Blends of poly(ethylene oxide) and poly(4-vinylphenol-co-2-hydroxyethyl methacrylate): thermal analysis, morphological behaviour and specific interactions

DSC and optical microscopy were used to determine the miscibility and crystallinity of blends of poly(ethylene oxide) (PEO) with poly(4-vinylphenol-co-2-hydroxyethyl methacrylate) (PVPh-HEM). A single glass transition temperature was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherullites is observed, as PVPh-HEM is added. FTIR was used to probe the intermolecular specific interactions of the blends and the miscibility of the blend is mainly attributed to PVPh-HEM/PEO intermolecular interactions via hydrogen bonding.     

Miscibility, thermal characterization and crystallization of poly(l-lactide) and poly(tetramethylene adipate-co-terephthalate) blend membranes

Binary blend membranes of biodegradable poly(l-lactide) (PLLA) with poly(tetramethylene adipate-co-terephthalate) (PTAT) copolymer were prepared by solution casting via air evaporation. The miscibility of PLLA/PTAT blends was studied by dynamic mechanical analysis (DMA) and thermal mechanical analysis (TMA) in a tensile mode. Differential scanning calorimetry (DSC) measurement was carried out. The surface microstructure and tensile properties of the blend membranes were examined using atomic force microscopy (AFM) and tensile tester. It was concluded that PLLA/PTAT blends should be partially miscible for all ranges of compositions. Higher roughness and porosity were observed for the blend containing 50% PTAT, suggesting more phase separation occurred. The DSC analysis showed that the fusion enthalpy and crystallinity (X_c) of the PLLA-rich phase decreased with increasing PTAT content. Solidification process strongly suggested that the crystallization rate was accelerated by blending with 25% PTAT content, which served as the nucleation agent. Furthermore, the crystallization rate coefficient (CRC) depended on the blending miscibility and cooling rate in the non-isothermal crystallization process. Besides, PTAT addition could be proved to enhance the thermal stability and elongation of resulting blend membranes, even superior to those properties of poly(lactic acid-co-glycolic acid) (PLGA).     

Study on the Crystallization Kinetic and Characterization of Poly(lactic acid) and Poly(vinyl alcohol) Blends

In this study, poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) blends, with PLA/PVA mass ratios of 100/0, 90/10, 80/20, 70/30, 60/40, 50/50, and 40/60, were prepared by means of the melt blending method. The result of torque measurements and thermal gravimtric analysis tests showed that the addition of PLA can decrease the melt viscosity of PVA and that the second degradation step of PVA nearly disappeared for the PLA₈₀/PVA₂₀ blend. The absorbance peaks of the carbonyl group and the hydroxyl group in the Fourier transform infrared spectra of PLA/PVA blends had significant shifts to lower wave numbers, indicating that there were interactions between these two groups. Combined with the result of the differential scanning calorimetry curves, this interaction would be favorable for improving miscibility. The X-ray diffraction patterns and the polarized light microscope (PLM) micrographs showed that PVA can serve as a nucleating agent to promote the crystallization of PLA in PLA/PVA blends. Moreover, the PLA₈₀/PVA₂₀ blend gave the highest growth rate of PLA spherulite.     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Rheological and morphological characteristics of multicomponent polysulfone/poly(vinyl alcohol) systems

A series of blends obtained from polysulfone (PSF) or chloromethylated polysulfone (CMPSF) and poly(vinyl alcohol) (PVA) in N‐methyl‐2‐pyrrolidone were investigated by means of attenuated total reflection Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), rheology and atomic force microscopy (AFM). Mechanisms through which specific interactions developed via hydrogen bonding in ternary systems affect the blend properties were established from FTIR spectra. The results confirm the presence of hydrogen bonding in PSF/PVA and CMPSF/PVA blends at 0.5 and 0.75 weight fractions of PVA, respectively. Consequently, the type of interactions and structural peculiarity of polymers in the blends as well as the composition of polymer mixtures modify the rheological functions, evidencing the orientation or mobility of chain segments in the shear field. The results derived from rheological measurements are consistent with those above, evidencing significant changes for blends with a greater amount of PVA (i.e. 50/50 and 25/75 (w/w) PSF/PVA and CMPSF/PVA blends, respectively). These blends represent the optimum compositions and possess specific properties, confirmed by the glass transition temperatures. Additionally, the specific microarchitecture of the blends, determined using AFM, represents excellent scaffolds as porous membranes for biomedical applications. © 2014 Society of Chemical Industry     

