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1.
The nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) (PMMA/SMA) blends over wide appropriate temperature and heating rate ranges was studied using time‐resolved small‐angle laser light scattering. During the non‐isothermal process, a quantitative logarithm function was established to describe the relationship between cloud point (Tc) and heating rate (k) as given by Tc = Alnk + T0, in which the parameter A, reflecting the heating rate dependence, is much different for different compositions due to phase‐separation rate and activation energy difference. For the isothermal phase‐separation process, an Arrhenius‐like equation was successfully applied to describe the temperature dependence of the apparent diffusion coefficient (Dapp) and the relaxation time (τ) of the early stage as well as the late stage of spinodal decomposition (SD) of PMMA/SMA blends. Based on the successful application of the Arrhenius‐like equation, the related activation energies could be obtained from Dapp and τ of the early and late stages of SD, respectively. In addition, these results indicate that it is possible to predict the temperature dependence of the phase‐separation behavior of binary polymer mixtures during isothermal annealing over a range of 100 °C above the glass transition temperature using the Arrhenius‐like equation. © 2012 Society of Chemical Industry  相似文献   

2.
The objective of this work was to study the miscibility and phase‐separation temperatures of poly(styrene‐co‐maleic anhydride) (SMA)/poly(vinyl methyl ether) (PVME) and SMA/poly(methyl methacrylate) (PMMA) blends with differential scanning calorimetry and small‐angle light scattering techniques. We focused on the effect of SMA partial imidization with aniline on the miscibility and phase‐separation temperatures of these blends. The SMA imidization reaction led to a partially imidized styrene N‐phenyl succinimide copolymer (SMI) with a degree of conversion of 49% and a decomposition temperature higher than that of SMA by about 20°C. We observed that both SMI/PVME and SMI/PMMA blends had lower critical solution temperature behavior. The imidization of SMA increased the phase‐separation temperature of the SMA/PVME blend and decreased that of the SMA/PMMA blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

3.
Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005  相似文献   

4.
Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry  相似文献   

5.
Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (Tg) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry  相似文献   

6.
Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and poly(styrene‐co‐acrylonitrile) (SAN) prepared by solution casting were investigated by differential scanning calorimetry. In the study of PHBV‐SAN blends by differential scanning calorimetry, glass transition temperature and melting point of PHBV in the PHBV‐SAN blends were almost unchanged compared with those of the pure PHBV. This result indicates that the blends of PHBV and SAN are immiscible. However, crystallization temperature of the PHBV in the blends decreased approximately 9–15°. From the results of the Avrami analysis of PHBV in the PHBV‐SAN blends, crystallization rate constant of PHBV in the PHBV‐SAN blends decreased compared with that of the pure PHBV. From the above results, it is suggested that the nucleation of PHBV in the blends is suppressed by the addition of SAN. From the measured crystallization half time and degree of supercooling, interfacial free energy for the formation of heterogeneous nuclei of PHBV in the PHBV‐SAN blends was calculated and found to be 2360 (mN/m)3 for the pure PHBV and 2920–3120 (mN/m)3 for the blends. The values of interfacial free energy indicate that heterogeneity of PHBV in the PHBV‐SAN blends is deactivated by the SAN. This result is consistent with the results of crystallization temperature and crystallization rate constant of PHBV in the PHBV‐SAN blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 673–679, 2000  相似文献   

7.
The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry  相似文献   

8.
Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors aT can be expressed by the Williams–Landel–Ferry equation: log aT = ?8.86(T ? Ts)/(101.6 + T ? Ts). The compositional dependency of Ts represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001  相似文献   

