether of bisphenol A (epoxy resin) and oligomeric n = 4 phthalonitrile (n = 4 PN) and epoxy resin were prepared. The cure behavior of the blends was studied under dynamic and isothermal curing conditions using differential scanning calorimetry, simultaneous thermogravimetric/differential thermal analysis, infrared spectroscopy, and rheological analysis. The studies revealed that phthalonitrile‐epoxy blends exhibited good processability and that they copolymerized with or without the addition of curing additive. In the absence of curing additive, the blends required higher temperatures and longer cure times. The thermal and dynamic viscoelastic properties of amine‐cured phthalonitrile‐epoxy copolymers were examined and compared with those of the neat epoxy resin. The properties of the epoxy resin improved with increasing biphenyl PN content and with n = 4 PN addition. Specifically, the copolymers exhibited higher glass transition temperatures, increased thermal and thermo‐oxidative stabililty, and enhanced dynamic mechanical properties relative to the commercially available epoxy resin. The results showed that the phthalonitrile‐epoxy blends and copolymers have an attractive combination of processability and high temperature properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

2.
Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with Tg results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007  相似文献   

3.
This work was aimed at studying the efficiency of graft copolymers at stabilizing the co-continuous morphology of polystyrene (PS)/polyamide 6 (PA6) blends during quiescent annealing. A series of graft copolymers with PS as backbone and PA6 as grafts, denoted as PS-g-PA6, with different molecular structures and compositions were used as compatibilizers. The co-continuous domain size of the blends without PS-g-PA6 increased almost linearly with annealing time. The addition of the PS-g-PA6 not only narrowed down the composition range of co-continuity of PS/PA6 blend but also slowed down and even stopped completely the coarsening of the co-continuous morphology during the quiescent annealing. Moreover, the efficiency of PS-g-PA6 depended very much on its molecular structure and/or composition. For graft copolymers with similar backbone and graft chain number, the longer the grafts, the higher their stabilizing efficiency. For a given backbone/graft composition, graft copolymers having fewer and longer grafts were more efficient at compatibilizing and stabilizing the co-continuous morphology.  相似文献   

4.
The epoxy/polystyrene system is characterized by a poor adhesion between the constituent phases, which determines its mechanical properties. The adhesion can be improved via blends based on epoxy resin and random copolymers, poly(styrene‐co‐allylalcohol) (PS‐co‐PA). In this work, the influence of PS‐co‐PA content and the good adhesion between the phases on the tensile properties and the fracture toughness achieved through instrumented Charpy tests have been investigated. The tensile strength and the deformation at break showed an increase in the PS‐co‐PA content while the Young's modulus remained the same. The tensile fracture surfaces revealed that the improvement of these magnitudes was mainly due to a crack deflection mechanism. Also, the fracture toughness of the blends was superior to that of the pure epoxy resin. The main operating toughening mechanism was crack deflection. The fractographic analysis showed that ~ 80% of the particles were broken, and the crack tended to divert from its original path through the broken PS‐co‐PA particles. The remaining particles were detached from the epoxy resin, and the holes left suffered plastic deformation. Analytical models were used to predict successfully the toughness due to these mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

5.
In this study, dual compatibilizers composed of the commercially available maleic anhydride‐grafted polypropylene (PP–MA) and a multifunctional epoxy resin were demonstrated to effectively compatibilize the immiscible and incompatible blends of PP and poly(butylene terephthalate) (PBT). The PP–MA with a low MA content is totally miscible with PP to make the PP phase quasi‐functionalized, so that the multifunctional epoxy has the chance to react with PBT and PP–MA simultaneously to form PP–MA‐co‐epoxy‐co‐PBT copolymers at the interface. These desired copolymers are able to anchor along the interface and serve as efficient compatibilizers. The compatibilized blends, depending on the quantity of dual compatibilizers employed, exhibit higher viscosity, finer phase domain, and improved mechanical properties. Epoxy does not show compatibilization effects for the PP/PBT blends without the presence of PP–MA in the blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2272–2285, 2001  相似文献   

