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1.
The pervaporation performances of a series of functionalized syndiotactic poly(styrene‐co‐4‐methylstyrene) (SPSM) membranes for various alcohol mixtures were investigated. The syndiotactic polystyrene copolymers, poly(styrene‐co‐4‐methylstyrene) (SPSM), were prepared by styrene with 4‐methylstyrene using a Cp*Ti(OCH3)3/methyl aluminoxane (metallocene/MAO) catalyst. The effect of functionalization on the thermal properties and polymer structure of the SPSM membranes were also investigated. The crystallinity of the functionalized SPSM membrane is lower than that of the unfunctionalized SPSM membranes. The water molecules preferentially permeate through the SPSM membranes. Compared with unfunctionalized SPSM membranes, the functionalized SPSM membrane effectively increases the membrane formation performances and the pervaporation performances. The optimun pervaporation performance (a separation factor of 510 and permeation rate of 220 g/m2h) was obtained by the bromination of SPSM (SPSMBr) membrane with a 90 wt % aqueous ethanol solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2247–2254, 2002  相似文献   

2.
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   

3.
Poly(styrene‐co‐butadiene) rubber (SBR) and polybutadiene rubber (BR)/clay nanocomposites have been prepared. The effects of the incorporation of inorganically and organically modified clays on the vulcanization reactions of SBR and BR were analysed by rheometry and differential scanning calorimetry. A reduction in scorch time (ts1) and optimum time (t95) was observed for both the rubbers when organoclay was added and this was attributed to the amine groups of the organic modifier. However, ts1 and t95 were further increased as the clay content was increased. A reduction in torque value was obtained for the organoclay nanocomposites, indicating a lower number of crosslinks formed. The organoclays favoured the vulcanization process although the vulcanizing effect was reduced with increasing clay content. The tensile strength and elongation of SBR were improved significantly with organoclay. The improvement of the tensile properties of BR with organoclay was less noticeable than inorganic‐modified clay. Nevertheless, these mechanical properties were enhanced with addition of clay. The mechanical properties of the nanocomposites were dependent on filler size and dispersion, and also compatibility between fillers and the rubber matrix. Copyright © 2004 Society of Chemical Industry  相似文献   

4.
Poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using reverse atom transfer radical polymerization (RATRP) in miniemulsion. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant applicable at higher temperatures was used for miniemulsion stabilization. Successful RATRP was carried out by using 4,4′‐dinonyl‐2,2′‐bipyridine (dNbPy) as ligand. Monodispersed droplets and particles with sizes in the range of 200 nm were revealed by dynamic light scattering (DLS). Conversion and molecular weight study was carried out using gravimetry and size exclusion chromatography (SEC) respectively. By adding clay content, a decrease in the conversion and molecular weight and an increase in the PDI value of the nanocomposites are observed. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis (TGA). Increased Tg values by adding clay content was also obtained using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) images of the nanoconposite with 1 wt % of nanoclay loading, display monodispersed spherical particles with sizes in the range of ~ 200 nm. SEM findings are more compiled with dynamic light scattering (DLS) results. Well‐dispersed exfoliated clay layers in the polymer matrix of the nanocomposite with 1 wt % nanoclay loading is confirmed by transmission electron microscopy (TEM) images and X‐ray diffraction (XRD) data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

5.
Clay‐dispersed poly(styrene‐co‐acrylonitrile) nanocomposites (PSAN) were synthesized by a free radical polymerization process. The montmorillonite (MMT) was modified by a cationic surfactant hexadecyltrimethylammonium chloride. The structures of PSAN were determined by wide‐angle X‐ray diffraction and FTIR spectroscopy. The dispersion of silicate layers in the polymer matrix was also revealed by transmission electron microscopy (TEM). It was confirmed that the clay was intercalated and exfoliated in the PSAN matrix. The increased thermal stability of PSAN with the addition of clay was observed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dielectric properties of PSAN were measured in the frequency range 100 Hz to 1 MHz at 35–70°C. It was found that the dielectric constant from the dipole orientation had been suppressed due to the intercalation of clay. The dielectric loss is strongly related to the residual sodium content of clay, which increases as the sodium content increases by the addition of clay. Copyright © 2004 Society of Chemical Industry  相似文献   

