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1.
Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.  相似文献   

2.
Butadiene‐isoprene copolymer/montmorillonite (BIR/MMT) nanocomposites were synthesized successfully via in situ anionic polymerization. The results of transmission electron microscopy and X‐ray diffractometer showed that the clay layers were exfoliated and high reaction temperature benefited the exfoliation of layers in BIR/MMT. The polymerization still exhibited “living” characteristics with the addition of organophilic montmorillonite (OMMT). However, the contents of 1,2‐polybutadiene and 3,4‐polyisoprene of the copolymer decreased with the addition of OMMT, because of its absorption effect on N,N,N′,N′‐tetramethylethanediamine as revealed by 1H NMR. Moreover, it was observed that the glass‐transition temperature of the BIR/MMT nanocomposites also decreased when compared with the BIR copolymers. The thermal stability of the nanocomposites was improved, because of the barrier property of exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 1167–1172, 2006  相似文献   

3.
Functional copolymer/organo‐silicate [N,N′‐dimethyldodecyl ammonium cation surface modified montmorillonite (MMT)] layered nanocomposites have been synthesized by interlamellar complex‐radical copolymerization of preintercalated maleic anhydride (MA)/ organo‐MMT complex as a ‘nano‐reactor’ with n‐butyl methacrylate (BMA) as an internal plasticization comonomer in the presence of radical initiator. Synthesized copolymers and their nanocomposites were investigated by dynamic mechanic analysis, X‐ray diffraction, SEM, and TEM methods. It was found that nanocomposite dynamic mechanical properties strongly depend on the force of interfacial MA … organo‐MMT complex formation and the amount of flexible n‐butyl ester linkages. An increase in both of these parameters leads to enhanced intercalation and exfoliation in situ processes of copolymer chains and the formation of hybrid nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

4.
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   

5.
BACKGROUND: Molecular brushes are types of macromolecules with densely grafted side chains on a linear backbone. The synthesis of macromolecular brushes has stimulated much interest due to their great potential in applications in various fields. Poly(L ‐lactide)–poly(ethylene glycol) methyl ether methacrylate (PLLA‐PEOMA) comb‐block‐comb molecular brushes with controlled molecular weights and narrow molecular weight distributions were successfully synthesized based on a combination of activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) and ring‐opening polymerization. The synthetic route is a combination of the ‘grafting through’ method for AGET ATRP of the PEOMA comb block and the ‘grafting from’ method for the synthesis of the PLLA comb block. Poly(2‐hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, and PLLA side chains and PEOMA side chains were grown from the backbones and the terminal sites of PHEMA, respectively. RESULTS: The number‐average degrees of polymerization of PLLA chains and poly[poly(ethylene glycol) methyl ether methacrylate] (PPEOMA) comb blocks were determined using 1H NMR spectroscopy, and the apparent molecular weights and molecular weight distributions of the brush molecules were measured using gel permeation chromatography. The crystallization of the components in the comb‐block‐comb copolymers was also investigated. The crystallization of PLLA side chains is influenced by PLLA chain length and the content of PPEOMA in the molecular brushes. The comb‐block‐comb copolymer composed of hydrophobic PLLA and hydrophilic PEOMA can self‐assemble into a micellar structure in aqueous solution. CONCLUSION: A combination of AGET ATRP and ring‐opening polymerization is an efficient method to prepare well‐defined comb‐block‐comb molecular brushes. The physical properties of the molecular brushes are closely related to their structures. Copyright © 2009 Society of Chemical Industry  相似文献   

6.
The effects of soft‐segment molecular weight and organic modification of montmorillonite (MMT) on thermal and mechanical properties of segmented polyurethane (PU) elastomers were investigated. The PU/MMT nanocomposites were prepared by in situ polymerization, and the compositions included soft segments with number average molecular weights of 1000, 2000, and 2900, and organic‐modified MMT (including MMT‐30B and MMT‐I30E). The nanocomposites produced were characterized using wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and mechanical testing. The TEM and XRD results revealed that both MMT‐30B and MMT‐I30E were intercalated, and partially exfoliated by the PU. Mechanical tests showed that the PU1000 series in soft‐segment molecular weight yielded superior tensile properties compared with the PU2000 and PU2900 series. Also, for a given molecular weight of soft segment in PU, the MMT‐30B nanocomposites exhibited greater increases in Young's modulus, tensile strength, and elongation at break than the MMT‐I30E counterpart, and the crystallinity of PU was enhanced by the clays. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

