Phase behavior of ternary polymer blends with hydrogen bonding

Atactic poly (methyl methacrylate) (aPMMA) was found to be almost completely immiscible with poly(vinyl acetate) (PVAc). Both aPMMA and PVAc are known to be miscible with poly(vinyl phenol) (PVPh) according to literature. Adding of PVPh into immiscible aPMMA/PVAc mixtures is likely to improve their miscibility. Therefore, PVPh can be used as cosolvent to cosolubilize aPMMA and PVAc. A ternary blend consisting of aPMMA, PVAc, and PVPh was prepared and determined calorimetrically in this article. According to the calorimetry data, the ternary blend was determined to be miscible. The reason for the observed miscibility is because the interactions between PVAc and PVPh are similar to those between aPMMA and PVPh. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2797–2802, 2004     

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     

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     

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     

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     

A high‐resolution solid‐state NMR investigation of molecular mobility of poly(methyl methacrylate)/poly(vinyl pyrrolidone)/poly(ethylene oxide) ternary blends

The ternary blends of poly(methyl methacrylate)/poly(vinyl pyrrolidone)/poly(ethylene oxide), PMMA/PVP/PEO, were prepared by melting process, using a Haake plastograph, and nuclear magnetic resonance spectroscopy (NMR) was used as a methodology to characterize the molecular mobility of blend components, because NMR has several techniques that allow us to evaluate polymeric materials in different time scales. The NMR results showed that the blends were miscible on a molecular level. The values of proton lattice relaxation time in the rotating frame (T₁ρH) indicate that the ternary blend interaction did not reduce the intermolecular distance, because it is dipole–dipole. The molecular motion of each component, even in the miscible amorphous phase and the addition of PEO, has a definitive effect on the PMMA molecular mobility. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1492–1495, 2006     

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     

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 of poly(2-chloroethyl methacrylate) with various polymethacrylates

The miscibility behavior of poly(2-chloroethyl methacrylate) (PCEMA) with various polymethacrylates was investigated by differential scanning calorimetry. PCEMA is miscible with poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(tetrahydrofurfuryl methacrylate) (PTHFMA), but is immiscible with poly(n-propyl methacrylate), poly(isopropyl methacrylate), poly(n-butyl methacrylate), and poly(cyclohexyl methacrylate). PCEMA/PEMA blends showed lower critical solution temperature (LCST) behavior but PCEMA/PMMA and PCEMA/PTHFMA blends degraded before phase separation could be induced. The miscibility behavior of PCEMA is similar to that of a chlorinated polymer.     

DSC and DMTA characterization of ternary blends

The phase behavior of ternary blends made of poly(epichlorohydrin) (PECH), poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). DMTA measurements have been shown to be more sensitive than DSC for the detection of a second phase, for the determination of the composition of each phase, and the distribution of PECH in each of them. About 70% PECH was required to obtain a single narrow T_g in the ternary system, which suggests a single homogeneous phase in the limit of sensitivity of DMTA. This study also emphasizes the importance of the composition of the immiscible polymer pair (i.e. the PVAc/PMMA pair in the PECH/PVAc/PMMA system), in addition to the thermodynamic interaction parameters, for controling the phase behavior of ternary systems.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Miscibility of poly(p-vinyl phenol) with polymethacrylates

Summary Poly(p-vinyl phenol) is miscible with poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(isopropyl methacrylate), and poly(tetrahydrofurfuryl methacrylate), but is immiscible with poly(n-butyl methacrylate). Except for poly(p-vinyl phenol)/ poly(methyl methacrylate) blends, the other miscible blends show pronounced positive deviations in their glass transition temperatures. The T_g-composition curves of the five miscible blend systems can be described by the Gordon-Taylor and the Kwei equations.     

Correlating miscibility of PVC/PMMA blend with polymer chain orientation

Blends of poly (vinyl chloride) (PVC) and poly (methyl methacrylate) (PMMA) with varying concentrations of the polymers were prepared in a film form by standard solution casting method, using methyl ethyl ketone (MEK) as a common solvent. The miscibility of the blend was studied by dynamic mechanical analysis. The chain orientation behaviors of PVC and PMMA in the stretched blend films were studied by infrared dichroism method. Up to 60 wt % PVC concentration in the blend, PVC showed negative values for orientation function whereas PMMA showed independent positive values for its orientation function. On further increasing PVC concentration in the blend, the orientation function of PVC flipped to positive values, and both PVC and PMMA showed same magnitude and trend in orientation behavior. The chain orientation behavior of individual polymers in the immiscible compositions of the blend was observed to be independent, while there was a high degree of cooperation for chain orientation in the miscible composition. Change in the miscibility of the blend was simultaneously accompanied by conformational changes in PVC. The change in orientation behavior is interpreted in terms of curling of polymer chains in the immiscible phase. The polymer chain curling hypothesis used here is applicable independent of the type of polymers in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 624–630, 2006     

Miscibility of poly(α-methyl siyrene-co-acrylonitrile) with polyacrylates and polymethacrylates

A copolymer formed from 30 percent acrylonitrile and 70 percent α methyl styrene by weight, or αMSAN, has been examined for miscibility in blends with various polyacrylates and polymethacrylates. None of the polyacrylates or poly(vinyl acetate) were miscible with α-MSAN at room temperature or above. The methyl and ethyl esters of the polymethacrylate series (PMMA, PEMA) proved to be miscible with α MSAN, but none of the higher homologues were miscible under these conditions. Blends of both PMMA and PEMA with α MSAN exhibited lower critical solution temperatures. The observed cloud points decreased as PMMA molecular weight increased up to 10⁵ where kinetic effects caused an apparent reversal of this trend. Atactic PMMA interacts more strongly with αMSAN than does either isotactic PMMA or atactic PEMA. These structural effects are compared with similar trends found in other systems.     