Poly(hydroxyether sulfone) and its blends with poly(ethylene oxide): miscibility, phase behavior and hydrogen bonding interactions

Poly(hydroxyether sulfone) (PHES) was synthesized through polycondensation of bisphenol S with epichlorohydrin. It was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy and differential scanning calorimetry (DSC). The miscibility in the blends of PHES with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PHES/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed single, composition-dependent glass transition temperatures (T_gs), indicating that the blends are miscible in amorphous state. At elevated temperatures, the PHES/PEO blends underwent phase separation. The phase behavior was investigated by optical microscope and the cloud point curve was determined. A typical lower critical solution temperature behavior was observed in the moderate temperature range for this blend system. FTIR studies indicate that there are the competitive hydrogen bonding interactions upon adding PEO to the system, which was involved with the intramolecular and intermolecular hydrogen bonding interactions, i.e. -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO between PHES and PEO. In terms of the infrared spectroscopic investigation, it is judged that from weak to strong the strength of the hydrogen bonding interactions is in the following order: -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO.     

Miscibility and interactions in poly(methylthiomethyl methacrylate)/poly(vinyl alcohol) blends

Poly(methylthiomethyl methacrylate) (PMTMA) is miscible with poly(vinyl alcohol) (PVA) over the whole composition range as shown by the existence of a single glass transition temperature in each blend. The interaction between PMTMA and PVA was examined by Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the thioether sulfur atoms of PMTMA, and the involvement of the carbonyl groups of PMTMA in interactions is not significant. The measurements of proton spin-lattice relaxation time reveal that PMTMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. In comparison, we have previously found that PMTMA is miscible with poly(p-vinylphenol) and the two polymers mix intimately on a scale of 1-3 nm.     

Miscibility and hydrolytic degradation in alkaline solution of poly(l-lactide) and poly(methyl methacrylate) blends

Poly(l-lactide) (PLLA) was melt blended with poly(methyl methacrylate) (PMMA) using a two-roll mill. The miscibility and hydrolytic degradation of the blend films were characterized. It was found that PLLA/PMMA blend has high miscibility in the amorphous state because only single T_g was observed in the DSC and DMA measurements. In alkaline solution, the hydrolytic degradation rate of the blends whose PMMA content is higher than 30 wt% was decelerated while the rate of the blends whose PMMA content is lower than 30 wt% was accelerated. That is, the hydrolytic degradation rate of the blends could be widely controlled by PMMA content in the blend. It was also found that only PLLA was hydrolyzed and eluted into alkaline solution, while PMMA remained during alkaline hydrolysis.     

Effect of dehydrochlorination of PVC on miscibility and phase separation of binary and ternary blends of poly(vinyl chloride), poly(ethylene-co-vinyl acetate) and poly(styrene-co-acrylonitrile)

The enhancement of miscibility at the lower critical solution temperature (LCST) of the blends poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN) and poly(vinyl chloride)/poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (PVC/EVA/SAN) was observed at the micron level. Such miscibility is attributed to the dehydrochlorination and formation of hydrogen bonds between blend components. However, macrolevel immiscibility of these blends heated to the LCST was observed. Such microdomain compatibility of these blends gives a synergistic character. Brittle-type failure observed for LCST samples testifies to the synergism in treated blends. ©1997 SCI     

Miscibility and intermolecular specific interactions in blends of poly(hydroxyether of bisphenol A) and poly(4-vinyl pyridine)

The blends of poly(hydroxyether of bisphenol A) (phenoxy) with poly(4-vinyl pyridine) (P4VPy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. The single, composition-dependent glass transition temperature (T_g) was observed for each blend, indicating that the system is completely miscible. The sigmoid T_g-composition relationship is characteristic of the presence of the strong intermolecular specific interactions in the blend system. FTIR studies revealed that there was intermolecular hydrogen bonding in the blends and the intermolecular hydrogen bonding between the pendant hydroxyl groups of phenoxy and nitrogen atoms of pyridine ring is much stronger than that of self-association in phenoxy. To examine the miscibility of the system at the molecular level, the high resolution ¹³C cross-polarization (CP)/magic angle spinning (MAS) together with the high-power dipolar decoupling (DD) NMR technique was employed. Upon adding P4VPy to the system, the chemical shift of the hydroxyl-substituted methylene carbon resonance of phenoxy was observed to shift downfield in the ¹³C CP/MAS spectra. The proton spin-lattice relaxation time T₁(H) and the proton spin-lattice relaxation time in the rotating frame T_1ρ(H) were measured as a function of the blend composition. In light of the proton spin-lattice relaxation parameters, it is concluded that the phenoxy and P4VPy chains are intimately mixed on the scale of 20-30 Å.     

