Binary and ternary polymer blends containing poly(vinylidene chloride‐co‐acrylonitrile)

Poly(vinylidene chloride‐co‐acrylonitrile) (Saran F), poly(hydroxy ether of bisphenol A) (phenoxy), poly(styrene‐co‐acrylonitrile) (PSAN), and poly(vinyl phenol) (PVPh) all have the same characteristic: miscibility with atactic poly(methyl methacrylate) (aPMMA). However, the miscibility of Saran F with the other polymer (phenoxy, PSAN, or PVPh) is not guaranteed and was thus investigated. Saran F was found to be miscible only with PSAN but not miscible with phenoxy and PVPh. Because Saran F and PVPh are not miscible, although they are both miscible with aPMMA, aPMMA can thus be used as a potential cosolvent to homogenize PVPh/Saran F. The second part of this report focused on the miscibility of a ternary blend consisting of Saran F, PVPh, and aPMMA to investigate the cosolvent effect of aPMMA. Factors affecting the miscibility were studied. The established phase diagram indicated that the ternary blends with high PVPh/Saran F weight ratio were found to be mostly immiscible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3068–3073, 2004     

Achieving miscible ternary polymer blends with hydrogen bonding

Poly(vinyl phenol) (PVPh) has previously been found to be successful in making immiscible poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) miscible. Poly(ethyl methacrylate) (PEMA) with one more methyl group than PMMA is also immiscible with PVAc. PEMA and PVAc are miscible with PVPh according to the literature. To determine whether PVPh can also cosolubilize PEMA/PVAc, PVPh samples of two different molecular weights have been mixed in this study with PEMA and PVAc to produce a ternary blend. On the basis of the calorimetry data, the ternary PEMA/PVAc/PVPh blend, regardless of the molecular weight of PVPh, has been determined to be miscible. The reason for the observed miscibility is probably that the interactions between PVAc and PVPh are similar in magnitude to those between PEMA and PVPh. A modified Kwei equation based on the binary interaction parameters proposed previously is used to describe the experimental glass‐transition temperature of the miscible ternary blend almost quantitatively well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 643–652, 2006     

Phase behavior of ternary polymer blends with favorable interactions

Atactic poly(methyl methacrylate) (aPMMA) and poly(vinyl pyrrolidone) (PVP) with a weight‐average molecular weight of 360,000 g/mol were found to be immiscible on the basis of preliminary studies. Poly(styrene‐co‐vinyl phenol) (MPS) with a certain concentration of vinyl phenol groups is known to be miscible with both aPMMA and PVP. Is it possible to homogenize an immiscible aPMMA/PVP pair by the addition of MPS? For this question to be answered, a ternary blend consisting of aPMMA, PVP, and MPS was prepared and measured calorimetrically. The role of MPS between aPMMA and PVP and the effects of different concentrations of vinyl phenol groups on the miscibility of the ternary blends were investigated. According to experimental results, increasing the vinyl phenol contents of MPS has an adverse effect on the miscibility of the ternary blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2064–2070, 2005     

Miscibility enhancement on the immiscible poly (vinyl pyrrolidone) and poly (ethyl methacrylate) with poly (vinyl phenol)

The miscibility behavior of ternary blends of poly (vinyl phenol) (PVPh)/poly (vinyl pyrrolidone) (PVP)/poly (ethyl methacrylate) (PEMA) was investigated mainly with calorimetry. PVPh is miscible with both PVP and PEMA on the basis of the single T_g observed over the entire composition range. FTIR was used to study the hydrogen bonding interaction between the hydroxyl group of PVPh and the carbonyl group of PVP and PEMA at various compositions. Furthermore, the addition of PVPh is able to enhance the miscibility of the immiscible PVP/PEMA and eventually transforms it into a miscible blend, especially when the ratio between PVP/PEMA is 3:1, probably because of favorable physical interaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1205–1213, 2006     

Reexamination of the miscibility of stereoregular poly(methyl methacrylate) with poly(vinyl phenol)