6.
Poly[(n‐butyl acrylate)‐block‐poly(methyl methacrylate)‐co‐(glycidyl methacrylate)] (BMG) diblock copolymers incorporating an epoxy‐reactive functionality in one block have been synthesized and used as modifiers for the model epoxy resin E‐51 cured with 4,4′‐diaminodiphenyl methane (DDM). The properties and morphologies of the modified epoxy thermosets were investigated by dynamic mechanical analysis (DMA), impact testing and scanning electron microscopy (SEM). The results reveal that addition of the block copolymers leaves the glass transition temperatures of the blends relatively unchanged, with small decreases in the storage moduli at room temperature. The toughening effect is dependent on the chemical structures of the block copolymers and an increase in the impact strength by a factor of two was obtained by the addition of ‘relatively symmetrical’ block copolymers. Moreover, the impact test results are consistent with the morphologies of the fracture surfaces as evidenced by SEM. Copyright © 2005 Society of Chemical Industry  相似文献   

7.
The graft copolymer of polystyrene and polyamide 6 (PS-g-PA6) was investigated by anionic polymerization of ε-caprolactam (CL), using the free radical copolymer of styrene and a kind of allyl monomer containing N-carbamated caprolactam group as macroactivator (PS-CCL). CL monomers were grafted onto PS-CCL backbone via initiating N-carbamated caprolactam (CCL) pendants along its backbone to form the graft copolymer in the presence of catalyst sodium caprolactamate. The macroactivator was characterized by Fourier-transform infrared spectroscopy and nuclear magnetic resonance, and the graft copolymer by the selective solvent extraction technique using methanol and chloroform as solvents. PS-g-PA6 copolymers with different PS content were synthesized to study the effect of PS on morphology, crystallinity, dimensional stability, and thermal properties, using scanning electron microscopy, X-ray diffraction, water absorption measurement, thermogravimetric analysis, and differential scanning calorimetry. The results show the percentage crystallinity of graft copolymer decreases with increasing PS content, but the addition of PS scarcely influences the crystalline structure of PA6. The graft copolymer has improved thermal properties and dimensional stability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

8.
Hydroxy‐terminated poly(arylene ether nitrile) oligomers with pendent tert‐butyl groups (PENTOH) were synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone in N‐methyl‐2‐pyrrolidone medium with anhydrous potassium carbonate as a catalyst at 200°C in a nitrogen atmosphere. The PENTOH oligomers were blended with diglycidyl ether of bisphenol A epoxy resin and cured with 4,4′‐diaminodiphenyl sulfone. The curing reaction was monitored with infrared spectroscopy and differential scanning calorimetry. The morphology, fracture toughness, and thermomechanical properties of the blends were investigated. The scanning electron micrographs revealed a two‐phase morphology with a particulate structure of the PENTOH phase dispersed in the epoxy matrix, except for the epoxy resin modified with PENTOH with a number‐average molecular weight of approximately 4000. The storage modulus of the blends was higher than that of the neat epoxy resin. The crosslink density calculated from the storage modulus in the rubbery plateau region decreased with an increase in PENTOH in the blends. The fracture toughness increased more than twofold with the addition of PENTOH oligomers. The tensile strength of the blends increased marginally, whereas the flexural strength decreased marginally. The dispersed PENTOH initiated several toughening mechanisms, which improved the fracture toughness of the blends. The thermal stability of the epoxy resin was not affected by the addition of PENTOH to the epoxy resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