9.
Dynamic viscoelastic properties of blends of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with various AN contents were measured to evaluate the influence of SAN composition, consequently χ parameter, upon the melt rheology. PMMA/SAN blends were miscible and exhibited a terminal flow region characterized by Newtonian flow, when the acrylonitrile (AN) content of SAN ranges from 10 to 27 wt %. Whereas, PMMA/SAN blends were immiscible and exhibited a long time relaxation, when the AN content in SAN is less than several wt % or greater than 30 wt %. Correspondingly, melt rheology of the blends was characterized by the plots of storage modulus G′ against loss modulus G″. Log G′ versus log G″ plots exhibited a straight line of slope 2 for the miscible blends, but did not show a straight line for the immiscible blends because of their long time relaxation mechanism. The plateau modulus, determined as the storage modulus G′ in the plateau zone at the frequency where tan δ is at maximum, varied linearly with the AN content of SAN irrespective of blend miscibility. This result indicates that the additivity rule holds well for the entanglement molecular weights in miscible PMMA/SAN blends. However, the entanglement molecular weights in immiscible blends should have “apparent” values, because the above method to determine the plateau modulus is not applicable for the immiscible blends. Effect of χ parameter on the plateau modulus of the miscible blends could not be found. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
This study attempted to correlate morphological changes and physical properties for a high rubber content acrylonitrile–butadiene–styrene (ABS) and its diluted blends with a poly(styrene‐co‐acrylonitrile) (SAN) copolymer. The results showed a close relationship between rubber content and fracture toughness for the blends. The change of morphology in ABS/SAN blends explains in part some deviations in fracture behavior observed in ductile–brittle transition temperature shifts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2606–2611, 2004  相似文献   

11.
Nanoblends were obtained from poly(styrene‐co‐acrylonitrile) (SAN) as a matrix, and poly(butylene terephthalate) (PBT) was used as a nanodispersed phase. Compatibilized SAN/PBT blends were prepared by reactive extrusion, and the PBT concentrations ranged between 3 and 30 wt %. Nanoblends were obtained for up to 10 wt % PBT concentrations in the presence of the compatibilizer. With 20 and 30 wt % PBT, the extruded material presented a droplet dispersed phase. The same blends were subjected to an injection‐molding process, which provided a cocontinuous phase morphology. The influence of the concentration of the dispersed phase and the type of morphology on the mechanical behavior of tensile test, flexural test, impact test, and deflection temperature of the blends was analyzed. The results show an important reduction in the particle size of the dispersed phase, which was due to the presence of the compatibilizer. Furthermore, the type of morphology and an excess of compatibilizer exerted a stronger influence on the mechanical properties than the particle size of the dispersed phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45030.  相似文献   

12.
The aim of the study was to investigate the synthesis of a copolymer bearing cyclic carbonate and its miscibility with styrene/acrylonitrile copolymer (SAN) or poly(vinyl chloride) (PVC). (2‐Oxo‐1,3‐dioxolan‐4‐yl)methyl vinyl ether (OVE) as a monomer was synthesized from glycidyl vinyl ether and CO2 using quaternary ammonium chloride salts as catalysts. The highest reaction rate was observed when tetraoctylammonium chloride (TOAC) was used as a catalyst. Even at the atmospheric pressure of CO2, the yield of OVE using TOAC was above 80% after 6 h of reaction at 80°C. The copolymer of OVE and N‐phenylmaleimide (NPM) was prepared by radical copolymerization and was characterized by FTIR and 1H‐NMR spectroscopies and differential scanning calorimetry (DSC). The monomer reactivity ratios were given as r1 (OVE) = 0.53–0.57 and r2 (NPM) = 2.23–2.24 in the copolymerization of OVE and NPM. The films of poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were cast from N‐dimethylformamide. An optical clarity test and DSC analysis showed that poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were both miscible over the whole composition range. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1809–1815, 2000  相似文献   

13.
The gloss properties of the polycarbonate (PC)/poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) (MABS) blend with styrene‐acrylonitrile‐co‐glycidyl methacrylate (SAN‐co‐GMA) as a compatibilizing agent were investigated. For the PC/poly(MABS)/SAN‐co‐GMA (65/15/20, wt %) blend surface, the reduction of gloss level was observed most significantly when the GMA content was 0.1 wt %, compared with the blends with 0.05 wt % GMA or without GMA content. The gloss level of the PC/poly(MABS)/SAN‐co‐GMA (0.1 wt % GMA) blend surface was observed to be 35, which showed 65% lower than the PC/poly(MABS)/SAN‐co‐GMA blend without GMA content. The gloss reduction was most probably caused by the insoluble fractions of the PC/poly(MABS)/SAN‐co‐GMA blend that were formed by the reaction between the carboxylic acid group in poly(MABS) and epoxy group in SAN‐co‐GMA. The results of optical and transmission electron microscope analysis, spectroscopy study, and rheological properties supported the formation of insoluble structure of the PC/poly(MABS)/SAN‐co‐GMA blend when the GMA content was 0.1 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46450.  相似文献   

