SPS及其镧离聚物对PS/PBMA共混体系相容性的影响

通过运用溶液成膜共混法制备了系列聚苯乙烯／聚人烯酸丁酯（ＰＳ／ＰＢＭＡ）共混物。借助差示扫描量热法（ＤＳＣ）、傅里叶变换红外光谱（ＦＴＩＲ）、扫描电子显微镜９ＳＥＭ）研究了磺化磺苯乙烯（ＳＰＳ）及其离物对共体系相容性的影响。共混物中ＳＰＳ磺化度越高,ＰＢＭＡ相的下班伦为温度向高温方向移动越明显 。ＳＰＳ镧离聚物（ＳＰＳ１．８－Ｌａ）为增容剂时,ＤＣＳ结果显示共混物２相Ｔｇ靠扰;ＳＥＭ归咎显示２相分     

Miscibility of polystyrene with poly(ethylene oxide) and poly(ethylene glycol)

The intrinsic viscosity of polystyrene–poly(ethylene oxide) (PS–PEO) and PS–poly(ethylene glycol) (PEG) blends have been measured in benzene as a function of blend composition for various molecular weights of PEO and PEG at 303.15 K. The compatibility of polymer pairs in solution were determined on the basis of the interaction parameter term, Δb, and the difference between the experimental and theoretical weight-average intrinsic viscosities of the two polymers, Δ[η]. The theoretical weight-average intrinsic viscosities were calculated by interpolation of the individual intrinsic viscosities of the blend components. The compatibility data based on [η] determined by a single specific viscosity measurement, as a quick method for the determination of the intrinsic viscosity, were compared with that obtained from [η] determined via the Huggins equation. The effect of molecular weights of the blend components and the polymer structure on the extent of compatibility was studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1471–1482, 1998     

Solution and solid‐state NMR investigation of poly(methyl methacrylate)/poly(vinyl pyrrolidone) blends

The development of polymer blends has become very important for the polymer industry because these blends have shown to be a successful and versatile alternative way to obtain a new polymer. In this study, binary blends formed by poly(methyl methacrylate) (PMMA) and poly(vinyl pyrrolidone) were prepared by solution casting and evaluated by solution and solid‐state NMR. Variations in the microstructure of PMMA were analyzed by ¹³C solution NMR. Solid‐state NMR promotes responses on physical interaction, homogeneity, and compatibility to use these blends to understand the behavior of the ternary blends. The NMR results led‐us to acquire information on the polymer blend microstructure and molecular dynamic behavior. From the NMR solution, it was possible to evaluate the microstructure of both polymer blend components; they were atactic. From the solid state, good compatibility between both polymer components was characterized. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 372–377, 2004     

Compatibility studies with blends based on poly(n‐butyl methacrylate) and polyacrylonitrile

In this study, poly(n‐butyl methacrylate) (PBMA) was prepared by a suspension polymerization process, and blending with polyacrylonitrile (PAN) in N,N‐dimethyl acetamide to prepare PAN/PBMA blends in various proportions. Hansen's three dimensional solubility parameters of PAN and PBMA were calculated approximately through the contributions of the structural groups. The compatibility in these blend systems was studied with theoretical calculations as well as experimental measurements. Viscometric methods, Fourier transform infrared spectroscopy, dynamic mechanical analysis, scanning electron microscopy, and thermogravimetric analysis were used for this investigation. All the results showed that a partial compatibility existed in PAN/PBMA blend system, which may be due to the intermolecular interactions between the two polymers. And, the adsorption experiment results showed that the addition of PBMA contributed to the enhancing adsorptive properties of blend fibers, which lays the foundation for further studying PAN/PBMA blend fibers with adsorptive function. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinetics of imidization of poly(amic acid) in miscible and immiscible polymer blends

Blends of commercial poly(amic acid), LARC-PAA polymer were prepared with thermoplastic polyimide P84. The blends were shown to be miscible over a certain composition range. Chemical imidization of LARC-PAA in the blends leads to phase separation. Thermal imidization of LARC PAA in the blends was carried out in the solid state. Miscible compositions of the blend remained miscible after imidization and showed a single glass transition for each blend. Immiscible compositions after imidization remained immiscible and showed two glass transition temperatures in the DSC scans. The kinetics of thermal imidization of PAA to polyimide (PI) in the solid state were studied using FTIR. In the immiscible blend the kinetics remained unaffected while in the miscible state the rate of imidization became faster than that of the pure PAA.     