Previously, isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) were mixed with poly(vinyl phenol) (PVPh) separately in tetrahydrofuran (THF) to make three polymer blend systems. According to calorimetry data, iPMMA was found to be miscible with PVPh; however, partial miscibility or immiscibility was found between aPMMA (or sPMMA) and PVPh. According to the article by C. J. T. Landry and D. M. Teegarden, Macromolecules, 1991, 24, 4310, THF is the reason for causing aPMMA and PVPh to phase separate, but 2‐butanone instead produces miscible blends. Therefore, in this article these three polymer systems were investigated again using 2‐butanone as solvent. Films were prepared under specific conditions to minimize the effect of aggregation in PMMA. The formation of hydrogen bonding between PMMA and PVPh and the attendant changes in the aggregation of PMMA segments were determined in the solid states by means of FTIR. Based on the results of calorimetry, iPMMA and aPMMA were found to be miscible with PVPh. For iPMMA/PVPh blends, different degrees of hydrogen bonding were observed based on DSC data and FTIR spectra when compared to previous study. An elevation of the glass transition temperatures (T_gs) of aPMMA/PVPh blends above weight average was detected and the T_g values were fitted well by the Kwei equation. But partial miscibility was still found between sPMMA and PVPh on account of the observation of two T_gs in most compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1425–1431, 2002     

Miscibility enhancement on the immiscible binary blend of poly(vinyl acetate) and poly(vinyl pyrrolidone) with bisphenol A

The miscibility behavior and hydrogen bonding of ternary blends of bisphenol A (BPA)/poly(vinyl acetate) (PVAc)/poly(vinyl pyrrolidone) (PVP) were investigated by using differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). The BPA is miscible with both PVAc and PVP based on the observed single T_g over the entire composition range. FTIR was used to study the hydrogen-bonding interaction between the hydroxyl group of BPA and the carbonyl group of PVAc and PVP at various compositions. Furthermore, the addition of BPA is able to enhance the miscibility of the immiscible PVAc/PVP binary blend and eventually transforms into miscible blend with single T_g, when a sufficiently quantity of the BPA is present due to the significant Δχ and the ΔK effect.     

Effect of the tacticity of poly(methyl methacrylate) on the phase diagram of its ternary blends

Previously, isotactic and atactic poly(methyl methacrylates) (PMMAs) were found to be miscible with poly(vinyl phenol) (PVPh) and poly(hydroxy ether of bisphenol‐A) (phenoxy) because all the prepared films were transparent and showed composition‐dependent glass transition temperatures (T_g's). However, syndiotactic PMMA was immiscible with PVPh because most of the cast films had two T_g's. On the contrary, syndiotactic PMMA was still miscible with phenoxy. According to our preliminary results, PVPh and phenoxy are not miscible. Also to our knowledge, nobody has reported any results concerning the effect of the tacticity of PMMA on its ternary blend containing PVPh and phenoxy. The miscibility of a ternary blend consisting of PVPh, phenoxy, and tactic PMMA was thus investigated and reported in this article. Calorimetry was used as the principal tool to study miscibility. An approximate phase diagram of the ternary blends containing different tactic PMMA was established, probably for the first time, based on differential scanning calorimetry data. Immiscibility was found in most of the studied ternaries but a slight difference due to the effect of tacticity of PMMA was definitely observed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2720–2726, 2002     

Effect of thermal treatments on the miscibility of poly(vinyl cinnamate) binary blends

Poly(vinyl cinnamate) (PVCN) could undergo thermal or photo crosslinking. PVCN was previously found to be miscible with poly(vinyl phenol) (PVPh) [also named poly(hydroxystyrene)]. In this article, the miscibility between PVCN with or without thermal crosslinking and poly(styrene‐co‐hydrostyrene) (designated as MPS) was investigated. PVCN was determined to be miscible with MPS with 15% of hydroxystyrene (MPS‐15) at two compositions but partially miscible or immiscible at PVCN/MPS‐15(50/50) composition. For MPS with 5% of hydroxystyrene (MPS‐5), two T_g values were detected indicating mostly immiscibility. However, PVCN after thermal crosslinking was determined to be miscible with both MPS‐5 and MPS‐15. Immiscibility was found between thermally crosslinked PVCN and PVPh different from miscibility in the original PVCN/PVPh blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility studies of binary and ternary mixtures of tactic poly(methyl methacrylates) with poly(vinylidene chloride‐co‐acrylonitrile)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (i, a, and s PMMAs) were mixed with poly(vinylidene chloride‐co‐acrylonitrile) (Saran F) separately in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) was used mainly to study the miscibility of these blends. iPMMA and aPMMA were found to be miscible with Saran F based on the transparency and a single glass transition temperature (T_g) of the films. However, sPMMA was immiscible with Saran F because of the observation of two T_gs and opacity in most compositions of the blend. aPMMA is known to be miscible with sPMMA. Therefore aPMMA is both miscible with Saran F and sPMMA but Saran F and sPMMA are immiscible. Preliminary results of the effect of adding of aPMMA to immiscible sPMMA and Saran F mixtures were also reported. First, binary mixtures of atactic and syndiotactic PMMAs were also prepared and confirmed to be miscible. Elevation of T_g of the aPMMA/sPMMA blend above weight average was observed probably due to stereocomplexation occurred between aPMMA and sPMMA. Then ternary blends of atactic and syndiotactic PMMAs and Saran F in the weight ratios of about 3/1/4, 2/2/4, and 1/3/4 were also measured calorimetrically. A single T_g was observed for these three compositions different from two T_gs detected in the sPMMA/Saran F (50.0/50.0, i.e., 4/4) blend. Obviously, the composition of Saran was fixed in the ternary blends. When the other half of the blends was changing from pure sPMMA to sPMMA and aPMMA mixture, the blends became miscible because of the addition of aPMMA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1313–1321, 2000     

