Miscibility window for the blends of poly(styrene-co-4-vinylphenymethylphenylsilanol) with poly(n-butyl methacrylate)

Polymer blends consisting of poly(styrene-co-4-vinylphenylmethylphenylsilanol) (ST-VPMPS) and poly(n-butyl methacrylate) (PBMA) have been investigated. The experimental results showed that miscible blends were formed when ST-VPMPS copolymers contained 9–56 mol % silanol functional groups. Comparison of the results with poly(styrene-co-4-vinylphenyldimethylsilanol) (ST-VPDMS)/PBMA blends revealed that the miscibility window was shifted to a higher silanol composition in the present system in which a stronger hetero-associated hydrogen bonding interaction was present. The results were discussed in terms of steric shielding and electron-withdrawing effects of the phenyl substituent bound directly to the silicon atom. © 1996 John Wiley & Sons, Inc.     

Novel Silanol-Containing Polymers and Their Blends

ABSTRACT

Novel 4-vinylphenyldimethylsilanol polymer (PVPDMS) and co-polymers (ST-VPDMS) were synthesized by the oxyfunctionalization re- action of the silane. The reaction was found to proceed efficiently and quantitatively. Miscibility studies indicated that about 4 molpercnt; of 4-vin- ylphenyldimethylsilanol (VPDMS) functional group in the copolymer could achieve miscibility with poly(n-butyl methacrylate) (PBMA) and poly(N-vinylpyrrolidone) (PVPr). However, for copolymers containingmore than 34 molpercnt; VPDMS, their blends with PBMA were immiscible. The observed miscibility window of ST-VPDMS/PBMA blends was as- cribed to the competition between the self-association of dimethylsilanol groups and intermolecular hydrogen bonding of dimethylsilanol groups with the carbonyl groups of PBMA. A comparison of the efficiency of the miscibility enhancement and the miscibility windows of VPDMS, p-(hexafluoro-2-isopropyl) styrene (HFPS), and phenolic-containing polymers was made in terms of such competition. The glass transition behavior of the miscible blends involving VPDMS and HFPS-containing styrene copolymers with PBMA were analyzed by the Schneider equation.     

Miscibility of poly(butyl methacrylate-CO-methacrylic acid) or poly(styrene-CO-methacrylic acid) with poly(styrene-CO-4-vinylpyridine) or poly(butyl methacrylate-CO-4-vinylpyridine)

The miscibility of blends of copolymers of different compositions of butyl methacrylate-co-methacrylic acid or styrene-co-methacrylic acid with styrene-co-4-vinylpyridine or butyl methacrylate-co-4-vinylpyridine was studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. It was found that these blends were miscible in part as a result of specific favorable interactions between the carboxylic acid and pyridine groups within the polymer chains. Evidence of such interactions was obtained from the single composition-dependent glass transition temperature and the FTIR results.     

Miscibility of poly(vinyl methyl ether) and poly(styrene-co-2-vinylnaphthalene) blends by FT-IR spectroscopy and Tg measurements

Miscibility of blends consisting of poly(vinyl methyl ether) (PVME) and poly(styreneco-2-vinylnaphthalene) [P(S-co-2VN)] was investigated by means of Fourier transform infrared (FT-IR) spectroscopy and thermal analysis. Copolymers containing 21, 51, and 84 wt % of styrene were synthesized by radical polymerization. Based on optical clarity and glass transition temperatures, it was shown that the miscibility in P(S-co-2VN)/PVME blends is largely affected by compositions of the copolymers as well as concentrations of the blend. From the FT-IR results, the relative intensity at 1100 cm^?1 peak of COCH₃ band of PVME and the position of naphthyl ring of 2VN were sensitive to the miscibility of the blends. It was observed that blends of PVME with P(S-co-2VN) of 84 wt % styrene or P(S-co-2VN) of 51 wt % styrene are miscible over the entire concentration ranges of the blends. Blends of PVME with P(S-co-2VN) containing 21 wt % of styrene are immiscible below 65 wt % PVME. In the miscible P(S-co-2VN)/PVME blends, there was observed a large shift in the naphthyl frequency at a characteristic wavelength of 748 cm^?1. © 1993 John Wiley & Sons, Inc.     