PAN/PMMA共混制备纳米碳纤维的结构与性能

以N,N-二甲基甲酰胺(DMF)为溶剂,以聚丙烯腈(PAN)为碳前驱体,聚甲基丙烯酸甲酯(PMMA)为热裂解聚合物,制备PAN/PMMA溶液共混体系,经湿法纺丝及碳化工艺制备了纳米碳纤维(CNFs);讨论了影响CNFs形态、尺寸的主要因素,通过傅里叶变换红外光谱、X射线衍射、拉曼光谱和电导率测试等对CNFs进行了表征。结果表明:相对分子质量为8.0×10~4的PAN与PMMA以质量比30/70进行共混纺丝和碳化,可以得到CNFs;增加原丝的拉伸倍数有利于减小CNFs的直径,当拉伸倍数提高到6时,CNFs直径为50～150nm;碳化温度为800℃时,CNFs出现石墨相结构;提高碳化温度有利于CNFs石墨化结构的形成与电导率的提高。     

Studies of polymer-cellulose blends prepared from solution

The conditions under which cellulose-cellulose triacetate (CTA) and cellulose-poly(acrylonitrile) (PAN) blends can be prepared from solution, are described in this paper. These two systems form transparent films when the blend contains less than 50% PAN or 60% CTA. Young's modulus, tensile strength, and elongation at rupture were measured for these blends. These values usually are between those of the corresponding homopolymers, except for the blend containing 10% polymer (PAN or CTA) which has a tensile strength value larger than that of cellulose. This result seems to indicate a certain level of compatibility for this blend. However, x-ray measurements indicate the presence of two crystal structures for these systems, suggesting that compatibility does not exist at the molecular level, in the crystalline fraction of the samples.     

New method of determining miscibility in binary polymer blends through hydrodynamic interaction: The free volume approach

A new method has been developed to determine the probability of miscibility in binary polymer blends through hydrodynamic interaction. This is achieved by the measurement of the free volume content in blends of carefully selected systems—styrene acrylonitrile (SAN)/poly(methyl methacrylate) (PMMA), PMMA/poly(vinyl chloride) (PVC), and PVC/polystyrene (PS)—with positron annihilation lifetime spectroscopy. The free volume content can predict the miscible/immiscible nature of the blends but provides no information on the extent of miscibility for different compositions of the blends. We have generalized a model used to understand the viscometric behavior of polymer/solvent systems to polymer/polymer systems through the free volume approach. This model provides two important parameters: a geometric factor (γ) and a hydrodynamic interaction parameter (α). γ depends on the molecular architecture, whereas α accounts for the excess friction at the interface between the constituents of the blend, and we propose that α can serve as a precursor to miscibility in a system and indicate which composition produces a high probability of miscibility. The efficacy of this proposition has been checked with measured free volume data for the three blend systems. The SAN/PMMA system produces a maximum α value of ?209 at 20% PMMA; PVC/PMMA produces a maximum α value of ?57 at 10% PMMA. Interestingly, for the PS/PVC system, α is close to zero throughout the entire concentration range. Therefore, we infer that α is perhaps an appropriate parameter for determining the composition‐dependent probability of miscibility in binary blend systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microstructure and compatibility of PVDF/PS blends in the presence of PVA

This research refers to a compatibility study of binary and ternary PVDF blends with PS and PVA by means of the determination of the polymer polymer interaction parameter χ₁₂ calculated from melting point depression analysis of the blends. In addition, a PVDF spherulite growth rate study was conducted in the binary and ternary blends with PS and/or PVA. The nucleation factor is determined by applying the Lauritzen–Hoffman theory. The results obtained show PVA to be capable of compatibilizing PVDF/PS systems when present in concentrations of 30 vol%.     