Phase behavior of hydrogen‐bonded ternary polymer blends

Although poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA) are only slightly different in structure, they are known to be immiscible. Polystyrene is not miscible with PEMA or PMMA. However, when polystyrene is modified to contain certain vinyl phenol groups to become poly(styrene‐co‐vinyl phenol) (PSVPh), it can be miscible with both PEMA and PMMA. What is the miscibility of a ternary blend consisting of PEMA, PMMA, and PSVPh? For this question to be answered, binary blends of PEMA (or PMMA) were first made with PSVPh. Their miscibility was examined. Then, ternary blends composed of PEMA, PMMA, and PSVPh were prepared and measured calorimetrically. The role of PSVPh between PEMA and PMMA and the effect of different contents of vinyl phenol groups on the miscibility of the ternary blends were investigated. On the basis of experimental results, increasing the vinyl phenol contents of PSVPh seemed to have an adverse effect on the miscibility of the ternary blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2088–2094, 2003     

A Viscometric Study of the Miscibility Behaviour of Poly(N-Vinyl Pyrrolidone) Blends

The miscibility behaviour of blends of poly(N-vinyl pyrrolidone) (PVP) with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and vinyl chloride–vinyl acetate (VCVAc) copolymer has been investigated on the basis of a viscometric approach. PVP is found to be miscible with PVC over the entire composition range, as is evident from the high values observed for the intrinsic viscosity of transfer. This is further supported by the single glass transition temperature observed in differential scanning calorimetry studies of the blend films. Blends of PVP with VCVAc copolymer exhibit microphase separation which is shown clearly in the scanning electron micrographs of the films. PVAc/PVP blends show interaction only at low PVAc contents, but in general are immiscible. © of SCI.     

The totally miscible in ternary hydrogen‐bonded polymer blend of poly(vinyl phenol)/phenoxy/phenolic

The individual binary polymer blends of phenolic/phenoxy, phenolic/poly(vinyl phenol) (PVPh), and phenoxy/PVPh have specific interaction through intermolecular hydrogen bonding of hydroxyl–hydroxyl group to form homogeneous miscible phase. In addition, the miscibility and hydrogen bonding behaviors of ternary hydrogen bond blends of phenolic/phenoxy/PVPh were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, and optical microscopy. According to the DSC analysis, every composition of the ternary blend shows single glass transition temperature (T_g), indicating that this ternary hydrogen‐bonded blend is totally miscible. The interassociation equilibrium constant between each binary blend was calculated from the appropriate model compounds. The interassociation equilibrium constant (K_A) of each individually binary blend is higher than any self‐association equilibrium constant (K_B), resulting in the hydroxyl group tending to form interassociation hydrogen bond. Photographs of optical microscopy show this ternary blend possess lower critical solution temperature (LCST) phase diagram. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

Influence of tacticity of poly(methyl methacrylate) on the compatibility with poly(vinyl phenol)

Isotactic, atactic, and syndiotactic poly(methyl methacrylate) (PMMA) were mixed with poly(vinyl phenol) (PVPh) separately in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy were used to study the miscibility of these blends. Isotactic PMMA was found to be more miscible with PVPh than atactic or syndiotactic PMMA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1773–1780, 1997     

Miscible blends of poly(4‐vinyl phenol)/poly (trimethylene terephthalate)