Miscibility and phase structure of binary blends of polylactide and poly(methyl methacrylate)

Blends of amorphous poly(DL‐lactide) (DL‐PLA) and crystalline poly(L‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were prepared by both solution/precipitation and solution‐casting film methods. The miscibility, crystallization behavior, and component interaction of these blends were examined by differential scanning calorimetry. Only one glass‐transition temperature (T_g) was found in the DL‐PLA/PMMA solution/precipitation blends, indicating miscibility in this system. Two isolated T_g's appeared in the DL‐PLA/PMMA solution‐casting film blends, suggesting two segregated phases in the blend system, but evidence showed that two components were partially miscible. In the PLLA/PMMA blend, the crystallization of PLLA was greatly restricted by amorphous PMMA. Once the thermal history of the blend was destroyed, PLLA and PMMA were miscible. The T_g composition relationship for both DL‐PLA/PMMA and PLLA/PMMA miscible systems obeyed the Gordon–Taylor equation. Experiment results indicated that there is no more favorable trend of DL‐PLA to form miscible blends with PMMA than PLLA when PLLA is in the amorphous state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 23–30, 2003     

Miscibility and crystallinity of poly(3-hydroxybutyrate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends

With the objective of developing new biodegradable materials, the miscibility and the crystallinity of blends of poly(3-hydroxybutyrate), P(3HB), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), have been studied. P(3HB) (300 kg mol⁻¹)/P(3HB-co-3HV)–10% 3HV (340 kg mol⁻¹) blends were prepared by casting in a wide range of proportions, and characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The experimental values for the glass transition temperatures (T_g) are in good agreement with the values provided by the Fox equation, showing that the blends are miscible. It was observed that the T_g and the melting temperature (T_m) decreases with the increase in the P(3HB-co-3HV)–10% 3HV content, while the crystallization temperature (T_c) increases. FT-IR analyses confirmed the decrease on the crystallinity of P(3HB)/P(3HB-co-3HV)–10% 3HV blends with higher copolymer contents. Bands related to the crystallinity were changed, due to the copolymer content that produced miscible and less crystalline blends.     

Poly(N-phenyl-2-hydroxytrimethylene amine): Its blends with poly(ϵ-caprolactone) and water-soluble polyethers

A new polymer with pendant hydroxyl groups, namely, poly(N-phenyl-2-hydroxytrime-thylene amine) (PHA), was synthesized by a direct condensation polymerization of aniline and epichlorohydrin in an alkaline medium. The new polymer is amorphous with a glass transition temperature (T_g) of 70°C. Blends of PHA with poly(ϵ-caprolactone) (PCL), as well as with two water-soluble polyethers, poly(ethylene oxide) (PEO) and poly(vinyl methyl ether) (PVME), were prepared by casting from a common solvent. It was found that all the three blends were miscible and showed a single, composition dependent glass transition temperature (T_g). FTIR studies revealed that PHA can form hydrogen bonds with PCL, PEO, and PVME, which are driving forces for the miscibility of the blends. © 1997 John Wiley & Sons, Inc.     

Melting behavior,miscibility, and hydrogen-bonded interactions of poly(ε-caprolactone)/poly(4-hydroxystyrene-co-methoxystyrene) blends

The miscibility of poly(4-hydroxystyrene-co-methoxystyrene) (HSMS) and poly(ε-caprolactone) (PCL) was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). HSMS/PCL blends were found to be miscible in the whole composition range by detecting only a glass transition temperature (T_g), for each composition, which could be closely described by the Fox rule. The crystallinity of PCL in the blends was dependent on the T_g of the amorphous phase. The greater the HSMS content in the blends, the lower the crystallinity. The polymer–polymer interaction parameter, χ₃₂, was calculated from melting point depression of PCL using the Nishi-Wang equation. The negative value of χ₃₂ obtained for HSMS/PCL blends has been compared with the value of χ₃₂ for poly(4-hydroxystyrene) (P4HS)/PCL blends. The specific nature, quantitative analysis, and average strength of the intermolecular interactions in HSMS/PCL and P4HS/PCL blends have been determined at room temperature and in the molten state by means of Fourier transform infrared spectroscopy (FTIR) measurements. The FTIR results have been in good correlation with the thermal behavior of the blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 95–104, 1998     

