Study of the miscibility of poly(ethyl methacrylate- co -4-vinylpyridine)/poly(styrene- co -cinnamic acid) blends (original) (raw)
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Journal of Applied Polymer Science, 2012
Miscibility of poly(ethyloxazo1ine) (PEOX) with poly(viny1 acetate) (PVAC), poly(vinyl alcohol) (PVAL) and poly(viny1 acetate-co-vinyl alcohol) (ACAL copolymers) has been investigated over a wide composition range. In some blends, due to the small difference between the glass transition temperatures of the components, the enthalpic relaxation method was used as miscibility criterion. Differential scanning calorimetry (DSC) results indicate that PEOX is immiscible with PVAC and PVAL but is miscible with ACAL copolymers in a certain range of compositions. The ACALPEOX phase diagram for different copolymer compositions has been determined. The variation of the glass transition temperature with blend composition for miscible systems was found to follow the Kwei equation. Infrared spectroscopy studies of blends reveal the existence of specific interactions via hydrogen bonding between hydroxyl groups in vinyl alcohol units and the carbonyl group in the tertiary amide, which appear to be decisive for miscibility.
Express Polymer Letters, 2007
The miscibility behavior of poly(styrene-co-cinnamic acid) (PSCA) with poly(methyl methacrylate) (PMMA), poly[(methyl methacrylate)-co-(4-vinylpyridine)] (PMMA4VP) and poly[(methyl methacrylate)-co-(2-vinylpyridine)] (PMMA2VP) was studied. DSC measurements indicated that PSCA23 containing 23 mol% of carboxylic acid units was miscible with PMMA, PMMA2VP and PMMA4VP as established from the observation of a single composition dependent glass transition temperature. Miscibility was induced via hydrogen bonding as evidenced by IR frequency shifts of the hydroxyl stretching vibrations of the acid copolymer in the blends. Interpolymer hydrogen bonding formation within the binary systems was also investigated by viscosimetric study of dilute solutions in toluene. For PMMA/PSCA5 blends the viscosity of the mixtures was close to the weight average viscosities of the individual polymer while for blend solutions of PSCA5 with PMMA2VP and PMMA4VP, the interactions were sufficiently strong to form interpolymer complexes with a decrease in viscosity in comparison to the additivity rule.
Thermochimica Acta, 2010
The miscibility and phase behaviour of poly (isobutyl methacrylate-co-4-vinylpyridine) containing 20 mol% of 4-vinylpyridine (IBM4VP20) and poly (styrene-co-acrylic acid) containing 27 or 32 mol% of acrylic acid (SAA27 or SAA32) mixtures were investigated by DSC, TGA and FTIR spectroscopy in the 25-180 • C temperature range. The results showed that sufficient specific carboxyl-pyridine hydrogen bonding interactions occurred between these copolymers and led to miscible blends as cast from THF and to inter-polymer complexes of significantly improved thermal stability when butan-2-one is the common solvent. The self-association effect on the inter-polymer interactions was evidenced by the decrease of complexation yields, observed when the carboxylic content is increased above 27 mol% as with SAA32.
Journal of Thermal Analysis and Calorimetry, 2011
Blends based on poly(styrene-co-itaconic acid) containing 11 or 27 mol % of itaconic acid (PSIA11, PSIA27) and poly(n-butyl methacrylate-co-4-vinylpyridine) containing 26 or 37 mol% of 4-vinylpyridine (PBM4VP26, PBM4VP37) were prepared. Their phase behavior and thermal properties were investigated by several techniques. Specific interactions that occurred between these copolymers were evidenced by FTIR from the appearance of characteristic new bands. The different T gcomposition behaviors of these systems evidenced by DSC and interpreted in terms of different types and strength of interactions that occurred within these blends, were analyzed by Kwei and ''BCKV'' (Brostow, Chiu, Kalogeras, Vassilikou-Dova) approaches. The positive deviation from the weight average of their constituent T g 's, observed with the PSIA11/PBM4VP26 and PSIA11/PBM4VP37 systems, is due to the presence of strong specific interactions that occurred within this system while the practically similar S shaped curves obtained with PSIA27/PBM4VP26 and PSIA27/PBM4VP37 blends indicate that, due to selfassociation of carboxylic groups within PSIA27, a reduced number of efficient specific interactions occurred within these blends even though containing relatively higher amounts of interacting species. A thermogravimetric analysis confirmed improved thermal stability of these blends over the individual copolymers.
