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1.
Poly(4‐vinylpyridine) (P4VP) nanocomposites have been prepared by using an in situ polymerization method in the presence of organically modified montmorillonite (MMT) clays with a quarternary salt of cocoamine containing a vinyl group, as well as trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. This resultant exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance when compared to the other nanocomposites, even with 2 % clay loading. Copyright © 2005 Society of Chemical Industry  相似文献   

2.
Polystyrene (PS) nanocomposites were prepared by the free‐radical polymerization of styrene in the presence of organically modified montmorillonite (MMT) clays. MMT clay was modified with a low‐molecular‐weight and quarternized block copolymer of styrene and 4‐vinylpyridine [poly(styrene‐b‐4‐vinylpyridine) (SVP)] with 36.4 wt % PS and 63.6 wt % poly(4‐vinylpyridine) (P4VP). Special attention was paid to the modification, which was carried out in different compositions of a solvent mixture of tetrahydrofuran (THF) and water. The swelling behavior of the MMT clay was studied by an X‐ray diffraction technique. The diffraction peak shifted to lower 2θ angles for all of the modified clays, which indicated the intercalation of the quarternized SVP copolymer into the MMT layers in different degrees. Higher interlayer distances, which showed a high degree of block copolymer insertion, were obtained for solvent compositions with THF in water. The resultant nanocomposites were characterized by X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, and dynamic mechanical analysis. The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in 50 or 66 wt % THF, whereas the other modifications all resulted in intercalated structures. The resulting exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance compared to the others, even with 2% clay loading. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

3.
Polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) was synthesized by two steps of reversible addition‐fragmentation transfer (RAFT) polymerization of styrene (St) and 4‐vinylpyridine (4VP) successively. After P4VP block was quaternized with CH3I, PS‐b‐quaternized P4VP/montmorillonite (PS‐b‐QP4VP/MMT) nanocomposites were prepared by cationic exchange reactions of quaternary ammonium ion in the PS‐b‐QP4VP with ions in MMT. The results obtained from X‐ray diffraction (XRD) and transmission electron microscopy (TEM) images demonstrate that the block copolymer/MMT nanocomposites are of intercalated and exfoliated structures, and also a small amount of silicates' layers remained in the original structure; differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results show that the nanocomposites displayed higher glass transition temperature (Tg) and higher thermal stability than that of the corresponding copolymers. The blending of PS‐b‐QP4VP/MMT with commercial PS makes MMT to be further separated, and the MMT was homogeneously dispersed in the polymer matrix. The enhancement of thermal stability of PS/PS‐b‐QP4VP/MMT is about 20°C in comparison with commercial PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1950–1958, 2006  相似文献   

4.
Copolymers of 4‐vinylpyridine and styrene [P(4VP–St)s] with varied molar ratios were synthesized by means of radical mass polymerization with 2,2′‐azobisisobutyronitrile as an initiator. The insoluble (linear) pyridinium‐type polymers in the octyl‐pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP–St) with 1‐bromooctane. A series of membranes were prepared for use in electrochemistry. These membranes, prepared with quaternized poly(styrene‐co‐4‐vinylpyridine), were characterized by IRspectroscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetory, tensile strength measurements, scanning electron microscopy, and an electrochemistry workstation. Our emphasis was to select a membrane with appropriate properties for use in the electrochemistry field. A promising membrane was selected to use in the field of electrochemistry by these characterizations. This study could be the preparation for a study on the electrochemical properties of pyridinium‐type polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2146–2153, 2005  相似文献   

5.
Polystyrene‐clay nanocomposite (PsCN) materials were synthesized and their properties of crystallinity, thermal behavior, and dielectric characteristics were investigated. A polymerizable cationic surfactant, [2‐(dimethylamino)ethyl]triphenylphonium bromide, was used for the intercalation of montmorillonite (MMT). The organophilic MMT was prepared by Na+‐exchanged MMT and ammonium cations of a cationic surfactant in an aqueous medium. Organophilic styrene monomers were intercalated into the interlayer regions of organophilic clay hosts followed by a free‐radical polymerization. Exfoliation to 2 wt % MMT in the polystyrene (PS) matrix was achieved as revealed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were also studied. The dielectric properties of PsCNs in the form of film with clay loading from 1.0 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 25–70°C. A decreased dielectric constant and low dielectric loss were observed for PsCN materials. The dielectric response at low frequency that originated from dipole orientation was suppressed due to the intercalation of clay materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1368–1373, 2004  相似文献   