Miscible blends of poly(vinyl phenyl ketone) and poly(4‐vinyl phenol)

An analysis by differential scanning calorimetry, modulated differential scanning calorimetry, and Fourier transform infrared spectroscopy (FTIR) indicates that blends of poly(vinyl phenyl ketone) (PVPhK) and poly(4‐vinyl phenol) (P4VPh) are miscible at ambient temperature. Miscibility, ascertained, is supported by the existence of a single glass transition for each composition of the PVPhK/P4VPh blends. The FTIR spectroscopy analysis demonstrates the formation of hydrogen bonds between carbonyl groups of PVPhK and hydroxyl groups of P4VPh. This specific interaction has a crucial role on the miscibility behavior of PVPhK/P4VPh blends. The evolution of the glass transition of the PVPhK, P4VPh, and its blends as a function of mixture composition shows negative deviations with to respect to the ideal mixing rule, and both Fox and Gordon–Taylor equations predict this behavior successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2404–2411, 2006     

Miscibility, mechanical and thermal properties of poly(lactic acid)/polyester-diol blends

We found new plasticizers with high molecular weight and low mobility for poly(lactic acid) (PLA). The new plasticizers are polyester-diols (PED) with nominal molecular weight 2000. Temperature dependence of oscillatory tensile moduli of PLA/PED blends in solid states was measured and miscible pairs of the blends were found. The miscible pairs are PLA/poly(ethylene adipate) and PLA/poly(diethylene adipate). Observation by scanning electron microscope and results of differential scanning calorimetry also indicate that these blends are miscible with PLA at weight ratio of PED less than or equal to 20%. In these blends, glass transition temperature is significantly lower than that of PLA. On the other hand, poly(butylene adipate) and poly(hexamethylene adipate) are partially miscible with PLA at weight ratio of PED 20%. The difference of the miscibility is discussed in terms of solubility parameter, which is calculated using the method by Small and configurational entropy.     

Biodegradable poly(alkylene succinate) blends: Thermal behavior and miscibility study

New binary blends composed of poly(ethylene succinate) and poly(propylene succinate) or poly(ethylene succinate) and poly(butylene succinate) were prepared. Both PESu/PPSu and PESu/PBSu systems belong to semicrystalline/semicrystalline pairs. The miscibility and crystallization behavior was investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and polarizing light microscopy (PLM). Blends of PESu and PPSu exhibited a single composition dependent glass transition temperature over the entire range of composition, indicating that the system is miscible. The melting point depression of the high melting temperature component, PESu, was analyzed according to the Nishi‐Wang equation. A negative polymer–polymer interaction parameter was obtained, indicating that the blends are thermodynamically miscible in the melt. The two components crystallized sequentially when the blends were cooled rapidly to a low temperature. DSC traces of PESu/PBSu blends after quenching showed two distinct composition dependent glass transition temperatures between those of the neat polymers, showing that the polymers are partially miscible. The amorphous PESu/PBSu blends in the intermediate compositions showed three cold‐crystallization peaks, indicating the influence of mixing. The crystallization rates of PBSu were reduced and those of PESu were increased. WAXD showed reduced crystallinity and peak broadening in the patterns of the blends of intermediate compositions, while no spherulites could be detected by PLM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 584–597, 2006     

Miscibility of poly(vinyl chloride) with chitin derivatives having poly(2-methyl-2-oxazoline) side chains

Binary blends of poly(vinyl chloride) (PVC) and chitin-graft-poly(2-methyl-2-oxazoline) showed miscibility in the blend fraction range of the latter lower than ca. 10 wt.-%. The glass transition temperature of PVC, which was determined by differential scanning calorimetry, changed to lower temperatures with increasing modified chitin contents up to 10 wt.-%. Segmental interaction between PVC and the graft copolymer was confirmed by the carbonyl stretching band shift in the FT-IR analysis.     