6.
Amphiphilic copolymers of poly(styrene‐co‐2‐hydroxyethyl acrylate) (SHEA) and poly(styrene‐coN, N‐dimethylacrylamide) (SAD) of different compositions were prepared by free radical copolymerization and characterized by different techniques. Depending on the nature of the solvent and the densities of interacting species incorporated within the polystyrene matrices, novel materials as blends or interpolymer complexes with properties different from those of their constituents were elaborated when these copolymers are mixed together. The specific interpolymer interactions of hydrogen bonding type and the phase behavior of the elaborated materials were investigated by differential scanning calorimetry (DSC) and Fourier transform infra red spectroscopy (FTIR). The specific interactions of hydrogen bonding type that occurred within the SHEA and within their blends with the SAD were evidenced by FTIR qualitatively by the appearance of a new band at 1626 cm?1 and quantitatively using appropriate spectral curve fitting in the carbonyl and amide regions. The variation of the glass transition temperature with the blend composition behaved differently with the densities of interacting species. The thermal degradation behavior of the materials was studied by thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

7.
Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(styrene‐co‐acrylonitrile) (abbreviated as PSAN) containing 25 wt % of acrylonitrile in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PSAN. The aPMMA/PSAN and sPMMA/PSAN blends were found to be miscible because all the prepared films were transparent and showed composition dependent glass transition temperatures (Tgs). The glass transition temperatures of the two miscible blends were fitted well by the Fox equation, and no broadening of the glass transition regions was observed. The iPMMA/PSAN blends were found to be immiscible, because most of the cast films were translucent and had two glass transition temperatures. Through the use of a simple binary interaction model, the following comments can be drawn. The isotactic MMA segments seemed to interact differently with styrene and with acrylonitrile segments from atactic or syndiotactic MMA segments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2894–2899, 1999  相似文献   

8.
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   

9.
The crosslinking of partially brominated poly(isobutylene‐co‐4‐methylstyrene) elastomer 1 by phenolic resin crosslinkers was investigated. The curing was modeled using small molecule analogs of the elastomer and the phenolic resin. In order to mimic the conditions that prevail within the highly aliphatic rubber, the study was carried out in isooctane using catalysts such as coated ZnO that are compatible with such low polar media. In situ NMR analysis was used to probe the reaction between the molecular analogs. p‐Isopropyl benzyl bromide was used as the elastomer analog and hydroxymethyl phenols were used as the resin analogs. Isotopic labeling allowed for independent yet simultaneous monitoring of the reactivity of the elastomer and resin analogs. The resin analog reacted with the elastomer analog via an electrophilic aromatic substitution, leading to the formation of a dibenzyl type ether and benzyl‐phenyl type ethers as reaction intermediates. At lower temperatures the elastomer analog reacted with itself in a competing “self‐cure” process that may be suppressed by increasing the homogeneity of the reaction mixture or by increasing the temperature of the reaction. The applicability of the mechanism was confirmed by successful model cure experiments involving a low molecular weight sample of elastomer 1 and the phenolic resin analog. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 680–685, 2001  相似文献   

10.
Organic–inorganic hybrid poly(styrene‐co‐butyl acrylate)/organically modified montmorillonite (PSBA/organo‐MMT) latex particles have been prepared by in situ emulsion polymerization. The effects of modifier variety and the level of organo‐MMT have been investigated on the basis of the characteristics and mechanical properties of the resulting hybrid emulsion polymers. Although the more hydrophilic intercalated organic modifiers increased the latex particle size, the hydrophobic ones decreased the particle size. A more heterogeneous copolymer chain intercalation was seen by widespread XRD reflection as the organo‐MMT (organoclay) level increases. The tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to determine the dispersion state of organoclay particles inside the nanocomposite copolymer films. Dynamic mechanical thermal analysis (DMTA) showed that adding the organoclay to the copolymer decreased the maximum loss tangent (tanδ) value and caused the shift to a lower temperature. Interestingly, the incorporation of organoclay decreased the glass storage modulus of the copolymer, while increased the rubbery storage modulus to some extent. In addition, a standard indenter for the nanoscratching of copolymer nanocomposite films was used under low applied loads of 150 and 250 μN. The nanoscratch results showed that incorporation of a 3 wt % hydrophobic organoclay, e.g., Closite15A, in the copolymer matrix enhanced considerably the near‐surface hardness and grooving resistance of the nanocomposite film at room temperature. In fact, copolymer nanocomposite films with higher near‐surface hardness and tanδ curve broadening exhibited more nanoscratch resistance through a specific variety of viscoelastic deformation, which did not create a bigger groove. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