6.
Poly (4‐vinylpyridine) (P4VP) brushes had been prepared by the surface‐initiated nitroxide‐mediated radical polymerization of 4‐VP on the surface of 3‐methacryloxyproyltrimethoxysilane (3‐MPS)‐modified magnetite nanoparticles with an average diameter of 30 nm. The grafting polymerization was accomplished by nitroxide‐mediated polymerization of 4‐VP, using 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyl‐oxy (HTEMPO·) free radical as capping agent and benzoyl peroxide (BPO) as initiator. X‐ray photoelectron spectra (XPS) measurement demonstrated that the alkoxysilane initiator layer had formed on the magnetite surface. Gel permeation chromatograph analysis and XPS measurement suggested that the amount of grafted P4VP increases with increasing grafting time. The amount of P4VP grafted on the surface could be determined to be 0.09 chains/nm2 by thermogravimetric analysis. The P4VP‐grafted magnetite particles exhibited the characteristics of multidomain system, distinct from the single domain attributes of the pure magnetite particles. Atomic force‐microscopy analysis revealed the diameter of the grafted P4VP magnetic latex particles is in the range of 120 nm to 150 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

7.
To study the effect of organophilic clay concentration on nonisothermal crystallization, poly(L ‐lactic acid) (PLLA)/montmorillonite (MMT) nanocomposites were prepared by mixing various amounts of commercial MMT (Cloisite® 30B) and PLLA. The effect of MMT content on melting behavior and crystal structure of nonisothermal crystallized PLLA/MMT nanocomposites was investigated by differential scanning calorimetry (DSC), small‐angle X‐ray scattering, and wide‐angle X‐ray diffraction (XRD) analyses. The study was focused on the effect of the filler concentration on thermal and structural properties of the nonisothermally crystallized nanocomposite PLLA/MMT. The results obtained have shown that at filler loadings higher than 3 wt %, intercalation of the clay is observed. At lower clay concentrations (1–3 wt %), exfoliation predominates. DSC and XRD analysis data show that the crystallinity of PLLA/MMT composites increases drastically at high clay loadings (5–9 wt %). In these nanocomposites, PLLA crystallizes nonisothermally in an orthorhombic crystal structure, assigned to the α form of PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

8.
Unsaturated polyester (UPE) resin including styrene monomer was mixed with organophilic montmorillonite (MMT) clay and its crosslinking polymerization reaction was done in the presence of free‐radical initiator. MMT clay was modified with cetyl trimethly ammonium bromide and trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric and dynamic mechanical analyses (TGA and DMA). The exfoliated nanocomposite structure was obtained when the MMT clay was modified in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. The exfoliated UPE nanocomposite exhibited better thermal and dynamic mechanical properties when compared with pure UPE and other composites, even with 3 wt% clay loading. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers  相似文献   

9.
The copolymers of 4‐vinylpyridine (4VP), styrene (St) and divinylbenzene (DVB) with varied compositions, P(4VP‐St‐DVB), were synthesized by suspension polymerization using 2,2′‐azobisisobutyronitrile (AIBN) as an initiator. The insoluble (crosslinked) pyridinium‐type polymers in benzyl–pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP‐St‐DVB) with benzyl bromide (BzBr), respectively. By using different halohydrocarbon RX in the quaternization of P(4VP‐St‐DVB), the insoluble pyridinium‐type polymers with various pyridinium group structures were obtained. The structures of P(4VP‐St‐DVB) and its quaternized product Q‐P(4VP‐St‐DVB) were identified by FTIR. The 4VP content in each copolymer P(4VP‐St‐DVB) was measured by nonaqueous titration; and the pyridinium group content (Cq) in each Q‐P(4VP‐St‐DVB) sample was determined by means of the back titration manner in argentometry and/or the elemental analysis method, respectively. In addition, the particle structure and the surface morphology of the thus‐prepared polymer were observed using SEM. According to a series of experimental results, the preparation and characterization of insoluble pyridinium‐type polymers are analyzed and discussed. This work can prepare the ground for a study on the antibacterial activity of insoluble pyridinium‐type polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 668–675, 2000  相似文献   

10.
Block copolymers can form various ordered structures by self‐assembly, and their composites with inorganic materials may give surprising properties. This review summarizes recent developments in the preparation, mechanism and application of various types of self‐assembly of polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP). The focus of the review is on how to control the self‐assembly of the dynamic and ordered structure of PS‐b‐P2VP based materials by applying effective factors such as thermal annealing, solvent annealing, block composition and blending. Moreover, the combination of the self‐assembly of PS‐b‐P2VP and various nanoparticles, with potentials in drug delivery, sensors and catalysis, is highlighted. © 2018 Society of Chemical Industry  相似文献   