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 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.     

Influence of molecular weight of poly (methyl methacrylate) on its miscibility with poly (vinyl chloride) in the solution

In this work, the molecular weight effect on miscibility between poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in cyclohexanone(CH) solutions at 30 °C was examined by the viscometric method. Three samples of PMMA were prepared by emulsion polymerization, which molecular weights were changed by tert-dodecyl-mercaptan (TDDM) content. The parameter Δb is used to predict polymer-polymer miscibility of PVC/PMMA/cyclohexanone blend. Δb values indicated that the highest molecular weight of PMMA is immiscible with PVC resin. The molecular weight of PMMA decrease with the increase of the contention of TDDM, and the contribution of miscibility PVC/PMMA blend in CH is better.     

Mixed monolayers of pmas with poly(styrene‐b‐methyl methacrylate) at the air/water interface

Poly(methyl methacrylate) (PMMA) is known to be immiscible with poly(styrene) (PS) in the bulk state. Poly(ethyl methacrylate) (PEMA), poly(propyl methacrylate) (PPMA), and poly(n‐butyl methacrylate) (PBMA) are also known to be immiscible with PMMA (or PS). Therefore, PMAs (PMMA, PEMA, PPMA, and PBMA) are predicted by the mean field theory to be immiscible with poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) in the bulk state. However, the miscibility of PMAs with PS‐b‐PMMA may be different in the two‐dimensional state. Therefore, the mixed monolayer behavior of PMAs and PS‐b‐PMMA was investigated from the measurements of surface pressure‐area per molecule (π‐A) isotherms at three different temperatures (10°C, 25°C, and 40°C). Calculation of compressibility from isotherms provided the inflection data from maximum and minimum peaks. The miscibility and nonideality of the mixed monolayers were examined by calculating the excess area as a function of composition. Mostly, negative deviations from ideality were observed in the mixed monolayers. This is likely because of favorable interaction between PMMA and PMAs in the monolayer state. The positive deviations occurred at 40°C with PBMA at a high surface pressure. Therefore, with confinement in the two‐dimensional state, the miscibility between PMAs and PS‐b‐PMMA was greatly improved in comparison with the bulk state. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Elongational viscosity for miscible and immiscible polymer blends. I. PMMA and AS with similar elongational viscosity

The effects of miscibility and blend ratio on uniaxial elongational viscosity of polymer blends were studied by preparing miscible and immiscible samples at the same composition by using poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-co-styrene) (AS). Miscible polymer blend samples for the elongational viscosity measurement were prepared by using three steps: solvent blends, cast film, and hot press. A phase diagram of blend samples was made by visual observation of cloudiness. Immiscible blend samples were prepared by maintaining the prepared miscible samples at 200°C, which is higher than cloud points using a LCST (lower critical solution temperature) phase diagram. The phase structure of immiscible blends was observed by an optical microscope. The elongational viscosity of all samples was measured at 145°C, which is lower than the cloud-point temperature at all blend ratios. The elongational viscosity of PMMA and AS was similar to each other. The strain-hardening property of miscible blends in the elongational viscosity was only slightly influenced by the blend ratio, and this was also the case with immiscible blends. The strain-hardening property was only slightly influenced, whether it was miscible or immiscible at each blend ratio. Polydispersity in molecular weight for blend samples was not changed by GPC (gel permeation chromatography) analysis. Almost no change in the polydispersity of the molecular weight for blends and the similarity of elongational viscosity between PMMA and AS resulted in little influence of the blend ratio and miscibility on the strain-hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 757–766, 1999     

Free volume microprobe studies on poly(methyl methacrylate)/poly(vinyl chloride) and poly(vinyl chloride)/polystyrene blends

Blends of Poly(methyl methacrylate) (PMMA)/Poly(vinyl chloride) (PVC) and Poly(vinyl chloride) (PVC)/Polystyrene (PS) of different compositions were prepared by solution casting technique. The blends were characterized using Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), and Positron Lifetime Spectroscopy. DSC data were found to be inadequate to describe whether PMMA/PVC blends are miscible or not, possibly because of the small gap in their glass transition temperatures. On the other hand, PVC/PS blends were clearly found to be immiscible by DSC. FTIR results for PMMA/PVC indicate the possible interactions between the carbonyl group of PMMA and α‐hydrogen of PVC. Free volume data derived from Positron lifetime measurements showed that the PMMA/PVC blends to be miscible in low PVC concentration domain. For the first time, the authors have evaluated the hydrodynamic interaction parameter α, advocated by Wolf and Schnell, Polymer, 42, 8599 (2001), to take into account the friction between the component molecules using the free volume data. This parameter (α) has a high value (?57) at 10 wt% of PVC, which could be taken to read miscibility for PMMA/PVC blends to be high. In the case of PVC/PS blends, the positron results fully support the DSC data to conclude the blends to be immiscible throughout the range of concentration. As expected, the hydrodynamic interaction parameter α does not show any change throughout the concentration in PVC/PS blends, further supporting the idea that α is another suitable parameter in the miscibility study of polymer blends. POLYM. ENG. SCI., 46:1231–1241, 2006. © 2006 Society of Plastics Engineers