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1.
C. J. G. Plummer J. L. Hedrick S. Hauert J. G. Hilborn H.-H. Kausch 《Journal of Polymer Science.Polymer Physics》1996,34(13):2177-2192
We have prepared triblock copolymers of poly(phenylene oxide) (PPO) and polysulphone (PSF) of the form PPO–PSF–PPO in order to assess their intrinsic mechanical properties and their potential as interfacial compatibilizers in polystyrene/PSF blends. For sufficiently long polysulphone block lengths, we observed microphase separation both in the triblock copolymers and in their blends with polystyrene. The triblock polymers, nevertheless, showed very similar microdeformation behavior to the PPO homopolymer, suggesting the phase separation to play a minor role. On the other hand, the compatibility of the poly(phenylene oxide) blocks and polystyrene ensured a high degree of interphase adhesion in blends containing both polystyrene and free PSF, even for relatively high homopolymer molecular weights. © 1996 John Wiley & Sons, Inc. 相似文献
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The compositions for which blends of copolycarbonates of tetramethyl bisphenol-A and hexafluoro bisphenol-A (TMPC-HFPC) with styrene-methyl methacrylate copolymers (SMMA) are miscible were determined experimentally. These copolymer compsition boundaries were compared to predictions based on the Flory-Huggins theory combined with the binary interaction model. The theoretical predictions employed interaction energies from the literature for the TMPC/PS, PS/PMMA, and TMPC/PMMA pairs, and values for the TMPC/HFPC, HFPC/PS, and HFPC/PMMA pairs were established or verified using independent experiments. The recommended set of interaction energies predicts that miscibility occurs in two separate regions of copolymer compositions. These predictions agree well with the experimental observations. The theoretical requirements for a single, continuous miscible region versus two disjointed miscible regions when the two limiting homopolymer pairs exhibit miscibility, that is, TMPC-PS and HFPC-PMMA in this example, are described. © 1994 John Wiley & Sons, Inc. 相似文献
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M. A. G. Jansen L. H. Wu J. G. P. Goossens G. DE Wit C. Bailly C. E. Koning 《Journal of polymer science. Part A, Polymer chemistry》2007,45(5):882-899
To increase the Tg in combination with a retained crystallization rate, bis(2‐hydroxyethyl)terephthalate (BHET) was incorporated into poly(butylene terephthalate) (PBT) via solid‐state copolymerization (SSP). The incorporated BHET fraction depends on the miscibility of BHET in the amorphous phase of PBT prior to SSP. DSC measurements showed that BHET is only partially miscible. During SSP, the miscible BHET fraction reacts via transesterification reactions with the mobile amorphous PBT segments. The immiscible BHET fraction reacts by self‐condensation, resulting in the formation of poly(ethylene terephthalate) (PET) homopolymer. 1H‐NMR sequence distribution analysis showed that self‐condensation of BHET proceeded faster than the transesterification with PBT. SAXS measurements showed an increase in the long period with increasing fraction BHET present in the mixtures used for SSP followed by a decrease due to the formation of small PET crystals. DSC confirmed the presence of separate PET crystals. Furthermore, the incorporation of BHET via SSP resulted in PBT‐PET copolymers with an increased Tg compared to PBT. However, these copolymers showed a poorer crystallization behavior. The modified copolymer chain segments are apparently fully miscible with the unmodified PBT chains in the molten state. Consequently, the crystal growth process is retarded resulting in a decreased crystallization rate and crystallinity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 882–899, 2007. 相似文献
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In this contribution, we describe the syntheses, characterization, and properties of ABA, CBA and CBC triblock copolymers with glassy (A), elastomeric (B), and crystalline (C) blocks. These three hard-soft-hard triblock copolymers were prepared via living ring-opening metathesis copolymerization by use of Grubbs third generation catalyst through one-pot sequential monomer addition and subsequent hydrogenation. These hard-soft-hard triblock copolymers based thermoplastic elastomers have been analyzed by proton NMR, differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), IR, and transmission electron microscopy (TEM). The mechanical properties of these triblock copolymers were also measured by monotonic and step cyclic tensile test. Compared with the ABA triblock copolymer, the CBC triblock copolymer containing highly crystalline hard end-blocks shows enhanced tensile strength and the best elastic recovery of 90.8%. The hybrid CBA triblock copolymer displays much improved elongation, which is almost twice as long as the other two TPEs, and excellent elastic recovery of 87.0%. 相似文献