11.
As a biodegradable functional polymer, poly[(sodium acrylate)‐co‐(4‐vinylpyridine)] [P(SA‐co‐4VP)] containing a small amounts of 4‐vinylpyridine groups were prepared and their biodegradability, dispersity, and complex performance were analyzed. The polymers can be useful as detergent builders and dispersants. It was found that the biodegradation of P(SA‐co‐4VP) was more conspicuous when content of the 4‐vinylpyridine in the copolymer was larger. This indicates that the 4‐vinylpyridine, which acts as biodegradable segments, should be incorporated into the polymer main chain in such a manner that they are digested by activated sludge. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1953–1957, 1999  相似文献   

12.
Polymeric nanocomposites were synthesized from functionalized soybean‐oil‐based polymer matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Acrylated epoxidized soybean oil combined with styrene was used as the monomer. Organophilic MMT (OrgMMT) was obtained using a quaternized derivative of methyl oleate, which was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized using X‐ray diffraction and atomic force microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated using thermogravimetric analysis and dynamic mechanical analysis. It was found that the desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt%, whereas a partially exfoliated or intercalated nanocomposite was obtained for 3 wt% loading. All the nanocomposites were found to have improved thermal and mechanical properties as compared with virgin acrylated epoxidized soybean‐oil‐based polymer matrix. The nanocomposite containing 2 wt% OrgMMT clay was found to have the highest thermal stability and best dynamic mechanical performance. Copyright © 2010 Society of Chemical Industry  相似文献   

13.
Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (Mw/Mn < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003  相似文献   

14.
The conductivities of blends of low‐density polyethylene and poly(4‐vinyl pyridine) (P4VP) were studied. The blends were synthesized by in situ sorption and thermal polymerization of 4‐vinylpyridine in low‐density polyethylene. They showed, after iodine doping, conductivities of 1.7 to 5.0 × 10?7 S cm?1 at 298 K, depending on the P4VP mass increment into the matrix. Their conductivities were one order of magnitude higher for measurements at 338 K. The optimum ratio of iodine to pyridine (n) which gave the highest conductivity was 0.21. The thermal stability of doped blends was acceptable for their uses as electrochemical devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 939–944, 2003  相似文献   

15.
Thermosensitive 4VP‐NIPAAm‐4G copolymer beads containing pyridyl groups were first prepared by suspension copolymerization of 4‐vinylpyridine (4VP), N‐isopropylacrylamide(NIPAAm), and tetraethylene glycol dimethacrylate (4G; crosslinking reagent) in a saturated Na2SO4 aqueous solution in the presence of surfactant and MgCO3 as dispersants. Then the copolymer beads containing pyridinium groups were obtained by the quaternization of the copolymer beads with various alkyl iodides (CH3I, C4H9I, C8H17I) in N,N‐dimethylformamide. The 4VP‐NIPAAm‐4G (15 : 97 : 3) copolymer bead and the 4VP‐NIPAAm‐4G copolymer beads quaternized with butyl iodide exhibited high thermosensitivity in water, although the 4VP‐NIPAAm‐4G copolymer beads quaternized with methyl iodide or octyl iodide hardly exhibited thermosensitivity. All the quaternized copolymer beads exhibited antibacterial activity against Escherichia coli (E. coli), although the 4VP‐NIPAAm‐4G copolymer bead did not. In particular, the copolymer bead quaternized with butyl iodide exhibited the highest antibacterial activity against E. coli at 30°C. It was also found that the antibacterial activity of the quaternized 4VP‐NIPAAm‐4G copolymer beads was greatly affected by not only chain length of alkyl groups in alkyl iodides, with which the 4VP‐NIPAAm‐4G copolymer beads were quaternized, but also by temperature of the solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

