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1.
The crystallization behavior of semicrystalline PEO homopolymer/triblock PS‐PEO‐PS copolymer blend system, which exhibited “Dry‐Brush” in the melt. A symmetric polystyrene–poly(ethylene oxide)–polystyrene triblock copolymer was blended with PEO homopolymer (h‐PEO) having the same molecular weight as that of the PEO block in the copolymer. Considering the composition of the blend (Wps ≥ 0.8), PEO spheres were formed in the blend. Because of the dry‐brush phase behavior of this blend, h‐PEO added was localized in the PEO microdomains, which increases the domain size without changing the microdomain morphology. The crystallization of PEO block was confined within the microdomains and the crystallization temperature was about 60°C lower than normal. Self‐seeding tests were performed to clarify the nucleation mechanism of the blend. Because the droplets size varies greatly, multicrystallization peaks were witnessed in the self‐seeding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

2.
An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry  相似文献   

3.
Homogeneous solutions of syndiotactic polystyrene (sPS) in diglycidylether of bisphenol A (DGEBA), containing 2.5, 5 and 7.5 wt % of thermoplastic with or without 0.5 and 1 wt % of poly(styrene‐b‐ethylene oxide) (PS‐b‐PEO) block copolymer, were polymerized using a stoichiometric amount of an aromatic amine hardener, 4,4′‐methylene bis (3‐chloro‐2,6‐diethylaniline) (MCDEA). The dynamic‐mechanical properties and morphological changes of sPS‐(DGEBA/MCDEA) compatibilized with different amount of PS‐b‐PEO have been investigated in this paper. The addition of the block copolymer produced significant changes in the morphologies generated. The size of the dispersed spherical sPS spherulites does not change significantly, but less spherulites of sPS appeared upon network formation in the systems with compatibilizer, what means that addition of compatibilizer in this system delayed crystallization of sPS in sPS‐(DGEBA/MCDEA) systems and change phase separation mechanism from crystallization‐induced phase separation (CIPS) and reaction‐induced phase separation (RIPS) almost only to RIPS. Moreover, PS‐b‐PEO with higher molecular weight of PS block seems to be a more effective compatibilizer than one with lower molecular weight of PS block. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 479–488, 2006  相似文献   

4.
A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by 1H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (Tg) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006  相似文献   

5.
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   

6.
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   

7.
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   

8.
The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, Tg, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers  相似文献   

9.
A crystalline block copolymer of poly(ethylene‐block‐ethylene oxide) (PE‐b‐PEO) was successfully grafted onto a carbon black surface by direct condensation of its terminal hydroxyl groups with carboxyl groups on the surface using N,N′‐dicyclohexylcarbodiimide as a condensing agent. The electric resistance of the composite from PE‐b‐PEO (PEO content is above 50 wt %)‐grafted carbon black drastically increased to 104–106 times of the initial resistance in a vapor of dichloromethane, chloroform, tetrahydrofuran, and carbon tetrachloride, which are good solvents for PE‐b‐PEO, and returned immediately to the initial resistance when the composite was transferred in dry air. However, the change of the electric resistance of these composites was less than one‐tenth in a poor solvent vapor at the same condition. The response of the electric resistance was reproducible and stable even after exposure to a good solvent vapor and dry air with 30 cycles or exposure to the vapor over 24 h. The effect of PEO content on the vapor response was also investigated. The composite from PE‐b‐PEO‐grafted carbon black responded to the low vapor concentration with a linear relationship between the electric resistance and the concentration of the vapor in dry air. This indicates that the composite can be applied as a novel gas sensor. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2437–2447, 2000  相似文献   

10.
Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free‐radical copolymerization of methacryloyl‐terminated PS and α‐vinylbenzyl‐ω‐hydroxy or α‐vinylbenzyl‐ω‐perfluoroalkyl (Rf) PEO macromonomers with the addition of Lewis acid (SnCl4). It was found from their dilute‐solution properties that PS/PEO end‐capped with Rf (PBRf), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N‐dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBRf‐type brush by chemical modification, using corresponding acid chloride. The substitution of Rf groups was ~70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006  相似文献   

11.
Polystyrene (PS)‐incorporated polyhedral oligomeric silsesquioxanes (POSS) organic–inorganic hybrid graft copolymer could be achieved by click coupling reaction between alkyne groups in POSS and azido groups in PS via “graft onto” strategy. Alkyne‐functionalized POSS was synthesized via thiol‐ene facile click reaction and subsequent amidation reaction with very high yield. Azido‐multifunctionalized PS could be synthesized by chloromethylation and subsequent azido reaction. The chemical structures of PS‐(CH2Cl)m, PS‐(CH2N3)m, and PS‐g‐POSS were determined by Fourier transform infrared and 1H NMR characterization. PS‐g‐POSS presented a better hydrophobic property with contact angle of 113° than that of PS (85°). And PS‐g‐POSS with ≤5% of grafting degree had lower glass transition temperature (Tg) than that of PS and then it increased up to 112°C with grafting degree. An obvious aggregation of POSS phase with 10–80 nm in size was formed in PS‐g‐POSS matrix. In addition, 5 wt % of PS‐g‐POSS was added to general purpose polystyrene (GPPS) to remarkably improve its tensile strength from 45 to 57 MPa. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