A new miscible blend of all compositions comprising poly(4‐vinyl phenol) (PVPh) and poly(trimethylene terephthalate) (PTT) was discovered and reported. The blends exhibit a single composition‐dependent glass transition and homogeneous phase morphology, with no lower critical solution temperature (LCST) behavior upon heating to high temperatures. Interactions and spherulite growth kinetics in the blends were also investigated. The Flory–Huggins interaction parameter (χ₁₂) and interaction energy density (B) obtained from analysis of melting point depression are negative (χ₁₂ = ?0.74 and B = ?32.49 J cm^?3), proving that the PVPh/PTT blends are miscible over a wide temperature range from ambient up to high temperatures in the melt state. FTIR studies showed evidence of hydrogen‐bonding interactions between the two polymers. The miscibility of PVPh with PTT also resulted in a reduction in spherulite growth rate of PTT in the miscible blend. The Lauritzen–Hoffman model was used to analyze the spherulite growth kinetics, which showed a lower fold‐surface free energy (σ_e) of the blends than that of the neat PTT. The decrease in the fold‐surface free energy has been attributed to disruption of the PTT lamellae exerted by PVPh in an intimately interacted miscible state. Copyright © 2004 Society of Chemical Industry     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl acetate)

The results of the miscibility between the chemically similar polymers poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) published so far show inconsistent statements concerning miscibility. The problems may be due to differences in molecular weights, tacticity, and preparation methods of the polymers. This investigation was carried out by using either chloroform or tetrahydrofuran (THF) as solvent to prepare the blends, because to our knowledge, nobody has reported any tacticity effect of PMMA on the miscibility with PVAc. Therefore, in this article, different tactic PMMAs were used to mix with PVAc and their miscibility was studied calorimetrically. The results showed little effect of solvent and tacticity. PMMA and PVAc were determined to be almost completely immiscible because of the observation of two T_g's. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 35–39, 2004     

Miscibility and specific interactions in blends of poly(vinyl phenyl ketone hydrogenated) with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The miscibility behavior of poly(vinyl phenyl ketone hydrogenated) (PVPhKH) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) are studied by differential scanning calorimetry, thermomechanical analysis, and FTIR spectroscopy. Two miscibility windows between 10 to 40 and 60 to 90 wt % PPO are detected. Only the blend with 50 wt % PPO is immiscible. The best fit of the Gordon–Taylor equation of the experimental glass‐transition temperatures for miscible PVPhKH/PPO blends is shown. A study by FTIR spectroscopy suggests that hydrogen bonding interactions are formed between the hydroxyl groups of PVPhKH and the ether groups of PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1887–1892, 2004     

Ternary miscibility in blends of three polymers with balanced binary interactions

This study demonstrates and discusses ternary miscibility in a three‐polymer blend system based on balanced binary interactions. A truly miscible ternary blend comprising poly(ε‐caprolactone) (PCL), poly(benzyl methacrylate) (PBzMA), and poly(vinyl methyl ether) (PVME), was discovered and reported. Miscibility with phase homogeneity (excluding the PCL crystalline domain) in a wide composition range has been demonstrated using criteria of thermal transition behavior, cloud point, and microscopy characterization. At ambient temperature, the three‐polymer ternary system is completely miscible within the entire composition range (i.e., no immiscibility loop). However, at slightly elevated temperatures above the ambient. phase separation readily occurred in this originally miscible ternary blend. A quite low “lower critical solution temperature” (LCST) near 75°C was found for the ternary blend, which is much lower than any of those for the binary pairs. Balanced interactions with no offsetting Δχ among the three binary pairs were a key factor leading to a ternary miscible system.     

Miscible blends containing bacterial poly(3‐hydroxyvalerate) and poly(p‐vinyl phenol)

The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999     

Miscibility of biodegradable aliphatic polyester and poly(vinyl acetate) blends

We report miscibility behavior for synthetic biodegradable aliphatic polyester (BDP) and poly(vinyl acetate) (PVAc) blends by investigating their thermal, rheological, and mechanical properties. Two separate glass transition temperature peaks for the BDP/PVAc blends proved that these blend systems are immiscible. From the rheological measurement, the shear viscosity as a function of shear rate is observed to increase with increasing PVAc content in BDP/PVAc blends, since PVAc has a relatively high molecular weight compared to BDP. Moreover, BDP blends with 10 wt % PVAc have excellent mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1348–1352, 2000