11.
Poly(styrene‐co‐methacrylic acid) containing 29 mol % of methacrylic acid (SMA‐29) and poly(isobutyl methacrylate‐co‐4‐vinylpyridine) containing 20 mol % of 4‐vinylpyridine (IBM4VP‐20) were synthesized, characterized, and used to elaborate binary and ternary nanocomposites of different ratios with a 3% by weight hexadecylammonium‐modified bentonite from Maghnia (Algeria) by casting method from tetrahydrofuran (THF) solutions. The morphology and the thermal behavior of these binary and ternary elaborated nanocomposites were investigated by X‐ray diffraction, scanning electron microscopy, FTIR spectroscopy, differential scanning calorimetry, and thermogravimetry. Polymer nanocomposites and nanoblends of different morphologies were obtained. The effect of the organoclay and its dispersion within the blend matrix on the phase behavior of the miscible SMA29/IBM4VP20 blends is discussed. The obtained results showed that increasing the amount of SMA29 in the IBM4VP20/SMA29 blend leads to near exfoliated nanostructure with significantly improved thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
The imidization of poly(styrene‐co‐maleic anhydride) with amines may improve some of its end‐use properties. The objective of this study was to examine the mechanism and kinetics with aniline (ANL) as an amine of the preparation of poly(styrene‐coN‐phenyl maleimide). The reaction was carried out in a tetrahydrofuran solution at 25–55°C and in an ethylbenzene solution at 85–120°C. The extent of the reaction was determined by conductance titration, a new and simple method. Two consecutive reactions were involved in the imidization: ring opening to produce an acido‐amide group and ring closing to form a corresponding imide group. The imidization rate was greatly influenced by the reaction temperature and the molar ratio of ANL to the anhydride. A model for the imidization kinetics over a wide range of reaction temperatures and concentration ranges was developed and validated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2744–2749, 2006  相似文献   

13.
The imidization of poly(styrene‐co‐maleic anhydride) (SMA) was conducted, and the glass‐transition temperatures (Tg's) of the resulting products were measured with differential scanning calorimetry. The contributions from functional groups of maleic anhydride, N‐phenylmaleamic acid, and N‐phenylmaleimide to Tg were examined. Tg increased in the order of SMA < styrene–N‐phenyl maleimide copolymer < styrene–N‐phenyl maleamic acid copolymer and followed the Fox equation. Tg of the imidized products of SMA could be controlled by the conversions of both ring‐opening and ring‐closing reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2418–2422, 2007  相似文献   

14.
Using direct polymer reaction of poly(styrene‐co‐maleic anhydride) (SMA), a synthesis of copolymer of styrene and N‐aryl succinimide (SMI) has been investigated. SMI copolymers were synthesized from SMA copolymers by a concerted two‐step reaction, which consisted of the condensation reaction (step 1) of SMA with aromatic amine to prepare a precursor, succinamic acid, for imide formation and the cyclodehydration reaction (step 2) of succinamic acid. In this article, the application of Searle's preparation method of N‐aryl or N‐alkyl maleimide to the direct polymer reaction for SMI was attempted. Compared with synthesis of monomeric imides, the imide formation in polymeric condition appeared to be a little more sensitive to the reaction condition. The optimum condition for maximum conversion was examined in terms of time, temperature, and the amount of reactants. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1187–1196, 1999  相似文献   