12.
Poly(methyl methacrylate) (PMMA) is known to be immiscible with poly(styrene) (PS) in the bulk state. Poly(ethyl methacrylate) (PEMA), poly(propyl methacrylate) (PPMA), and poly(n‐butyl methacrylate) (PBMA) are also known to be immiscible with PMMA (or PS). Therefore, PMAs (PMMA, PEMA, PPMA, and PBMA) are predicted by the mean field theory to be immiscible with poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) in the bulk state. However, the miscibility of PMAs with PS‐b‐PMMA may be different in the two‐dimensional state. Therefore, the mixed monolayer behavior of PMAs and PS‐b‐PMMA was investigated from the measurements of surface pressure‐area per molecule (π‐A) isotherms at three different temperatures (10°C, 25°C, and 40°C). Calculation of compressibility from isotherms provided the inflection data from maximum and minimum peaks. The miscibility and nonideality of the mixed monolayers were examined by calculating the excess area as a function of composition. Mostly, negative deviations from ideality were observed in the mixed monolayers. This is likely because of favorable interaction between PMMA and PMAs in the monolayer state. The positive deviations occurred at 40°C with PBMA at a high surface pressure. Therefore, with confinement in the two‐dimensional state, the miscibility between PMAs and PS‐b‐PMMA was greatly improved in comparison with the bulk state. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

13.
Mono‐ and bifunctional poly(phenylene oxide) (PPO) macroinitiators for atom transfer radical polymerization (ATRP) were prepared by esterification of mono‐ and bishydroxy telechelic PPO with 2‐bromoisobutyryl bromide. The macroinitiators were used for ATRP of styrene to give block copolymers with PPO and polystyrene (PS) segments, namely PPO‐block‐PS and PS‐block‐PPO‐block‐PS. Various ligands were studied in combination with CuBr as ATRP catalysts. Kinetic investigations revealed controlled polymerization processes for certain ligands and temperature ranges. Thermal analysis of the block copolymers by means of DSC revealed only one glass transition temperature as a result of the compatibility of the PS and PPO chain segments and the formation of a single phase; this glass transition temperature can be adjusted over a wide temperature range (ca 100–199 °C), depending on the composition of the block copolymer. Copyright © 2005 Society of Chemical Industry  相似文献   

14.
A thermosensitive amphiphilic triblock copolymer, poly(d,l ‐lactide) (PLA)‐b‐poly(N‐isopropyl acrylamide) (PNIPAAM)‐b‐PLA, was synthesized by the ring‐opening polymerization of d,l ‐lactide; the reaction was initiated from a dihydroxy‐terminated poly(N‐isopropyl acrylamide) homopolymer (HO‐PNIPAAM‐OH) created by radical polymerization. The molecular structure, thermosensitive characteristics, and micellization behavior of the obtained triblock copolymer were characterized with Fourier transform infrared spectroscopy, 1H‐NMR, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The obtained results indicate that the composition of PLA‐b‐PNIPAAM‐b‐PLA was in good agreement with what was preconceived. This copolymer could self‐assemble into spherical core–shell micelles (ca. 75–80 nm) in aqueous solution and exhibited a phase‐transition temperature around 26 °C. Furthermore, the drug‐delivery properties of the PLA‐b‐PNIPAAM‐b‐PLA micelles were investigated. The drug‐release test indicated that the synthesized PLA‐b‐PNIPAAM‐b‐PLA micelles could be used as nanocarriers of the anticancer drug adriamycin (ADR) to effectively control the release of the drug. The drug‐delivery properties of PLA‐b‐PNIPAAM‐b‐PLA showed obvious thermosensitive characteristics, and the release time of ADR could be extended to 50 h. This represents a significant improvement from previous PNIPAAM‐based drug‐delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45304.  相似文献   

15.
In virtue of the potential biomedical application of carbon nanotube (CNT), the CNT was hybridized into a supramolecular hydrogel based on the selective inclusion of α‐cyclodextrin (α‐CD) onto poly(ethylene oxide) (PEO) segments of a triblock copolymer, i.e., PEO‐block‐poly(propylene oxide)‐block‐PEO. Different from the previous report, the content of α‐CD, in contrast to that of ethylene oxide unit, was decreased to decrease the network density in hydrogel and hence improve the diffusion of encapsulated substances. As a result, the modulus of the hydrogels climbed slightly after introducing CNT. Furthermore, as the essential properties for wound dressing, the antimicrobial activity, the skin‐adhesion, and water‐retention of such supramolecular hybrid hydrogels were also verified. On the other hand, the supramolecular hybrid hydrogels inherited the shear‐thinning property and are suitable as an injectable biomaterial. The cell viability assay confirmed the equivalent cytotoxicity of the supramolecular hybrid hydrogels to that of the native hydrogels without CNT. Consequently, such CNT‐hybridized supramolecular hydrogel shows a great potential in the biomedical application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