14.
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   

15.
PS/AES blends were prepared by in situ polymerization of styrene in the presence of AES elastomer, a grafting copolymer of poly(styrene‐co‐acrylonitrile) – SAN and poly(ethylene‐co‐propylene‐co‐diene)–EPDM chains. These blends are immiscible and present complex phase behavior. Selective extraction of the blends' components showed that some fraction of the material is crosslinked and a grafting of PS onto AES is possible. The morphology of the noninjected blends consists of spherical PS domains covered by a thin layer of AES. After injection molding, the blends show morphology of disperse elastomeric phase morphology in a rigid matrix. Two factors could contribute to the change of morphology: (1) the stationary polymerization conditions did not allow the mixture to reach the equilibrium morphology; (2) the grafting degree between PS and AES was not high enough to ensure the morphological stability against changes during processing in the melting state. The drastic change of EPDM morphology from continuous to disperse phase has as consequence a decrease in the intensity of the loss modulus peaks corresponding to the EPDM glass transition. However, the storage modulus at temperatures between the glass transition of EPDM and PS/SAN phases does not change significantly. This effect was attributed to the presence of the SAN rigid chains in the AES. © 2009 Wiley Periodicals, Inc. Journal of Applied Polymer Science, 2009  相似文献   

16.
The miscibility or complexation of poly(styrene‐co‐acrylic acid) containing 27 mol % of acrylic acid (SAA‐27) and poly(styrene‐coN,N‐dimethylacrylamide) containing 17 or 32 mol % of N,N‐dimethylacrylamide (SAD‐17, SAD‐32) or poly(N,N‐dimethylacrylamide) (PDMA) were investigated by different techniques. The differential scanning calorimetry (DSC) analysis showed that a single glass‐transition temperature was observed for all the mixtures prepared from tetrahydrofuran (THF) or butan‐2‐one. This is an evidence of their miscibility or complexation over the entire composition range. As the content of the basic constituent increases as within SAA‐27/SAD‐32 and SAA‐27/PDMA, higher number of specific interpolymer interactins occurred and led to the formation of interpolymer complexes in butan‐2‐one. The qualitative Fourier transform infrared (FTIR) spectroscopy study carried out for SAA‐27/SAD‐17 blends revealed that hydrogen bonding occurred between the hydroxyl groups of SAA‐27 and the carbonyl amide of SAD‐17. Quantitative analysis carried out in the 160–210°C temperature range for the SAA‐27 copolymer and its blends of different ratios using the Painter–Coleman association model led to the estimation of the equilibrium constants K2, KA and the enthalpies of hydrogen bond formation. These blends are miscible even at 180°C as confirmed from the negative values of the total free energy of mixing ΔGM over the entire blend composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1011–1024, 2007  相似文献   

17.
In this work, ternary polymer blends based on (polyamide 6)/(poly[styrene‐co‐acrylonitrile])/(poly[styrene‐b‐{ethylene‐co‐butylene}‐b‐styrene]) (SEBS) triblock copolymer and a varying concentration of the reactive (maleic anhydride)‐grafted SEBS were prepared by using a melt‐blending process. The effects of the material parameters (composition of ternary blends and SEBS/[{maleic anhydride}‐grafted SEBS] concentration ratio) and blending sequence on the morphological and mechanical properties of ternary blends were studied. Taguchi experimental design methodology was employed to design the experiments and select the material and processing parameters for the optimized mechanical properties. Tensile properties (Young's modulus and yield stress) and impact strength were considered as the response variables. It was demonstrated that there is a meaningful relationship between the composition of blends, processing parameters, observed phase structure, and obtained mechanical properties. The mechanical tests showed that the highest impact strength was achieved as the dispersion of the rubbery phase achieved an optimum size of about 1 μm. J. VINYL ADDIT. TECHNOL., 23:329–337, 2017. © 2015 Society of Plastics Engineers  相似文献   