7.
Composites of organomodified (OMMT) and pristine montmorillonite (MMT) intercalated by styrene‐N‐phenyl maleimide (PMI) copolymer were prepared by emulsion intercalative polymerization. X‐ray diffraction (XRD) and transmission electron microscopy results show that the dispersability of clay in the matrix was greatly improved by the incorporation of polar moiety PMI. The dispersability of OMMT in the matrix is better than MMT. XRD patterns of the extracted nanocomposites showed that d001 of the clay are much larger than that of the original OMMT and MMT, which indicates that the interaction of copolymer with the clay layers was greatly improved by incorporation with polar monomer PMI. The thermal property of the composites was greatly improved by the intercalation with clay. The DSC results showed that the glass transition of the composites became inconspicuous, which indicated that the movement of the polymer segment was extremely confined by the clay layer. The consistency factor of the melts of the composites increased monotonically with a decreasing flow index showing stronger shear thinning property of the composites. The rheological activity energy of the composites decreased more than that of the pure copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1010–1015, 2005  相似文献   

8.
Summary: A new technique, ultrasonically initiated in situ emulsion polymerization, was employed to prepare intercalated polystyrene/Na+‐MMT nanocomposites. FTIR, XRD, and TEM results confirm that the hydrophobic PS can easily intercalate into the galleries of hydrophilic montmorillonite via ultrasonically initiated in situ emulsion polymerization, taking advantages of the multi‐effects of ultrasonic irradiation, such as dispersion, pulverization, activation, and initiation. Properly reducing SDS concentration is beneficial to widen the d‐spacing between clay layers. However, the Na+‐MMT amount has little effect on the d‐spacing of nanocomposites. The glass transition temperature of nanocomposites increased as the percentage of clay increased, although the average molecular weight of PS decreased, and the decomposition temperature of the 1obtained nanocomposites moves to higher temperature.

TEM of PS/Na+‐MMT nanocomposite prepared by ultrasonically initiated in situ emulsion polymerization.  相似文献   


9.
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   

10.
Acrylic copolymer/montmorillonite (MMT) nanocomposites for warp sizing were prepared in the presence of Na+‐MMT by the in situ intercalative polymerization of acrylic acid, acrylamide, and methyl acrylate in water solution. The properties of the solution and cast film were tested according to an application in sizing process of the nanocomposite size with various MMT contents. The results indicate that, for an exfoliated structure corresponding to the MMT content increasing to 7 wt %, the performance parameters of solution viscosity, glass‐transition temperature, and tensile strength of the film increased and the moisture sorption, abrasion loss, and elongation at break of the film decreased. When the intercalated structure of MMT was 9 wt %, the gathered MMT layers acted as a common inorganic filler in the copolymer matrix, with limited contribution to the properties of the composite. The adhesion work of the nanocomposite solution was calculated by use of the Young–Dupre relation, which showed maximum values at an MMT content of 3 wt % on the surfaces of both the polyester and cellulose films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

11.
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   

12.
The investigation of clay based polymer nanocomposites has opened the door for the development of novel, ecofriendly advanced nano materials that can be safely recycled. Because of their nanometer size dispersion, these nanocomposites often have superior physical and mechanical properties. In this study, novel nanocomposites of poly(o‐toluidine) (POT) and organically modified montmorillonite (MMT) were synthesized using camphor sulfonic acid (CSA), cetyl pyridinum chloride (CPCl), and N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) to study the role of surfactant modification on the intercalation. The in situ intercalative polymerization of POT within the organically modified MMT layers was analyzed by FTIR, UV–visible, XRD, SEM as well as TEM studies. The average particle size of the nanocomposites was found to be in the range 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

13.
Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl3 as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000  相似文献   