Study of the miscibility of poly(vinyl pyridines) with poly(vinyl acetate), poly(vinyl alcohol) and their copolymers

Miscibility of poly(4-vinyl pyridine) (P4VP) and poly(2-vinyl pyridine) (P2VP) with poly(viny acetate) (PVAc), poly(vinyl alcohol) PVA and poly(vinyl acetate-co-alcohol) (ACA copolymers) has been investigated over a wide composition range. Differentiaal scanning calorimetry (DSC) results indicate that P2VP is immiscible with PVAC, PVA, and their copolymers over the whole composition range. In turn, P4VP appears to be immiscible with PVAC and PVA, but miscible with some ACA copolymers in certain range of composition. The P4VP-ACA phase diagram for different copolymer compositions has been determined. The variation of the glass transition temperature with composition for miscible mixtures was found to follow the Gordon-Taylor equation, with the parameter κ dependent upon copolymer composition. FTIR analysis of blends reveal the existence of specific interactions via hydrogen bonding between hydroxyl groups and the nitrogen of the pyridinic ring, which appear to be decisive for miscibility. © 1994 John Wiley & Sons, Inc.     

Interdiffusion measurements of modified poly(arylether sulfone)s using nuclear reaction analysis

The interdiffusion and miscibility behavior of three different types of modified poly(arylether sulfone)s with deuterated poly(arylether sulfone) is studied by depth profiling using the nuclear reaction D(³He, α)p. The diffusion coefficients are found to be in the range of 10⁻¹⁵ and 10⁻¹⁴ cm²/s at 195°C. A random copolymer of poly(arylether sulfone) containing 4,4-bis-(4′-hydroxyphenyl)valeric acid units is only partially miscible with deuterated poly(arylether sulfone) when the comonomer content is 8.8 mol %, whereas blends with comonomer contents of 1.7 and 4.5 mol % are miscible as indicated by complete interdiffusion. The transition from miscibility to immiscibility is caused by repulsive interactions of copolymer segments and can be explained in terms of a mean-field theory of random copolymer blends. Also, poly(arylether sulfone)s grafted with 0.4 wt % maleic anhydride or having pyromellitic anhydride endgroups are miscible with deuterated poly(arylether sulfone)s. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2083–2091, 1997     

Miscibility of poly(ϵ-caprolactone) and of poly(styrene-co-acrylonitrile) with poly(styrene-co-acrylic acid)

The miscibility of poly (?-caprolactone) (PCL) with poly (styrene-co-acrylic acid) (SAA) and of poly (styrene-co-acrylonitrile) (SAN) with SAA was examined as a function of the comonomer composition in the copolymers. For PCL/SAA blends it was found that PCL is miscible with SAA within a specific range of copolymer compositions. Segmental interaction energy densities were evaluated by analysis of the equilibrium melting point depression and application of a binary interaction model. The results suggest that the intramolecular repulsion in SAA copolymer plays an important role in inducing the miscibility. Additionally, the critical AA content in SAA for the blend to be homogeneous was predicted by correlating the segmental interaction energy densities with the binary interaction model. For SAN/SAA blends, it was also found that SAA is miscible with SAN within a specific range of copolymer compositions. From the binary interaction model, segmental interaction energy denisties between different monomer units were estimated from the miscibility map and were found to be positive for all pairs, indicating that the miscibility of the blends is due to the strong repulsion in the SAA copolymers.     

Transition from miscibility to immiscibility in blends of poly(methyl methacrylate) and styrene-acrylonitrile copolymers with varying copolymer composition: a DSC study

The glass transition and the structural relaxation processes have been studied in blends of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt.% blend of PMMA with the SAN copolymer containing 30 wt.% of AN is immiscible, while blends with copolymers containing between 13 and 26 wt.% of AN are miscible. Thus the upper limit of miscibility is between 26 and 30 wt.% of AN. The temperature dependence of the relaxation times of the conformational rearrangements of polymer chains around the glass transition have been determined in the blends and pure components by modelling DSC thermograms obtained after different thermal histories in each sample. The slope in the Arrhenius diagram logτ vs 1/T around the glass transition temperature is significantly smaller in the blend which is closer to the upper limit of miscibility than in the other miscible blends in which SAN copolymer contains less AN. The change of slope can be ascribed to a distribution in the glass transition temperatures of the different rearranging regions, reflecting the appearance of a microheterogeneity in the blend that cannot be detected as a double glass transition in the blend.     