16.
Compatibilization of blends of linear low‐density polyethylene (LLDPE)–poly(methyl methacrylate) (PMMA) and LLDPE–copolymer of methyl methacrylate (MMA) and 4‐vinylpyridine (poly(MMA‐co‐4VP) with poly(ethylene‐co‐methacrylic acid) (EMAA) have been studied. Mechanical properties of the LLDPE–PMMA blends increase upon addition of EMAA. In order to further improve interfacial adhesion of LLDPE and PMMA, 4‐vinyl pyridine units are introduced into PMMA chains, or poly(MMA‐co‐4VP) is used as the polar polymer. In LLDPE–poly(MMA‐co‐4VP)–EMAA blends, interaction of MAA in EMAA with 4VP of poly(MMA‐co‐4VP) causes a band shift in the infrared (IR) spectra. Chemical shifts of N1s binding energy in X‐ray photoelectronic spectroscopy (XPS) experiments indicate a transfer of proton from MAA to 4VP. Scanning electron microscopy (SEM) pictures show that the morphology of the blends were improved upon addition of EMAA. Nonradiative energy transfer (NRET) fluorescence results attest that there exists interdiffusion of chromophore‐labeled LLDPE chains and chromophore‐labeled poly(MMA‐co‐4VP) chains in the interface. Based on experimental results, the mechanism of compatibilization is studied in detail. Compatibilization is realized through the interaction between MAA in EMAA with 4VP in poly(MMA‐co‐4VP). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 967–973, 1999  相似文献   

17.
Newly proposed polymer electrolyte membranes (PEMs) composed of an electrospun poly(vinylidene fluoride) (PVDF) fibrous mat embedded in a poly(4‐vinylpyridine) (P4VP) matrix were successfully fabricated in order to improve the mechanical and dimensional stabilities and ionic conductivity of membranes in lithium rechargeable batteries. Fourier transform infrared spectroscopic analysis showed that as a result of the use of a high voltage during electrospinning the crystalline structure of PVDF changed partially from α‐phase to β‐phase. Energy‐dispersive X‐ray spectroscopy confirmed the existence of crosslinked P4VP in the PVDF fibrous mat. The electrolyte uptakes of PVDF and PVDF/P4VP composite mats were higher than that of PVDF cast film. The tensile properties of PVDF/P4VP composite mat were considerably improved compared to those of the pristine PVDF fibrous mat under both dry and wet (soaked with electrolyte) conditions. In addition, the mechanical and dimensional stabilities of the PVDF/P4VP composite PEM were further enhanced due to crosslinking between the P4VP chains. Furthermore, the PVDF/P4VP composite PEM exhibited an ionic conductivity that was an order of magnitude higher than that of traditional PVDF film. © 2012 Society of Chemical Industry  相似文献   

18.
The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na+ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002  相似文献   

19.
Summary: Hydrogenated acrylonitrile butadiene rubber (HNBR) was melt compounded with montmorillonite (MMT) and organophilic modified MMTs prior to sulfur curing. In contrast to the micro‐composite formation resulting from the compounding of the HNBR and pristine MMT, the modified MMTs (i.e., octadecylamine: MMT‐ODA, octadecyltrimethylamine: MMT‐ODTMA, methyltallow‐bis(2‐hydroxyethyl) quaternary ammonium: MMT‐MTH intercalants) produced nanocomposites. It was found that the organoclay with primary amine intercalant (cf. MMT‐ODA) gave confined structures along with the exfoliated/intercalated structures. This was traced to its reactivity with the curatives. By contrast, the organoclays containing less reactive quaternary ammonium compounds (cf. MMT‐ODTMA, MMT‐MTH) were exfoliated and intercalated based on X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results. The hydroxyl functional groups of the MMT‐MTH supported the clay dispersion. The better adhesion between MMT‐MTH and HNBR was explained by hydrogen bonding between the hydroxyl groups of the intercalant and the acrylonitrile group of the HNBR matrix. This HNBR/MMT‐MTH nanocomposite showed the best mechanical properties as verified by tensile mechanical tests and dynamic mechanical thermal analysis (DMTA). The high tensile strength along with the high elongation at break for the rubber nanocomposites were attributed to the ability of the ‘clay network’ to dissipate the input energy upon uniaxial loading.

Scheme of failure development in rubber/organoclay mixes with poor (a) and good (b) dispersion of the clay layers.  相似文献   


20.
Poly(styrene‐block‐4‐vinylpyridine) (PS4VP)–CdS nanocomposites containing different concentrations of CdS were synthesized by an in situ method. Scanning electron microscopy and transmission electron microscopy results indicate that the morphologies of PS4VP–Cd(II) and PS4VP–CdS were controlled by the Cd(II) concentration and the solvent, respectively. The effects of the CdS concentration on the crystal style of CdS in PS4VP–CdS and the photoluminescence (PL) properties of the PS4VP–CdS were also examined. By a comparison of the PL spectra of PS4VP–CdS in solutions, films, and powders, the PL mechanism of PS4VP–CdS was also delivered. The PS4VP–CdS nanocomposite shows potential for application in water‐soluble fluorescence probes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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