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Ralf Lach Roland Weidisch Konrad Knoll 《Journal of Polymer Science.Polymer Physics》2005,43(4):429-438
The influence of the morphology on the mechanical properties of binary styrene–butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer and a thermoplastic elastomer (TPE) with different molecular architectures was studied with bulk samples prepared from toluene. Both block copolymers contained SB random copolymer middle blocks, that is, the block sequence S–SB–S. The two miscible triblock copolymers were combined to create a TPE with increased tensile strength without a change in their elasticity. The changes in the equilibrium morphology of the miscible triblock copolymer blends as a function of the TPE content (lamellae, bicontinuous morphology, hexagonal cylinders, and worms) resulted in a novel morphology–property correlation: (1) the strain at break and Young's modulus of blends with about 20 wt % TPE were larger than those of the pure thermoplastic triblock copolymer; (2) at the transition from bicontinuous structures to hexagonal structures (~35 wt % TPE), a change in the mechanical properties from thermoplastic to elastomeric was observed; and (3) in the full range of wormlike and hexagonal morphology (60–100 wt % TPE), elastomeric properties were observed, the strength greatly increasing and high‐strength elastomers resulting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 429–438, 2005 相似文献
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C. K. Kim M. Aguilar-vega D. R. Paul 《Journal of Polymer Science.Polymer Physics》1992,30(10):1131-1142
Dynamic mechanical and gas transport properties for homogeneous homopolymer blends and random copolymers of bisphenol-A and tetramethyl bisphenol-A polycarbonates (PC-TMPC) were determined. The gas transport measurements were performed at 35°C for the gases He, H2, O2, Ar, N2, CH4, and CO2. The results show that the copolymers have lower permeability, apparent diffusion, and solubility coefficients than the blends. Permeability coefficients for blends follow a semilogarithmic ideal mixing rule while copolymers exhibit negative deviations from this. Specific volume measurements show that the free volume available for gas transport is slightly larger in copolymers than in blends of the same composition. These apparently contradictory results may relate to the differences in local mode chain motions observed for the copolymer and blend series. The γ relaxation processes in PC and TMPC seem to operate independently in the blends (no intermolecular coupling) while there is clear evidence for intramolecular coupling in the copolymers. © 1992 John Wiley & Sons, Inc. 相似文献
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Shu‐Hui Qin Kun‐Yuan Qiu 《Journal of polymer science. Part A, Polymer chemistry》2001,39(9):1450-1455
The block copolymerization of tert‐butyl methacrylate (tBMA) with a difunctionalized polystyrene (PS) macroinitiator was investigated. The polymerizations were performed under UV light irradiation using PS bearing α‐ and ω‐functionalized end groups containing diethyldithiocarbamyl groups as a macroiniferter. Kinetic studies indicate the molecular weights of triblock copolymers increased linearly with the conversion. Block copolymers with different lengths of PtBMA segments were easily prepared by varying the ratio of tBMA and PS macroiniferter or by controlling the monomer conversion. The formations of block copolymers were characterized by gel permeation chromatographic, 1H NMR, and DSC analyses. PtBMA segments of the triblock copolymer were subsequently hydrolyzed quantitatively to poly(methacrylic acid) segments using concentrated HCl as a catalyst in a refluxing solution of dioxane, and then an amphiphilic ABA triblock copolymer was produced. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1450–1455, 2001 相似文献
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M. Larrañaga P. Arruti E. Serrano K. de la Caba P. M. Remiro C. C. Riccardi I. Mondragon 《Colloid and polymer science》2006,284(12):1419-1430
The influence of addition of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO–PPO–PEO) copolymers on final morphologies of modified epoxy matrices has been investigated as a function of PEO:PPO molar ratio and cure conditions by comparison with the cured epoxy blends only containing poly(ethylene oxide) (PEO) or poly(propylene oxide) (PPO) homopolymers. Atomic force microscopy (AFM) has been used to characterize structural features of blends. Whilst diglycidyl ether of bisphenol-A (DGEBA)/4,4’-diaminodiphenylmethane (DDM)/PPO system macrophase separates, the interactions between PEO and cured epoxy are responsible for miscibility of DGEBA/DDM/PEO system. Depending on PEO:PPO molar ratio, micro- or macrophase separated morphologies have been obtained for block copolymer modified epoxy matrices. Moreover, the influence of both copolymer content and cure temperature on final morphologies has also been investigated by both experimental and theoretical analysis. 相似文献