9.
The cure kinetics and morphology of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin modified with a poly (ether ether ketone) based on tertiary butyl hydroquinone (PEEK-T) cured with diamino diphenyl sulphone (DDS) were investigated using differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA). The results obtained from DSC were applied to autocatalytic and diffusion controlled kinetic models. The reaction mechanism broadly showed autocatalytic behaviour regardless of the presence of PEEK-T. At higher PEEK-T concentration, more diffusion controlled mechanism was observed. The rate of curing reaction decreased with increase in thermoplastic content and also with the lowering of curing temperature. The activation energies of the blends are higher than that of the neat resin. The blends showed a phase separated morphology. The dispersed phase showed a homogeneous particle size distribution. The Tg of the neat resin decreased with the decrease in cure temperature. Two Tg's corresponding to the epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum. The storage modulus of 10 and 20 phr PEEK-T blends are found to be greater than the neat resin.  相似文献   

10.
Maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer (ABS‐g‐MA) was used as an impact modifier of polyamide 6 (PA6). Epoxy resin was introduced into PA6/ABS‐g‐MA blends to further improve their properties. Notched Izod impact tests showed that the impact strength of PA6/ABS‐g‐MA could be improved from 253 to 800 J/m with the addition of epoxy resin when the ABS‐g‐MA content was set at 25 wt %. Differential scanning calorimetry results showed that the addition of epoxy resin made the crystallization temperature and melting temperature shift to lower temperatures; this indicated the decrease in the PA6 crystallization ability. Dynamic mechanical analysis testing showed that the addition of epoxy resin induced the glass‐transition temperature of PA6 and the styrene‐co‐acrylonitrile copolymer phase to shift to higher temperatures due to the chemical reactions between PA6, ABS‐g‐MA, and epoxy resin. The scanning electron microscopy results indicated that the ABS‐g‐MA copolymer dispersed into the PA6 matrix uniformly and that the phase morphology of the PA6/ABS‐g‐MA blends did not change with the addition of the epoxy resin. Transmission electron microscopy showed that the epoxy resin did not change the deformation mechanisms of the PA6/ABS‐g‐MA blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
The hydrogen bonding and miscibility behaviors of poly(styrene‐co‐methacrylic acid) (PSMA20) containing 20% of methacrylic acid with copolymers of poly(styrene‐co‐4‐vinylpyridine) (PS4VP) containing 5, 15, 30, 40, and 50%, respectively, of 4‐vinylpyridine were investigated by differential scanning calorimetry, thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). It was shown that all the blends have a single glass transition over the entire composition range. The obtained Tgs of PSMA20/PS4VP blends containing an excess amount of PS4VP, above 15% of 4VP in the copolymer, were found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are able to form interpolymer complexes. The FTIR study reveals presence of intermolecular hydrogen‐bonding interaction between vinylpyridine nitrogen atom and the hydroxyl of MMA group and intensifies when the amount of 4VP is increased in PS4VP copolymers. A new band characterizing these interactions at 1724 cm−1 was observed. In addition, the quantitative FTIR study carried out for PSMA20/PS4VP blends was also performed for the methacrylic acid and 4‐vinylpyridine functional groups. The TGA study confirmed that the thermal stability of these blends was clearly improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
The compatibility of styrene‐block‐butadiene‐block‐styrene (SBS) triblockcopolymer in epoxy resin is increased by the epoxidation of butadiene segment, using hydrogen peroxide in the presence of an in situ prepared catalyst in water/dichloroethane biphasic system. Highly epoxidized SBS (epoxy content SBS >26 mol%) give rise to nanostructured blends with epoxy resin. The cure kinetics of micro and nanostructured blends of epoxy resin [diglycidyl ether of bisphenol A; (DGEBA)]/amine curing agent [4,4′‐diaminodiphenylmethane (DDM)] with epoxidized styrene‐block‐butadiene‐block‐styrene (eSBS 47 mol%) triblock copolymer has been studied for the first time using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as kinetic constants and activation energy. The cure reaction rate is decreased with increasing the concentration of eSBS in the blends and also with the lowering of cure temperature. The compatibility of eSBS in epoxy resin is investigated in detailed by Fourier transform infrared spectroscopy, optical and transmition electron microscopic analysis. The experimental data of the cure behavior for the systems, epoxy/DDM and epoxy/eSBS(47 mol%)/DDM show an autocatalytic behavior regardless of the presence of eSBS in agreement with Kamal's model. The thermal stability of cured resins is also evaluated using thermogravimetry in nitrogen atmosphere. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers  相似文献   