16.
Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by 1H NMR, 13C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (Tc) and melting endothermic peaks (Tm) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

17.
A series of polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (PS/PDMS/PS) triblock copolymers had been synthesized by atom transfer radical polymerization (ATRP). The products had been characterized by Fourier transform infrared, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, contact angle, and scanning electron microscope. The results indicate that the PS chains have been successfully blocked onto the PDMS back bone, and the PS‐b‐PDMS‐b‐PS triblock copolymers have low‐surface tension, good thermal stability, and microphase separation configuration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

18.
In this contribution, we reported to utilize polystyrene‐block‐polybutadiene‐block‐polystyrene (PS‐b‐PB‐b‐PS), a commercial triblock copolymer to toughen epoxy thermosets. First, a PS‐b‐PB‐b‐PS triblock copolymer was chemically modified with hydroboration‐oxidation reaction, with which the midblock was hydroxylated whereas the endblocks remained unaffected. It was found that the degree of hydroxylation was well controlled. One of the hydroxylated PS‐b‐PB‐b‐PS samples was then used as the macromolecular initiator to synthesize a poly(ε‐caprolactone)‐grafted PS‐b‐PB‐b‐PS via the ring‐opening polymerization. It was found that the PS‐b‐PB‐b‐PS with poly(ε‐caprolactone) grafts can be successfully employed to nanostructure epoxy thermosets; the “core‐shell” microdomains composed of PB and PS were generated in the nanostructured thermosets. The nanostructured thermosets displayed improved fracture toughness. POLYM. ENG. SCI., 59:2387–2396, 2019. © 2019 Society of Plastics Engineers  相似文献   

19.
BACKGROUND: Chemical or physical crosslinking of supramolecular assemblies gives them stability in a wide range of environments. Much attention is paid to multilayer (onion‐like) polymeric micelles because their functionality is higher than classic core‐shell micelles. This work reports on the formation and crosslinking of onion‐like micelles prepared by mixing two different block copolymers containing a crosslinkable poly(dimethylaminoethyl methacrylate) (PDMAEMA) block. RESULTS: Block copolymers of a crosslinkable PDMAEMA block were synthesized by atom transfer radical polymerization of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) from poly(propylene oxide) (PPO) or poly(ethylene oxide) (PEO) macroinitiators. The (PDMAEMA13)‐block‐PPO69block‐(PDMAEMA13) triblock formed wormlike core‐shell micelles, which were converted into ellipsoidal onion‐like micelles on mixing with the PEO45block‐P(DMAEMA8co‐MMA4) diblock. Onion‐like micelles were crosslinked by quaternization of DMAEMA units. CONCLUSION: Formation of onion‐like micelles by mixing two different AB (ABA) and B′C block copolymers and their subsequent crosslinking is a valuable approach towards stabilized supramolecular assemblies of a higher complexity and functionality than the individual constitutive components. Copyright © 2008 Society of Chemical Industry  相似文献   

20.
Blend systems of polystyrene‐block‐poly(ethylene‐co‐(ethylene‐propylene))‐block‐polystyrene (SEEPS) triblock copolymer with three types of hydrocarbon oil of different molecular weight were prepared. The E″ curves as a function of temperature exhibited two peaks; one peak at low temperature (? ?50°C), arising from the glass transition of the poly[ethylene‐co‐(ethylene‐propylene)] (PEEP) phase and a high temperature peak (? 100°C), arising from the glass transition of the polystyrene (PS) phase. The glass transition temperature (Tg) of the PEEP phase shifted to lower temperature with increasing oil content. The shifted Tg depended on the types of oil and was lower for the low molecular weight oil. The Tg of PS phase of the present blend system, were found to be constant and independent of the oil content, when molecular weight of the oil is high. However, for the lower molecular weight oil, the Tg of the PS phase also shifted to lower temperatures. This fact indicates that the oil of high molecular weight is merely dissolved in the PS phase. The E′ at (75°C, at which temperature both of PEEP and PS phases are in glassy state, was found to be independent of oil content. In contrast, at 25°C, at which temperature the PEEP phase is in rubbery state, the E′ decreased sharply with increasing oil content. This result indicates that the hydrocarbon oil was a selective solvent in the PEEP phase. It mainly dissolved in the PEEP phase, although slightly dissolved into the PS phase as well, when molecular weight of oil is low. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

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