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Radivoje Vukovi Grozdana Bogdani Vjera Kureevi Milivoj Tomakovi Frank E. Karasz William J. MacKnight 《Journal of Polymer Science.Polymer Physics》1994,32(6):1079-1087
The miscibility of random copolymers of o-chlorostyrene and p-chlorostyrene [P (oClSt-co-pClSt)] with partially phenylsulfonylated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO) copolymers has been studied, using differential scanning calorimetry (DSC) to establish Tg behavior. It already has been established that the isomeric effect of the chlorine substitution on miscibility is large. Thus the para-chloro-substituted styrenic homopolymer is miscible with all SPPOs containing more than ~ 5 mol % phenylsulfonylation, whereas the ortho-chloro-substituted homopolymer is immiscible with the entire range of SPPO copolymer compositions (and also with the respective homopolymers). As a result of this asymmetric behavior of the homopolymers, the width of the window of miscibility in blends now investigated containing copolymers with high pClSt content and SPPO is much greater than in the corresponding blends containing copolymers with large mole fraction of oClSt. These differences are reflected in the corresponding χ parameters calculated from analysis of the data. It was also found that the miscibility is temperature dependent and that the regime in the copolymer-copolymer composition plane shrank as the equilibrium temperature increased, results indicative of LCST behavior. © 1994 John Wiley & Sons, Inc. 相似文献
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在聚 (丙烯腈 苯乙烯 ) [P(S AN) ]中苯乙烯 (S)苯环的对位引入羟基基团获得聚 (丙烯腈 对羟基苯乙烯 ) [P(AN VPh) ],P(AN VPh)与聚碳酸酯 (PC)体系及P(AN VPh)与聚四甲基双酚 A碳酸酯 (TMPC)体系的相容性实验结果表明 ,由于对羟基苯乙烯 (VPh)的引入 ,使体系中同时存在“分子间特殊相互作用”和“分子内排斥性相互作用”两种效应 ,从而使体系的相容性获得改善 .P(AN VPh)共聚物中AN的摩尔百分含量在 12 3%~ 4 9 5 %范围内时 ,P(AN VPh) PC共混物体系为热力学均相体系 ,采用TMPC替代PC与P(AN VPh)共混时 ,共聚物中AN的摩尔百分含量在 0~ 5 8 9mol%范围内TMPC P(AN VPh)共混物体系为热力学相容体系 .通过Flory Huggins平均场理论计算与拟合所获得的相容窗口相图与实验值较为吻合 ,同时获得相互作用参数χTMPC -VPh=- 0 19. 相似文献
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利用DSC、DMA、TEM和XPS对[PSF-PDMS-PHS]n/PSF共混物的相容性及表面组成进行了研究.结果表明,PDMS在共混物表面的富集与PSF均聚物和[PSF-PDMS-PHS]n中硬段的相容性有关;PDMS在相容的共混物体系表面的富集与对应的多嵌段共聚物组成基本相近;不相容共混物体系表面PDMS的富集程度相对较高,当共混物本体中有机硅含量从1%增至5%,表面层PDMS的含量迅速增加,可达到嵌段共聚物中PDMS的含量. 相似文献
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The compatibility of random copolymers of styrene and p-fluorostyrene, P(S-pFS), and styrene and o-fluorostyrene, P(S-oFS), with poly-(2,6-dimethyl-1,4-phenylene oxide), PPO, has been studied by differential scanning calorimetry (DSC). It was found that compatibility depends on copolymer composition as well as on the position of substituted fluorine. P(S-pFS) copolymers of p-fluorostyrene content less than 56 mole % are miscible with PPO in all proportions, using the criteria of a single glass transition and optical clarity. However, P(S-oFS) copolymers with less than 91 mole % of o-fluorostyrene are compatible with PPO. Copolymers P(S-pFS) containing 46–56% of pFS undergo phase separation upon annealing at elevated temperatures indicating that a lower critical solution temperature (LCST) exists. At the same time, P(S-oFS) copolymers with less than 80% of o-fluorostyrene blended with PPO do not show phase separation even by annealing at 325°C for the same time. 相似文献
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Yuri M. Boiko Dmitri V. Lebedev Liubov P. Myasnikova 《Colloid and polymer science》2013,291(6):1519-1523
The isothermal luminescence decay kinetics in near-surface nanolayers of plasma-activated bulk samples of amorphous polystyrene (PS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their miscible blends with weight ratios PS/PPO of 75/25 and 50/50 has been studied at 77 K. The intensities of isothermal luminescence (I) of homopolymer and blend surfaces have been compared. It has been found that the ratio between the luminescence intensities for PS and PPO (I(PS)/I(PPO)) may be as high as 50, while the luminescence intensities for the PS–PPO blends are close to I(PPO). The results obtained indicate that the PPO concentration in the surface layers of the blends is higher than that in the bulk. 相似文献