The assessment of miscibility and morphology of poly(ε-caprolactone) and poly(para-chlorostyrene) blends

The miscibility and morphology of poly(ε-caprolactone) (PCl) and poly(para-chlorostyrene) (PpClS) blend were investigated by using thermal analysis, morphological analysis, viscometry, and the study of melting point depression. A single glass transition temperature was observed by differential scanning calorimetry (DSC) for PCl/PpClS blends in the whole compositional range (0/100, 25/75, 50/50, 62.5/37.5, 75/25, 90/10). Morphology of the polymers and their blends was studied by scanning electron microscopy (SEM). The Fourier transform infrared spectra of the samples were obtained by spectrometer. Up to 12 cm⁻¹ shifts in carbonyl stretching band of PCl was detected in the spectra of PpClS rich blends. The viscosity of PCl, PpClS and their blends has also been studied to investigate the miscibility according the miscibility criteria Δb, and Δ[η]. Using this data, the interaction parameters α and μ, based on the Chee and Sun et al. approaches were determined. These criteria indicated that the blend is miscible in all proportions up to 90% of PCl content in the blends. The melting point depression of PCl in the blends was examined to obtain the interaction parameter, χ₁₂ for this system. The parameter, χ₁₂ was found to be composition dependent. Negative values of the obtained interaction parameter also support the miscibility of this system up to the 90% PCl in the blend.     

Ionic miscibility enhancement in poly(tetrafluoroethylene)/poly(ethyl acrylate) blends. I. Dynamic mechanical studies

It is shown that ion-ion interactions resulting from a proton transfer induce considerable miscibility in blends of functionalized poly(tetrafluoroethylene) with ethyl acrylate copolymers containing 4-vinyl pyridine. Dynamic mechanical measurements, in conjunction with transparency of the samples, are used to evaluate miscibility. It is shown that mixing conditions exert a profound effect on the properties of the final blend. The glass transition of the blend is shown to be strong function of the blend composition, as is characteristic of highly miscible systems.     

Comparative studies on miscibility and phase behavior of linear and star poly(2‐methyl‐2‐oxazoline) blends with poly(vinylidene fluoride)

The comparative studies on the miscibility and phase behavior between the blends of linear and star‐shaped poly(2‐methyl‐2‐oxazoline) with poly(vinylidene fluoride) (PVDF) were carried out in this work. The linear poly(2‐methyl‐2‐oxazoline) was synthesized by the ring opening polymerization of 2‐methyl‐2‐oxazoline in the presence of methyl p‐toluenesulfonate (MeOTs) whereas the star‐shaped poly(2‐methyl‐2‐oxazoline) was synthesized with octa(3‐iodopropyl) polyhedral oligomeric silsesquioxane [(IC₃H₆)₈Si₈O₁₂, OipPOSS] as an octafunctional initiator. The polymers with different topological structures were characterized by means of Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. It is found that the star‐shaped poly(2‐methyl‐2‐oxazoline) was miscible with poly(vinylidene fluoride) (PVDF), which was evidenced by single glass‐transition temperature behavior and the equilibrium melting‐point depression. Nonetheless, the blends of linear poly(2‐methyl‐2‐oxazoline) with PVDF were phase‐separated. The difference in miscibility was ascribed to the topological effect of PMOx macromolecules on the miscibility. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 942–952, 2006     

Polymer-polymer miscibility in blends of a new poly(aryl ether ketone) with poly(ether imide)

Polymer miscibility was found for a blend system comprising of a new poly(aryl ether ketone) and a poly(ether imide). Phase homogeneity was preliminarily confirmed using optical and scanning electron microscopy, indicating that the scales of phase homogeneity in the blends were beyond the resolution limits of either microscopy. A composition-dependent, single glass transition temperature (T_g) in the PAEK/PEI blends within the full range of composition was observed using differential scanning calorimetry (DSC). The thermal transition breadth also suggests that the scales of mixing are fine and uniform.