Achievement of quasi-nanostructured polymer blends by solid-state shear pulverization and compatibilization by gradient copolymer addition

Nanoblends, in which dispersed-phase domains exhibit length scales of order 100 nm or less, are made using a continuous, industrially scalable, mechanical process called solid-state shear pulverization (SSSP). An 80/20 wt% polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend processed by SSSP and consolidated by platen pressing, without melt processing, exhibits a quasi-nanostructured morphology with many irregular, minor-phase domain sizes of ∼100 nm or less. After short-residence-time single-screw extrusion, the pulverized blend exhibits spherical dispersed-phase domains with a number-average diameter of 155 nm. Thus, SSSP followed by certain melt-processing operations can yield nanoblends. However, the pulverized blend exhibits significant coarsening of the dispersed-phase domains during long-term, high-temperature static annealing, indicating that SSSP followed by other melt processes may yield microstructured blends. In order to suppress coarsening, a styrene (S)/methyl methacrylate (MMA) gradient copolymer is synthesized by controlled radical polymerization. When 5 wt% S/MMA gradient copolymer is added to the PS/PMMA blend during SSSP, the resulting blend exhibits a nanostructure nearly identical to that of the blend without gradient copolymer, and coarsening is nearly totally suppressed during long-term, high-temperature static annealing. Thus, SSSP with gradient copolymer addition can yield compatibilized nanoblends. Morphologies obtained in the pulverized PS/PMMA nanoblend are compared with those in blends of PS/poly(n-butyl methacrylate) and PS/high-density polyethylene made using identical SSSP conditions, providing for commentary on the ability of SSSP to produce nanostructured blends as a function of blend components.     

Compatibility and biodegradability of blendsof starch cinnamate with various polymers

The compatibility of blends of starch cinnamate (StCn) with polyvinyl chloride (PVC), polystyrene (PS), and styrene acrylonitrile copolymer (SAN) has been examined through viscometry at 30°C. The results of the three systems are compared with the already reported PMMA/StCn system. From the intrinsic viscosity, relative viscosity, reduced viscosity, and density measurements the PVC/StCn and SAN/StCn blends were found to be compatible while PS/StCn blend was found to be incompatible. The compatibility of the blends was also confirmed by SEM analysis. The compatibility of these blends based on heat of mixing and polymer-polymer interaction parameter was also examined. Blends were observed to be compatible on the basis of heat of mixing theory but not on the basis of polymer - polymer interaction parameters. Biodegradation studies of compatible blends containing 30% StCn showed 13%, 15%, 18%, and 23% weight loss in case of PMMA, SAN, and PVC blends after 120 days.     

Preparation method and physical,mechanical, thermal characterization of poly(vinyl alcohol)/poly(acrylic acid) blends

A series of blends of poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) were prepared by solution mixing and casting. Glycerol was used as plasticizer. The blends were characterized for their physicochemical and thermo-mechanical properties. The FTIR results revealed the molecular level interaction between PVA and PAA at all blend ratios. The incorporation of PAA significantly reduced the storage modulus of PVA at a given temperature. PVA gradually lost its crystalline character with the increase of PAA and became fully amorphous when the PAA content in the blend exceeded 50 wt%. The kinetic parameters of the semi-crystalline blends were determined using the Avarami–Erofeev model, which showed excellent fitting with the experimental data from DSC. The loss in crystallinity of PVA also contributed to an increase in swelling of the blend when the PAA content is increased. The morphology study by FE-SEM demonstrated that there is no phase separation among the blend components at all blend ratios.     

Phase behavior, morphology and interfacial structure in thermoset/thermoplastic elastomer blends of poly(propylene glycol)-type epoxy resin and polystyrene–b-polybutadiene

Thermoset/thermoplastic elastomer (TPE) blends of poly(propylene glycol) (PPG)-type epoxy resin (ER) and a diblock copolymer, polystyrene–b-polybutadiene (SB, with 30% styrene content), were prepared using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The miscibility and thermal transition behavior of DDM-cured ER/SB blends were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The existence of three separate glass transitions, which are independent of the blend composition, indicates that SB is immiscible with DDM-cured ER. Neither the PS block nor the PB block exhibits miscibility with the cured ER. There exist three phases in the blends: a PS microphase, an ER-rich phase and a PB microphase. The phase structure and morphology of the ER/SB blends were studied using both scanning and transmission electron microscopy (SEM and TEM); a variety of morphologies were observed, depending on the blend composition. For the blends with 5 and 10 wt% SB, SB domains with irregular shapes and broadly distributed sizes are dispersed in a continuous cured ER matrix. For the blends with 20–60 wt% SB, interpenetrating bicontinuous phase structures are observed. For the blends with 70 wt% and more SB, a dispersion of cured ER particles in the SB matrix is obtained. The TEM observation showed that the two phases in the blends exhibit a good interfacial adhesion. The interfacial layer between the ER and SB phases varies from 100 to 300 nm for the blend with 20 wt% SB content, SB micelles are formed surrounding the SB domains in the ER matrix. Small-angle X-ray scattering (SAXS) experiments reveal that the SB diblock polymer still exhibits a lamellar microphase structure within the SB phase and the long spacing of lamellae nearly does not change in the blends. The SB diblock copolymer is microphase separated in the macroscopically phase separated ER/SB blends.     