18.
FTIR study of the hydrogen bonding interactions within blends of different ratios of poly(styrene‐co‐acrylic acid) containing 18, 27, and 32 mol% of acrylic acid (SAA) and poly(styrene‐coN,N‐dimethylacrylamide) containing 17 mol% of N,N‐dimethylacrylamide (SAD‐17) was carried out qualitatively and quantitatively in the temperature range varying from room temperature to 210°C. Two new bands characterizing these interactions appeared in the 1800–1550 cm–1 region at 1730 cm–1 and 1616 cm–1 and are attributed to “liberated” carbonyl group of the acidic copolymer and the “associated amide” carbonyl group, respectively. Equilibrium constants describing both the self‐association K2 and inter‐association KA and the enthalpy of hydrogen bonding formation in the different blends were experimentally determined using a curve fitting analysis of the infra‐red spectra as a function of temperature using the appropriate equations derived from the Painter‐Coleman association model. The obtained results confirm the miscibility of these blends in the considered temperature range from the negative values of the total free energy of mixing ΔGM. Optimization of the extent of intermolecular interactions between the two polymers in these blends is investigated. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

19.
Polymer blend of poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) and poly(styrene‐co‐acrylonitrile) (SAN), which has broad commercial interest, has limited miscibility. A triblock terpolymer, polystyrene‐block‐polybutadiene‐block‐poly(methyl methacrylate) (SBM), is often used as compatibilizer to improve the miscibility of PPE/SAN. In this work, dissipative particle dynamics and molecular dynamics of Material Studio were used to study the essentials that influence miscibility of the blend systems, and then Flory–Huggins parameter χ, radial distribution function (RDF) and morphologies are analyzed. It shows that the blends with more content of styrene in SAN (above 90 wt%), whose mass percentage is 60%, are best miscible. For the systems of PPE/SAN added with SBM, the miscibility increases and then decreases with the increase of SBM content. A longer chain of styrene (S) in SBM leads to wrapped structure of PMMA by PB, wrapped by PS, resulting in decrease of the miscibility. From studies and simulation of χ and RDF, the best blend system for commercial and industrial use is the one with mass ratio of PPE/SAN/SBM 36/54/10, in which S content in SAN is above 90 wt%. For SBM, the ratio of chain length styrene (S)/butadiene (B) is lessthan 1, while B and M are the same in chain length. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

20.
Immiscible blends of poly(2,6‐dimethyl‐1,4‐phenylene ether)/poly(styrene‐co‐acrylonitrile) (PPE/SAN) were batch‐foamed using CO2 as a blowing agent as a function of foaming temperature, foaming time, and blend composition. Evaluation of the resulting cellular morphology revealed an enhanced foamability of SAN with PPE contents up to 20 wt% as indicated by a similar volume expansion but a significantly reduced mean cell size. This behavior is related to a heterogeneous nucleation activity by the dispersed PPE phase. A further increasing PPE content, however, leads to increasing foam densities as well as nonuniform foam morphologies. The changes in the foaming behavior can be correlated with the melt rheological properties and the corresponding blend morphology. Shear‐rheological investigations revealed an onset of percolation of the dispersed PPE phase between 20 and 40 wt%, and a transition towards cocontinuity at 60 wt%. The materials response under uniaxial elongational flow, as assessed by Rheotens measurements, revealed an increase in elongational viscosity scaling with the PPE content, similar to the shear data. However, the strain hardening behavior was reduced by increasing PPE contents and, at 20 wt%, the drawability revealed a significant drop‐both phenomena limiting the foamability of polymers. In summary, the present study discusses fundamental aspects of foaming immiscible PPE/SAN blends. POLYM. ENG. SCI., 48:2111–2125, 2008. © 2008 Society of Plastics Engineers  相似文献   

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