Macromolecular Symposia, 2008
Summary: The miscibility and thermal behaviour of binary mixtures of poly(styrene‐co‐itaconic acid) containing 11 or 27 mol % of itaconic acid (PSIA‐11 or PSIA27) with poly(butyl methacrylate) (PBMA)or poly(butyl methacrylate‐co‐4‐vinylpyridine) containing 10 or 26 mol% of 4‐vinylpyridine (PBM4VP‐10, PBM4V‐P26) were investigated by differential scanning calorimetry, scanning electron microscopy, FTIR spectroscopy and thermogravimetry. The results showed that 11 mol % of itaconic acid and 10 mol % of 4‐vinylpyridine respectively introduced within the polystyrene and poly(butyl methacrylate) matrices induced the miscibility of this pair of polymers due to specific interactions of hydrogen bonding type with partial pyridine protonation that occurred between the two copolymers as evidenced by FTIR from the appearance of two new bands at 1607 cm−1 and 1640 cm−1. Increasing itaconic acid content from 11 to 27 mol % led to a decrease of the intensity of the specific interactions within PSI...
Polymer, 2002
The miscibility of poly(methylmethacrylate) (PMMA) and (tri¯uoroethyl methacrylic ester±MMA) copolymers (MMA±MATRIFE) with poly(vinylidene¯uoride) (PVDF) and VDF copolymers was studied by differential scanning calorimetry (DSC) as a function of thē uorinated copolymer crystallinity and¯uoroalkyl methacrylic ester content in the methacrylic copolymer. Miscibility limits were found identical whatever be the blend preparation technique, although solution mixing induced some polymer fractionation, thus giving slightly higher blend glass transition temperature. The miscibility domain widths are reduced when using MMA±MATRIFE copolymers as compared to PMMA-containing blends and miscibility limits are dependent on the MATRIFE content in the methacrylic copolymer. Moreover, PVDF or VDF copolymer melting enthalpy decrease is associated to a partial dissolution of the semi-crystalline polymer in PMMA or MMA±MATRIFE copolymer above the total miscibility limit. The evolution of dynamic moduli as a function of blends composition con®rms the miscibility limits determined by DSC. The Flory±Huggins interaction parameters were determined through the melting point depression analysis and compared to correlate the intensity of inter-or intra-molecular interactions between the polymers to the postulated`acidity' of hydrogen atoms in various VDF-containing polymers. The interaction parameter x 12 increases with the¯uoroalkyl methacrylic ester content, corresponding to a prevalence of intra-molecular on inter-molecular interactions in these blends. Similarly, PVDF offers higher x 12 values as compared to VDF±TFE or particularly to VDF±TrFE copolymers. These results highlight the importance of the nature of¯uorinated polymers and of the inter-or intra-molecular character of dipolar interactions on both, copolymer miscibility and interaction parameter values.
Thermochimica Acta, 2012
Due to the presence of specific interactions that occurred between poly(styrene-co-4-vinylpyridine) and poly(styrene-co-acrylic acid), novel materials as blends or interpolymer complexes of enhanced thermal stability were elaborated by simply mixing these copolymers and varying their initial blend composition in tetrahydrofuran or butan-2-one. The observed glass transition temperature-composition behaviors of miscible blends of these copolymers, cast from THF or interpolymer complexes obtained in butan-2-one, were analyzed according to Kwei and BCKV approaches that described well the experimental data of these systems, though better fits were obtained with the BCKV approach. A good fit of the S-shaped T g-composition behavior, was obtained using Brostow's approach only. The presence of specific interactions within these materials was evidenced by FTIR spectroscopy. The thermal stability of all elaborated materials was analyzed by thermogravimetry.