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Amphiphilic triblock copolymers of poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) (PHB-PEG-PHB) were directly synthesized by the ring-opening copolymerization of β-butyrolactone monomer using PEG as macroinitiator. Their structure, thermal properties and crystallization were investigated by 1H NMR, differential scanning calorimetry (DSC) and X-ray diffraction. It was found that both PHB and PEG blocks were miscible. With the increase in the PHB block length, the triblock copolymers became amorphous because amorphous PHB block remarkably depressed the crystallization of the PEG block. Biodegradable nanoparticles with core-shell structure were prepared in aqueous solution from the amphiphilic triblock copolymers, and characterized by 1H NMR, SEM and fluorescence. The hydrophobic PHB segments formed the central solid-like core, and stabilized by the hydrophilic PEG block. The nanoparticle size was close related to the initial concentrations of the nanoparticle dispersions and the compositions of the triblock copolymers. Moreover, the PHB-PEG-PHB nanoparticles also showed good drug loading properties, which suggested that they were very suitable as delivery vehicles for hydrophobic drugs. 相似文献
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Lisaleigh Kane David A. Norman Scott A. White Mark W. Matsen Michael M. Satkowski Steven D. Smith Richard J. Spontak 《Macromolecular rapid communications》2001,22(5):281-296
While theoretical and experimental efforts have thoroughly addressed microphase‐ordered AB diblock copolymer blends with a parent homopolymer (hA or hB) or a second block copolymer, surprisingly few studies have considered comparable ABA triblock copolymers in the presence of hB or an AB diblock copolymer. In this study, we elucidate the roles of additive molecular weight and constraint by examining three matched series of miscible ABA/hB and ABA/AB blends. Self‐consistent field theory is employed to analyze molecular characteristics, e. g., segmental distributions, microdomain periods and midblock bridging fractions, as functions of blend composition. Predictions are compared to morphological characteristics discerned by transmission electron microscopy and small‐angle X‐ray scattering. The corresponding mechanical properties of these blends are measured by dynamic mechanical analysis. The results of this comprehensive work reveal that addition of hB swells the B‐lamellae of the ABA copolymer and has a generally deleterious effect on both the dynamic elastic modulus and midblock bridging fraction. In contrast, addition of a lamellar or cylindrical AB copolymer to the same ABA copolymer can promote an increase or decrease in lamellar period and bridging fraction, depending on relative block sizes. 相似文献
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含联苯结构聚醚醚酮酮共聚物和共混物的制备及性能研究 总被引:8,自引:0,他引:8
聚醚醚酮(PEEK)是八十年代初投入市场的全芳香结构热塑性耐高温特种工程塑料,它的7’。一143“C,Tm一334C“‘,最大结晶度为48%,典型制品结晶度为20%~30%[”.PEEK可用通常的设备成型,其制件、纤维、涂料及复合材料在电子电器、机械设备、交通运输、宇航、原子能工程、军事等领域有广泛的用途[’j.聚醚醚酮酮(PEEKK)是继PEEK之后,由德国Hoechst公司开发出来的又一种全芳香结构热塑性耐高温特种工程塑料[‘j.为了研究该类聚合物的结构和性能的关系,我们在实验室中合成了PEEKK和含联苯结构聚醚醚酮酮(PE-*… 相似文献
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Jan Genzer 《Macromolecular theory and simulations》2002,11(5):481-493
We use a three‐dimensional self‐consistent field model to study the adsorption of A‐B copolymers from A‐B copolymer/A homopolymer blends on planar substrates comprising two chemically distinct regions C and D. The interplay between the spatial distribution of the surface chemical heterogeneities and the monomer sequence distribution in the copolymer is examined for diblock (A‐B), triblock (A‐B‐A), inverted triblock (B‐A‐B), and alternating (A‐alt‐B) copolymers. Our results demonstrate that when the chemically heterogeneous motifs on the substrate are detected by the copolymer adsorbing segments, the copolymers can transcribe them with high fidelity into three dimensions. The way the surface pattern gets transferred is dictated by the monomer sequence distribution. We show that relative to alternating copolymers, block copolymers are generally better at capturing the chemical pattern shape and transcribing it into the polymer mixture. Moreover, block copolymers with shorter adsorbing blocks are capable of better recognizing the substrate motifs. In order to address the interplay between the monomer sequence distribution in the copolymer and the interaction energies, we systematically vary the repulsion between A and B, and the attraction between B and D. Our calculations reveal that increasing i) the interaction between the copolymer adsorbing segments (B) and the “sticky” points at the substrate (D), and/or ii) the repulsion between the copolymer segments (A and B) increases the total amount of the copolymer adsorbed at the mixture/substrate interface, and decreases (increases) the fidelity of the substrate chemical pattern recognition by compositionally symmetric (asymmetric) copolymers. 相似文献
20.
Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm-1 region due to COCH3 band of PVME and peak position of 698 cm-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. ©1995 John Wiley & Sons, Inc. 相似文献