14.
With D,L ‐lactic acid and Nϵ‐carbobenzoyloxy‐L ‐lysine [Lys(Z)] as the starting monomer material and tin dichloride as the catalyst, the drug carrier material poly(lactic acid‐coNϵ‐carbobenzoyloxy‐L ‐lysine) was synthesized via direct melt polycondensation. The copolymer was systematically characterized with intrinsic viscosity testing, Fourier transform infrared spectroscopy, 1H‐NMR, gel permeation chromatography, differential scanning calorimetry, and X‐ray diffraction. The influences of different feed molar ratios were examined. With increasing molar feed content of Lys(Z), the intrinsic viscosity, weight‐average molecular weight, and polydispersity index (weight‐average molecular weight/number‐average molecular weight) gradually decreased. Because of the introduction of Lys(Z) with a big aromatic ring into the copolymer, the glass‐transition temperature gradually increased with increasing feed charge of Lys(Z), and all of the copolymers were amorphous. The copolymers, with weight‐average molecular weights from 10,500 to 6900 Da, were obtained and could reach the molecular weight level of poly(lactic acid) modified by Lys(Z) via the ring‐opening polymerization of the cyclic intermediates, such as lactide and morpholine‐2,5‐dione. However, a few terminal carboxyl groups might have been deprotected during the polymerization reaction under high temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
Effective encapsulation of montmorillonite intermediate particles (I‐MMT) within poly (vinyl acetate‐co‐methyl methacrylate) (PVAMMA) copolymer by in situ suspension polymerization was performed. The I‐MMT encapsulation, layer exfoliation behavior, chemical composition, particle size distribution and thermostability of PVAMMA/I‐MMT nanocomposite microspheres were characterized by electron microscopies, X‐ray diffraction (XRD), laser particle analyzer, and thermogravimetric analysis (TGA). Swelling behaviors of the nanocomposite microspheres in various cationic salt solutions (NaCl and CaCl2) and anionic salt solution (NaCl and Na2SO4) were also investigated. Results showed that the properties of layer dispersion surface and expansion of these nanocomposite microspheres were well achieved. The synthetic yields of the nanocomposites decreased as the I‐MMT loading increased. These nanocomposite microspheres had an average size from 96.8 μm to 138.4 μm with narrow particle size distribution, loose, and porous surface morphology. XRD patterns clearly proved the exfoliation of MMT layers in the copolymer matrix, which was consistent with TEM analysis. These nanocomposite microspheres showed higher negative zeta potential and higher thermal stability than those of the copolymer microspheres, which was due to the layer exfoliations in encapsulated microspheres. These selected microspheres with 10 to 70 μm diameters provided effectively plugging in the micrometer‐sized core channels through deformation and migration process in plugging experiments, which made them be the candidate materials for modifying the porous reservoir to enhance oil recovery in petroleum engineering. POLYM. COMPOS., 35:1104–1116, 2014. © 2013 Society of Plastics Engineers  相似文献   

16.
A random copolymer of N‐isopropyl acrylamide (NIPAAm) and acrylic acid (AAc) with an AAc content of 3.1 ± 0.19 mmol of carboxylic acid groups per gram of the copolymer and with a number‐average molecular weight of 1400 was synthesized by free‐radical polymerization with 2,2′‐azoisobutyronitrile in dimethylformamide. Then, monopeptide, dipeptide, and tripeptide (i.e., alanine) conjugates of this copolymer were prepared with their carboxyl‐end‐protected (with methyl ester hydrochloride) form of alanine, with a water‐soluble carbodiimide. Of the carboxylic acids, 93, 69, and 57% were conjugated (loaded) with alanine at the monopeptide, dipeptide, and tripeptide conjugation steps, respectively. The chemical structures of the copolymer and conjugates were analyzed by Fourier transform infrared and 1H‐NMR, which revealed the conjugate formation. Amino acid conjugation caused significant decreases in the lower critical solution temperatures (LCST) of the copolymer, especially at pH 7.4. The LCST values of the dipeptide and tripeptide conjugates of poly(NIPAAm‐co‐AAc) at both pH 4.0 and 7.4 shifted to significantly higher temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2012–2019, 2003  相似文献   