Miscibility of C60-end-capped poly(ethylene oxide) with poly(vinyl chloride)

The miscibility of blends of single [60]fullerene (C₆₀)-end-capped poly(ethylene oxide) (FPEO) or double C₆₀-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy Cl2p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the α-hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be −0.169, −0.142, −0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C₆₀ slightly impairs the interaction between PEO and PVC.     

Polymorphic and miscibility behavior in crystalline/crystalline blends of poly(pentamethylene terephthalate) with poly(heptamethylene terephthalate)

BACKGROUND: The phase behavior of blends of semicrystalline aryl polyesters with long methylene segments (? (CH₂)_n? with n = 5 or 7) in the repeat units has not been much studied. Thus, crystalline/crystalline blends comprising monomorphic poly(pentamethylene terephthalate) (PPT) and polymorphic poly(heptamethylene terephthalate) (PHepT) were prepared and the crystal growth kinetics, polymorphism behavior and miscibility in this blend system were probed using polarized‐light optical microscopy, differential scanning calorimetry and wide‐angle X‐ray diffraction. RESULTS: The PPT/PHepT blends of all compositions were first proven to be miscible in the melt state or quenched amorphous phase, whose interaction strength was determined (χ₁₂ = ? 0.35), showing favorable interactions and phase homogeneity. Although the spherulites of neat PPT and PHepT could exhibit ring bands at different crystallization temperature (T_c) ranges (100–110 and 50–65 °C, respectively), the spherulites of PPT/PHepT (50/50) blend became ringless in the range 50–110 °C. Growth analysis and polymorphic behavior in the crystalline phases of the blends provided extra evidence for the miscibility between these two crystalline polymers. Spherulitic growth rates of PPT in the PPT/PHepT blends were significantly reduced in comparison with those of neat PPT. In addition, miscible blending of a small fraction of monomorphic PPT (20 wt%) with polymorphic PHepT altered the crystal stability and led to the originally polymorphic PHepT exhibiting only the β‐crystal form when melt‐crystallized at all values of T_c. CONCLUSION: The highly intimate mixing in polymer chains of crystalline PPT and PHepT causes significant disruption in ring‐band patterns and reduction in crystallization rates of PPT as well as alteration in the polymorphic behavior of PHepT. Copyright © 2009 Society of Chemical Industry     

Miscibility and hydrogen bonding in blends of poly(vinyl acetate) with phenolic resin

The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state ¹³C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (T_g) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both ¹³C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T_1ρ^H), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.     

Miscibility and phase behavior in thermosetting blends of polybenzoxazine and poly(ethylene oxide)

Thermosetting polymer blends composed of polybenzoxazine (PBA-a) and poly(ethylene oxide) (PEO) were prepared via in situ curing reaction of benzoxazine (BA-a) in the presence of PEO, which started from the initially homogeneous mixtures of BA-a and PEO. Before curing, the BA-a/PEO blends displayed the single and composition-dependant glass transition temperatures (T_g's) in the entire blend composition, and the equilibrium melting point depression was also observed in the blends. It is judged that the BA-a/PEO blends are completely miscible. The miscibility was mainly ascribed to the contribution of entropy to mixing free energy since the molecular weight of BA-a is rather low. However, phase separation occurred after curing reaction at the elevated temperature, which was confirmed by differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM). It was expected that the PBA-a/PEO blends would be miscible since PBA-a possesses a great number of phenolic hydroxyls in the molecular backbone, which are potential to form the intermolecular hydrogen bonding interactions with oxygen atoms of PEO and thus would fulfill the miscibility of the blends. To interpret the experimental results, we investigated the variable temperature Fourier transform infrared spectroscopy (FTIR) of the blends via model compound. The FTIR results indicate that the phenolic hydroxyl groups could not form the efficient intermolecular hydrogen bonding interactions at the elevated temperatures (e.g. the curing temperatures), i.e. the phenolic hydroxyl groups existed mainly in the non-associated form in the system. Therefore, the decrease of the mixing entropy still dominates the phase behavior of thermosetting blends at the elevated temperature.     