13.
Wenchun Fan  Sixun Zheng 《Polymer》2008,49(13-14):3157-3167
Polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymers with linear and tetra-armed star-shaped topological structures were synthesized via sequential atomic transfer radical polymerization (ATRP). With pentaerythritol tetrakis(2-bromoisobutyrate) as the initiator, the star-shaped block copolymers with two sequential structures (i.e., s-PMMA-b-PS and s-PS-b-PMMA) were prepared and the arm lengths and composition of the star-shaped block copolymers were controlled to be comparable with those of the linear PS-b-PMMA (denoted as l-PS-b-PMMA). The block copolymers were incorporated into epoxy resin to access the nanostructures in epoxy thermosets, by knowing that PMMA is miscible with epoxy after and before curing reaction whereas the reaction-induced phase separation occurred in the thermosetting blends of epoxy resin with PS. Considering the difference in miscibility of epoxy with PMMA and/or PS, it is judged that the reaction-induced microphase separation occurred in the systems. The design of these block copolymers allows one to investigate the effect of topological structures of block copolymers on the morphological structures of the thermosets. By means of atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS), the morphology of the thermosets was examined. It is found that the nanostructures were formed in the thermosets containing l-PMMA-b-PS and s-PS-b-PMMA block copolymers. It is noted that the long-range order of the nanostructures in the epoxy thermosets containing l-PMMA-b-PS is obviously higher than that in the system containing s-PS-b-PMMA. However, the macroscopic phase separation occurred in the thermosetting blends of epoxy resin with s-PMMA-b-PS block copolymer.  相似文献   

14.
The epoxy resin/curing agent/montmorillonite nanocomposite was prepared by a casting and curing process. The intercalation and exfoliation behaviors of epoxy resin in the presence of organophilic montmorillonite were investigated by X‐ray diffraction (XRD) and dynamic mechanical thermal analysis (DMTA). For the diethylenetriamine curing agent, the intercalated nanocomposite was obtained; and the exfoliated nanocomposite would be formed for tung oil anhydride curing agent. The curing condition does not affect the resulting kind of composite, both intercalation or exfoliation. For intercalated nanocomposite, the glass transition temperature Tg, measured by DMTA and affected by the curing temperature of matrix epoxy resin is corresponded to that of epoxy resin without a gallery. The α′ peak of the loss tangent will disappear if adding montmorillonite into the composite. It was also found that the Tg of the exfoliated nanocomposite decreases with increasing montmorillonite loading. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 842–849, 2002; DOI 10.1002/app.10354  相似文献   

15.
In this work, maleic anhydride‐grafted polypropylene (PP‐g‐MAH) and maleic anhydride‐grafted poly(acrylonitrile‐butadiene‐styrene) (ABS‐g‐MAH) at 2 : 1 mass ratio were added as a compatibilizer in the PP/ABS blends. The compatibilizing effect was evaluated by adding the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ). The reaction in reactive extrusion, morphological structure, and properties of PP and ABS blends were investigated by using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray spectrum, transmission electron microscope (TEM), dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC), and mechanical properties tests. The results showed that the compatibilizing effect was greatly improved because of the addition of the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ) because the link structure of PP‐g‐MAH and ABS‐g‐MAH was formed by the reaction of anhydride group with epoxy group catalyzed by the imidazole. The size of the dispersed phase decreased dramatically, the interfacial adhesion between ABS particles and PP matrix was improved, and the tensile strength and flexural modulus of the PP/ABS blends increased further. The optimizing properties were obtained at 3 phr E51/2E4MZ. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40898.  相似文献   