Applications of polymer blends: Emphasis on recent advances

In the past decade, polymer blend technology has achieved an important position in the field of polymer science. With increased academic and industrial research interest, the application of polymer blend technology to commercial utility has grown significantly. This review on the applications of polymer blends will cover the major commercial blends in the categories of styrene-based polymer blends, poly(vinyl chloride) blends, polyacrylate blends, polyester and polycarbonate blends, polyolefin blends, elastomer blends, polyelectrolyte complexes, and interpenetrating polymer networks. New developments in polymer blend applications will be discussed in more detail. These systems include linear low-density polyethylene blends with either low- or high-density polyethylene, styrenemaleic anhydride terpolymer/ABS (acrylonitrile-butadiene-styrene) blends, polycarbonate/poly(butylene tetephthalate) blends, new PPO/polystyrene blends, and tetramethyl bisphenol A polycarbonate/impact polystyrene blends. Areas for future research to enhance the potential for polymer blend applications will be presented. The need for improved methods for predicting miscibility in polymer blends is discussed. Weldline strength is a major property deficiency of two-phase systems (even those with mechanical compatibility), and future research effort appears warranted to resolve this deficiency. The use of polymeric compatibilization additives to polymer blends has shown promise as a method to improve mechanical compatibility in phase-separated blends, and will be expected to be the subject of future research programs. Finally, the reuse of polymer scrap is discussed as a future application area for polymer blends. Unique applications recently proposed for polymer blends include immobilization of enzymes, permselective membranes, reverse osmosis membranes, selective ion-exchange systems, and medical applications using polyelectrolyte complexes.     

Mechanical and morphological behavior in polystyrene based compatible polymer blends

Mechanical and morphological behavior of polystyrene (PS) based compatible polymer blend systems were studied using a tensile tester and scanning electron and optical microscopes. Four different binary compatible blend systems were employed and characterized: PS and poly (2,6-dimethyl 1,4-phenylene oxide) (PPO), PS and poly(vinylmethylether)(PVME), PS and poly(α-methyl styrene)(PαMS), and PPO and PαMS. The compositional dependence of the mechanical properties showed a synergistic effect with respect to modulus, but a negative deviation from the rule of mixtures relationship for strain at break. From the scanning electron microscope (SEM) observations, a deformation mode transition from crazing to crazing and shear banding occurs at ˜25 wt% PPO in the PS/PPO blends, as indicated by the patch and river patterns above this composition. In the PS/PVME blends, a similar transition was observed at >10 wt% PVME. The PS/PαMS blends showed brittle fracture regardless of composition. The PPO/PαMS blends showed a brittle fracture for a PαMS content >25 wt%. Optical microscope (OM) observations showed that blending of PS/PPO and PS/PVME resulted in a decrease of craze density and length as the PPO and PVME content was increased. PS/PαMS and PPO/PαMS blends showed few crazes, all of which were localized near the fracture surface. The mechanical and morphological behavior can be explained using models of intermolecular interactions and entanglement density in compatible blends, respectively. Overall the mechanical property and the consequent morphological behavior were similar to the effect of antiplasticization.     