Compatibility of poly(vinyl chloride) with epoxidized copolymers of butadiene-styrene

The compatibility of poly(vinyl chloride) (PVC) with epoxidized styrene-butadiene copolymers is examined at different levels of epoxidation. The copolymers modified were a random (SBR) containing 45 wt% styrene and a triblock (SBS) with 30 wt% bound styrene. Blends were examined in the complete composition range and the approximate levels of epoxidation to ensure blend miscibility were determined. Epoxidized SBS (ESBS) was more effective in miscibility compared with ESBR requiring a lesser degree of epoxidation (43 versus 46 mol%). Tensile properties of the ESBS/PVC blends showed the efficiency of ESBS as a polymeric plasticizer even at levels of epoxidation (ca. 35 mol%) where immiscibility sets in.     

Morphology and Dielectric Properties of Polyhydroxybutyrate (PHB)/Poly(methylmethacrylate)(PMMA) Blends with Some Antimicrobial Applications

Poly(3-hydroxy)butyrate (PHB) is a microbial polyester, which provides the advantages of biodegradability and biocompatibility but it is brittle and has low abilities for some chemical modifications. To overcome such problems reactive blending was done with a glassy acrylic polymer, poly(methylmethacrylate) (PMMA) with different compositions. The dielectric response of PHB/PMMA blend with different compositions were investigated as a function of frequency and at different temperatures. The results revealed the existence of single a-relaxation process indicating the miscibility of amorphous fractions of PHB and PMMA. Also the morphological study of such blends doesn't show macro phase separation of PMMA on the surface scan which may be attributed to the compatibility in melt between PHB and PMMA particles in the PHB matrix. The biological activity of such investigated systems against some pathogenic microorganisms was found to increase by increasing the amount of PMMA in the blend     

Miscibility and phase behavior of poly(D,L-lactide)/poly(p-vinylphenol) blends

The miscibility of poly(D ,L -lactide) (PDLLA) and poly(p-vinylphenol) (PVPh) blends has been studied by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). Phase separation was observed in blends over a wide composition range. A PDLLA-rich phase was found to coexist with an almost pure PVPh phase. The quenched blend samples showed two glass transitions (T_gs), except for a blend with a low PVPh content. However, the T_g value of the PDLLA-rich phase showed a gradual increase with increasing PVPh content. No evidence of interassociation (hydrogen bond formation) between PDLLA and PVPh was found by FTIR. The phase behavior of the blends was simulated using an association model. The results suggested that the equilibrium constant of interassociation between PDLLA and PVPh was small. The phase compositions of the two separated phases were calculated using Fox, Gordon-Taylor, and Couchman equations. The amount of PVPh in the PDLLA-rich phase increased with increasing PVPh content in the blend. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 811–816, 1998     

PA6/PVA共混物的相容性与力学性能研究

制备了聚酰胺6/聚乙烯醇(PA6/PVA)共混物,通过DMA、FTIR、DSC和力学性能测试等方法对共混物进行了表征,利用Hoffman-Weeks方程和Flory熔点下降方程求得了PA6的平衡熔点和两种聚合物的相互作用参数,研究了共混物的相容性和力学性能。结果表明:在氢键的作用下,PA6/PVA共混物具有良好的相容性;PA6与PVA相互作用参数为-0.085,进一步证明了PA6/PVA共混物是热力学相容体系;当PVA含量为50%时,PA6/PVA共混物的相容性和力学性能最佳。     

Advance application of Raman spectroscopy for quantitative analysis of noncrystalline components in thin films of poly(ε-caprolactone)/poly(butadiene) blends

A quantitative analysis method for the distribution of noncrystalline poly(butadiene) component in poly(ε-caprolactone)/poly(butadiene) (PCL/PB) binary blends have been analyzed by advance application of Raman spectroscopy, optical microscopy, and differential scanning calorimetry (DSC) techniques. Thin films of different compositions of PCL/PB binary blends were prepared from solution and isothermally crystallized at a certain temperature. After calibration with real data, quantitative analyses by Raman spectroscopy revealed the amorphous PB are trapped inside the PCL crystals. Polarized optical microscopy and real time atomic force microscopy were used to collect data for the crystal morphology and crystal growth rate. For pure PCL crystals, a morphology of truncated lozenge shape was observed, independent of crystallization temperature and regardless of the blends compositions. For the pure PCL and their blends, almost unique crystal growth rate was found. The miscibility behaviors using DSC were drawn through melting point depression method. The Hoffman-Weeks extrapolations of the blends were found to be linear and identical with those of the neat PCL. The interaction parameter for the blends indicating that the PCL and PB blends have no intermolecular interaction, confirming the blends are immiscible. Despite the immiscibility of the blend, the PCL crystals do not bend during the growth process and do not reduce the growth rate as they do for miscible blend systems.     

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).