16.
This work was aimed at studying the emulsification efficiency of graft copolymers and the effect of feeding mode on the emulsification efficiency using the emulsification curve approach. The blends were composed of polystyrene (PS) and polyamide 6 (PA6). PS was always the matrix and PA6 the dispersed phase. A series of graft copolymers of PS and PA6, denoted as PS-g-PA6, with different molecular structures were used as emulsifiers. Feeding mode had a very significant effect on the size of the dispersed phase domains at short mixing time and its effect decreased or became negligible at long mixing time. This indicates that feeding mode affected mostly the time necessary for the PS-g-PA6 emulsifier to reach and emulsify the PS/PA6 interfaces. The molecular structure of the PS-g-PA6 graft copolymer also had a profound effect on its emulsification efficiency. The longer the PA6 grafts (from 1.7 to 5.1 kg/mol), the higher the emulsification efficiency. On the other hand, the number of PA6 grafts had little effect on the emulsification efficiency when the PA6 grafts were short (1.6-1.7 kg/mol). The effect of the blend composition was also investigated.  相似文献   

17.
We have examined the effect of fibre addition on the glass transition temperature (T g ) of two epoxy resin systems (an amine cured and an anhydride cured epoxy system) using dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The presence of fibres changes the glass transition temperature (T g ) of an anhydride cured epoxy resin but does not affect that of an amine cured epoxy. The data suggest that two counteracting mechanisms are responsible for these changes: firstly, the presence of fibres causes a restriction of the molecular motion in the resin system, and secondly, the presence of carboxyi and keto-enol groups on the fibre surface inhibit curing of the resin close to the fibre, i.e. in the interphase region. The former increases the T g and is a long range effect whereas the latter decreases the T g and is a localised phenomenon. Changes in the dynamic properties of the interphase region are only detected when the samples are loaded in the longitudinal direction and not in the transverse direction where bulk matrix properties dominate. Sizing the fibres before their incorporation into the epoxy resin eliminates the variation in interfacial properties arising from differences in fibre surface chemistry.  相似文献   

18.
Poly(glycidyl methacrylate-co-ethyl methacrylate) and poly(glycidyl methacrylate-co-butyl methacrylate) random copolymers (with 50–50 mol % of monomers) were made radiopaque by grafting iodine moieties through the ring opening reaction of the epoxy groups. The percentage weight of grafted iodine in the copolymers was found to be as high as 19%. The iodinated copolymers showed higher glass transition temperature and thermal stability in comparison with the parent copolymers. Iodinated copolymer of poly(glycidyl methacrylate-co-ethyl methacrylate) has improved glass transistion temperature than iodinated poly(glycidyl methacrylate-co-butyl methacrylate). Radiographic analysis of these iodinated copolymers showed excellent radiopacity. The in vitro cytotoxicity tests revealed cytocompatibility with cells. These radiopaque copolymers are expected to find application as dental and orthopedic cements. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

19.
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   

20.
Thermal and morphology properties of polyamide-12 (PA12)/poly(butylene terephthalate) (PBT) blends with hyperbranched poly(ethyleneimine)-g-polyamide-12 (PEI-g-PA12) as reactive compatibilizer were studied by a combination of Optical Microscopy, DSC and 13C NMR. This compatibilizer was synthesized by simple amidation reactions. The addition of PEI-g-PA12 greatly modified the morphology of PA12/PBT blends, which were originally an incompatible polymer pair. At the beginning of the addition of compatibilizers, the sizes of PA12 and PBT rich phases decreased and the blends dispersed better. Then the phase structures became more diffused with time. At last, bi-phase morphology disappeared totally and one homogeneous structure was obtained at 260 °C. The higher the PEI-g-PA12 compatibilizer content was, the faster the morphology changed. Our DSC measurements provided a consistent picture of the crystallization behavior of PA12 and PBT components. The comparison of 13C NMR spectrums between PA12/PBT and PA12/PBT/PEI-g-PA12 undergoing the same thermal treatment indicated that compatibilization was originated from the formation of hyperbranched PBT-co-PEI-co-PA12 copolymers.  相似文献   

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