15.
The miscibility of blends of bisphenol‐A polycarbonate (BAPC) and tetramethyl bisphenol‐A polycarbonate (TMPC) with copolymers of poly(styrene‐co‐4‐hydroxystyrene) (PSHS) was studied in this work. It has been demonstrated that BAPC is miscible with PSHS over a region of approximately 45–75 mol % hydroxyl groups in the copolymer. TMPC has a wider miscible window than BAPC when blended with PSHS. The blend miscibility was considered to be driven by the intermolecular attractive interactions between the hydroxyl groups of the PSHS and the π electrons of the aromatic rings of both polycarbonates (PCs). As the FTIR measurements showed, after blending of BAPC with PSHS, there is no visible shift of the carbonyl band of BAPC at 1774 cm−1, whereas the stretching frequency of the free hydroxyl groups of the copoly‐ mers at 3523 cm−1 disappeared. The large positive values of the segment interaction energy density parameter Bst‐HS calculated from the group contribution approach indicated that the intramolecular repulsive interaction may also have played a role in the promotion of the blend miscibility. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 639–646, 1999  相似文献   

16.
The liquid crystallization of general polymer (GP) with maleic anhydride in the main chain has been realized through molecular recognition and self‐assembly based on intermolecular hydrogen bonds. Poly[styrene‐co‐(N‐4‐carboxylphenyl)maleimide] (SMIBA) was synthesized by imidization and dehydration of Poly(styrene‐co‐maleic anhydride) (SMA) with p‐aminobenzoic acid (ABA) for use as an H‐bonded donor polymer. 4‐Methoxy‐4′‐stilbazole (MSZ) and 4‐nitro‐4′‐stilbazole (SZNO2) were prepared as an H‐bonded acceptor. SMIBA was complexed with MSZ or SZNO2 by slow evaporation from pyridine solution to form a self‐assembly, which exhibits the mesophase, while neither of the individual components is mesogenic. The phase diagrams of a variety of mixtures between of SMIBA and stilbazoles have been established using DSC and POM. They show complete miscibility and high thermal stability of the liquid crystalline phase over the whole composition range. The tuning of liquid crystalline properties was achieved by changing the composition of the mixture and involving it with a mixture of SZNO2 and MSZ. IR measurements strongly support the existence of an H‐bonded complex between the carboxylic acid of SMIBA and the pyridine group of stibazoles. Unlike conventional side‐chain liquid crystalline polymer (SLCP), supramolecular SLCP with a lower molecular weigh polymeric donor has higher thermal stability of the liquid crystalline phase due to the microphase separated in the hydrogen bonding case. Liquid crystallization of GP, such as SMA, induced by hydrogen bonds, offers a new route to prepare functional material with controlled molecular architecture from readily accessible and simpler precursors. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 97–105, 1999  相似文献   

17.
Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

18.
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   

19.
Microlayers of polycarbonate (PC) with poly(methylmethacrylate) (PMMA) or poly(styrene‐co‐acrylonitrile) (SAN) were processed with varying layer thicknesses. Adhesion between PC and PMMA was found to be an order of magnitude higher than between PC and SAN, as determined with the T‐peel method. To probe the effect of the adhesion difference on yielding and deformation of PC/PMMA and PC/SAN microlayers, the macroscopic stress–strain behavior was examined as a function of layer thickness and strain rate, and the results were interpreted in terms of the microdeformation behavior. During yielding, crazes in thick SAN layers opened up into cracks; however, PC layers drew easily because local delamination relieved constraint at the PC/SAN interface. Adhesion of PC/PMMA was too strong for delamination at the interface when PMMA crazes opened up into cracks at low strain rates. Instead, PMMA cracks tore into neighboring PC layers and initiated fracture. At higher strain rates, good adhesion produced yielding of thick PMMA layers, a phenomenon not observed with thick SAN layers. The change in microdeformation mechanism of PMMA with increasing strain rate produced a transition in the yield stress of PC/PMMA microlayers. Microlayers of both PC/SAN and PC/PMMA with thinner layers (individual layers 0.3–0.6 μm thick) exhibited improved ballistic performance compared to microlayers with thicker layers (individual layers 10–20 μm thick), which was due to cooperative yielding of both components. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1545–1557, 2000  相似文献   

20.
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