The effect of incorporation of POSS units on polymer blend compatibility

In this work, the compatibility of poly(methyl methacrylate) (PMMA) and polystyrene (PS) polymers with their polyhedral oligomeric silsesquioxane (POSS) copolymers combined by solution blending is investigated, to determine the effect of incorporation of the POSS unit on polymer compatibility. The morphology of these tethered POSS copolymer/polymer blends was studied by electron microscopy, thermal analysis, and density. Although the basic PS/PMMA blend was clearly immiscible, it was also found that the incorporation of POSS into the PS chain led to incompatibility when the POSScoPS copolymer was blended with PS homopolymer. However, conversely, in the case where the POSS moiety was included as part of a copolymer with PMMA, the copolymer was miscible with the PMMA homopolymer. The presence of isobutyl units on the corners of POSS cage is clearly sufficient to encourage miscibility with PMMA. Interestingly, blends of the two different POSS copolymers led to an immiscible structure, despite having the common POSS units, the interactions between the POSS moieties clearly not being sufficient to drive compatibility. The POSS copolymers have also been used as interfacial agents in immiscible PS and PMMA blend, and it has been found that the appearance of the interface bonding is improved, although the phase morphology is only slightly changed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚乙烯醇薄膜的共混改性

从聚合物结构方面分析了聚乙烯醇（PVA）薄膜的水溶性,提出用共混改性方法提高PVA薄膜的溶解性能。研究了聚丙烯酸不同中和度,不同共混组分组成对薄膜水溶性和力学性能的影响,并利用差示扫描量热法（DSC）、傅立叶红外光谱（FTIR）、广角X射线衍射（WXRD）等手段对共混改性机理进行了分析。     

Thermal behavior,morphology, and the determination of the Flory–Huggins interaction parameter of polycarbonate–polystyrene blends

Blends of bisphenol-A polycarbonate (PC) and polystyrene (PS) prepared by screw extrusion and solution casting have been investigated with weight fractions of PC in the blends varying from 0.95 to 0.05. From the measured glass transition temperatures (T_g) and specific heat increments (ΔC_p) at the T_g, the polystyrene appears to dissolve more in the PC phase than does the PC in the PS phase. The blend appears to be near eqilibrium under extrusion conditions so that the polymer–polymer interaction parameter of PC/PS blends was calculated and found to be 0.038±0.004 for extruded blends at 250°C. Scanning electron microscopy supports the conclusion that the compatibility increases more in the region of PS-rich compositions than in the regions of PC-rich compositions of the PC/PS blends.     

Effect of blend composition on the morphology development of electrospun fibres based on PAN/PMMA blends

BACKGROUND: The aim of the work presented was to determine the morphology development and relevant change in fibre diameter of a binary polymer blend system during an electrospinning process. The size of the fibre diameter is one of the important factors determining the general properties of non‐woven mats formed from electrospun fibres. RESULTS: The morphology and diameter of electrospun polyacrylonitrile (PAN)/poly(methyl methacrylate) (PMMA) blends were investigated as a function of blend ratio using scanning electron microscopy. The diameter of the electrospun PAN/PMMA fibres decreased with increasing PMMA content up to 50 wt%, and then increased again with further increase of PMMA. After thermal treatment, the fibres shrank, and an irregularly shaped morphology was observed. CONCLUSION: The electrospinning of incompatible PAN/PMMA blends leads to a microphase‐separation morphology of fibres. A phase inversion occurs at a PMMA content of between 50 and 75 wt%. Due to the phase inversion, the fibre diameter shows a minimum value at the relevant composition. Copyright © 2008 Society of Chemical Industry     

Miscibility and carbon dioxide transport properties of poly(3-hydroxybutyrate) (iPHB) and its blends with different copolymers of styrene and vinyl phenol

This work summarizes the miscibility and transport properties of different polymer blends obtained by mixing a bacterial, isotactic poly(3-hydroxybutyrate) (iPHB) with copolymers of styrene and vinyl phenol (Sty-co-VPh copolymers). Given that iPHB and pure commodity poly(styrene) (PS) form immiscible blends, PS has been modified by copolymerizing it with vinyl phenol (VPh) units, in an attempt to promote blend miscibility. VPh units have appropriate functional groups that interact with iPHB ester moieties. The potential miscibility was investigated by differential scanning calorimetry (DSC) measuring the glass transition temperatures of blends of different compositions. As an additional test, the interaction parameter between the two components, using the iPHB melting point depression caused by the second component, was also measured. Copolymers containing less than 90% styrene showed miscibility with iPHB.Given the remarkable barrier properties of iPHB to gases and vapours, the study has been completed by measuring transport properties of carbon dioxide through different iPHB/Sty-co-VPh copolymer blends, using gravimetric sorptions in a Cahn electrobalance. A clear difference was observed between the behaviour of rubbery blends and those that exhibit a glassy behaviour at the selected experimental temperature (303 K).