17.
In this article, 1‐octene and styrene was copolymerized by the supported catalyst (TiCl4/ID/MgCl2). Subsequently, by sulfonation reaction, sulfonated poly(1‐octene‐co‐styrene)s which were amphiphilic copolymers were prepared. The copolymerization behavior between 1‐octene and styrene is moderate ideal behavior. Copolymers prepared by this catalyst contain appreciable amounts of both 1‐octene and styrene. Increase in the feed ratio of styrene/1‐octene leads to increase in styrene content in copolymer and decrease in molecular weight. As the polymerization temperature increases, the styrene content in the copolymers increases, however, the molecular weight decreases. Hydrogen is an efficient regulator to lower the molecular weights of poly(1‐octene‐co‐styrene)s. The sulfonation degree of the sulfonated poly(1‐octene‐co‐styrene)s increased as the styrene content in copolymer increased or the molecular weight decreased. Thirty‐six hour is long enough for sulfonation reaction. The sulfonated poly(1‐octene‐co‐styrene)s can be used as effective and durable modifying agent to improve the wettability of polyethylene film and have potential application in emulsified fuels and for the stabilization of dispersions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

18.
Organophilic montmorillonite (MMT) was prepared by ion exchange between Na+ ions in the clay and twin benzyldimethyloctadecylammonium bromine cations in an aqueous medium. The organophilic MMT particles were easily dispersed and swollen in styrene monomer. Polystyrene–MMT nanocomposites were prepared by the free‐radical polymerization of styrene containing dispersed clay. The intercalation spacing in the nanocomposites and the degree of dispersion of these composites were investigated with X‐ray diffraction and transmission electron microscopy, respectively. The nanocomposites had higher weight‐average molecular weights, lower glass‐transition temperatures, and better thermal stability (the decomposition temperature was improved by ca. 70°C) than the virgin polystyrene. The rheological behavior of the polystyrene–MMT nanocomposites was also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 201–207, 2005  相似文献   

19.
A novel thermo‐ and pH‐responsive thiol‐end‐capped ABC triblock copolymer, namely poly(acrylic acid)‐block ‐poly(N ‐isopropylacrylamide)‐block ‐poly(? ‐caprolactone)–SH (PAA‐b ‐PNIPAAm‐b ‐PCL‐SH), was synthesized using a combination of ring‐opening polymerization and reversible addition–fragmentation chain transfer polymerization techniques. The chemical structures of all samples were characterized by means of Fourier transform infrared and 1H NMR spectroscopies. The molecular weight of each segment was investigated using both 1H NMR spectroscopy and gel permeation chromatography. The self‐assembly behavior of the PAA‐b ‐PNIPAAm‐b ‐PCL‐SH triblock copolymer under thermal and pH stimuli was fully investigated by means of fluorescence and UV–visible spectroscopies as well as dynamic light scattering measurements. The critical micelle concentration for the synthesized triblock copolymer was determined to be 0.0178 g L?1 using the fluorescence probe technique. The average size of PAA‐b ‐PNIPAAm‐b ‐PCL‐SH micelles was determined to be 25 nm using transmission electron microscopy observations, and its lower critical solution temperature was determined to be 41–43 °C using UV–visible spectroscopy. © 2017 Society of Chemical Industry  相似文献   

20.
Double‐modified montmorillonite (MMT) was first prepared by covalent modification of MMT with 3‐aminopropyltriethoxysilane and then intercalation modification by tributyl tetradecyl phosphonium ions. The obtained double‐modified MMT was melt compounded with polypropylene (PP) to obtain nanocomposites. The dispersion of the double‐modified MMT in PP was found to be greatly improved by the addition of PP‐graft‐maleic anhydride (PP‐g‐MA) as a “compatibilizer,” whose anhydride groups can react with the amino groups on the surface of the double‐modified MMT platelets and thus improve the dispersion of MMT in PP. Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, scanning electron microscopy, and tensile test were used to characterize the structure of the double‐modified MMT, morphology, and the thermal and mechanical properties of the nanocomposites. The results show that PP‐g‐MA promotes the formation of exfoliated/intercalated morphology and obviously increases the thermal properties, tensile strength, and Young's modulus of the PP/double‐modified MMT nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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