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     

Miscibility of poly(styrene-co-acrylonitrile) and poly(α-methyl styrene-co-acrylonitrile) with copolymers of methyl methacrylate

Poly(α-methyl styrene-co-acrylonitrile) was found to be miscible with poly(methyl methacrylate-co-ethyl methacrylate) and with poly(methyl methacrylate-co-n-butyl methacrylate). All these blends exhibited lower critical solution temperatures. Poly(styrene-co-acrylonitrile) was also found to be miscible with poly(methyl methacrylate-co-ethyl methacrylate) and with poly(methyl methacrylate-co-n-butyl methacrylate). However, phase separation of these blends could not be induced by heating up to 300°C.     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.     

Miscible blends of poly(n-vinyl-2-pyrrolidone) with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate)

Summary Poly(N-vinyl-2-pyrrolidone) is miscible with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate) as shown by the optical clarity and the glass transition behaviour of the blends. The miscible blends degrade before phase separation could be induced by heating. The three T_g-composition curves can be fitted by the Gordon-Taylor equation. The implication of the Gordon-Taylor k parameters of the blends is discussed.     

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.     

Miscibility of some phenoxy/polymethacrylate blends

Summary It has been reported that phenoxy is miscible with poly(methyl methacrylate), poly(tetrahydrofurfuryl methacrylate) and poly(tetrahydropyranyl-2-methyl methacrylate). However, we have found that phenoxy is immiscible with poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(n-butyl methacrylate), poly(methylthiomethyl methacrylate), poly(methoxymethyl methacrylate) and poly(methoxycarbonylmethyl methacrylate). The miscibility behavior of various phenoxy/polymethacrylate blends cannot be satisfactorily explained by a non-hydrogen-bonded solubility parameter approach.     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

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     

Miscibility of poly(vinylidene fluoride) and potassium salt of poly(methyl methacrylate-ran-methacrylic acid)

The crystalline–amorphous polymer pair of poly(vinylidene fluoride) and poly(methyl methacrylate) is known to be miscible over a wide composition range. The effects of ionic moieties on the miscibility were studied by replacing the poly(methyl methacrylate) with a series of random copolymers of methyl methacrylate and potassium salt of methacrylic acid. The interaction parameter (χ) for the miscible blends in their molten state was obtained by thermal analysis using a melting-point depression calculation. The parameter decreased to a minimum at c.2% ion content (χ=minus;0.514) and approached a positive value at above 10% ion concentration.     

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     

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     

Blends containing polymers of epichlorohydrin and ethylene oxide. Part I: Polymethacrylates

The phase behavior of blends of various polymethacrylates with poly(epichlorohydrin) (PECH); poly(ethylene oxide) (PEO); and a copolymer of epichlorohydrin and ethylene oxide [P(ECH/EO)], was examined using differential scanning calorimetery (DSC), dynamic mechanical properties, and optical indications of phase separation on heating, namely lower critical solution temperature (LCST) behavior. Poly(methyl methacrylate) (PMMA), was shown to be miscible with PECH, PEO, and P(ECH/EO), while only PECH was found miscible with the higher polymethacrylates: poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(n-butyl methacrylate), and poly(cyclohexyl methacrylate). However, even PECH was found to be only partially miscible with poly(isopropyl methacrylate). In many cases, unusually broad glass transitions were observed by DSC for blends which are believed to be the result of equilibrium composition fluctuations. All mixtures showed LCST behavior and based on this and excess volume measurements, to the extent possible, qualitative conclusions were made concerning the relative strength of the interactions among the various blend pairs. For PECH, it appears that the interaction with polymethacrylates decreases with increasing size of the alkyl pendant group, with poly(cyclohexyl methacrylate) being a possible exception. The interaction with PMMA is apparently about the same for PECH and PEO, but somewhat less for P(ECH/EO). The latter is consistent with an intrachain attraction of ECH and EO believed to exist. The reasons for similar interactions of PEO and PECH with PMMA are not understood; however, it is clear that the chlorine moiety of PECH is needed for miscibility with higher polymethacrylates.     

Decreasing miscibility with greater heterogeneity in ternary polymer blend: poly(cyclohexyl methacrylate), poly(α‐methyl styrene) and poly(4‐methyl styrene)

A ternary blend system comprising poly(cyclohexyl methacrylate) (PCHMA), poly(α‐methyl styrene) (PαMS) and poly(4‐methyl styrene) (P4MS) was investigated by thermal analysis, optical and scanning electron microscopy. Ternary phase behaviour was compared with the behaviour for the three constituent binary pairs. This study showed that the ternary blends of PCHMA/PαMS/P4MS in most compositions were miscible, with an apparent glass transition temperature (T_g) and distinct cloud‐point transitions, which were located at lower temperatures than their binary counterparts. However, in a closed‐loop range of compositions roughly near the centre of the triangular phase diagram, some ternary blends displayed phase separation with heterogeneity domains of about 1 µm. Therefore, it is properly concluded that ternary PCHMA/PαMS/P4M is partially miscible with a small closed‐loop immisciblity range, even though all the constituent binary pairs are fully miscible. Thermodynamic backgrounds leading to decreased miscibility and greater heterogeneity in a ternary polymer system in comparison with the binary counterparts are discussed. © 2003 Society of Chemical Industry     

Miscible blends of poly(styrene-co-acrylonitrile) and poly(α-methyl styrene-co-acrylonitrile) with poly(methyl methacrylate) containing sterically hindered amine group

Poly(methyl methacrylate) containing a small amount of pendant 2,2,6,6-tetramethylpiperidinyl group was found to be miscible with poly(styrene-co-acrylonitrile) and with poly(α-methyl styrene-co-acrylonitrile). The poly(α-methyl styrene-co-acrylonitrile) blends exhibited lower critical solution temperatures. Phase separation of the poly(styrene-co-acrylonitrile) blends could not be induced by heating up to 270°C.     

Miscibility behavior of blends of poly(alkyl methacrylate)s with poly(p-methylstyrene-co-methacrylonitrile)

The miscibility behavior of various poly(p-methylstyrene-co-methacrylonitrile) (pMSMAN)/poly(alkyl methacrylate)s blends was studied using differential scanning calorimetry. pMSMAN is miscible with poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(isopropyl methacrylate), and poly(n-butyl methacrylate) over certain copolymer composition ranges, but is immiscible with poly(isobutyl methacrylate) and poly(n-amyl methacrylate). The width of the miscibility window decreases with increasing size of the pendant ester group of the poly(alkyl methacrylate), and is wider than that of the corresponding poly(p-methylstyrene-co-acrylonitrile) blend system. Various segmental interaction parameters are calculated using a binary interaction model. © 1995 John Wiley & Sons, Inc.     

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     

Effects of the chemical structure on the miscibility level and properties of phenoxy/polymethacrylate blends

The important effect that even a small change in the nature of the side chain of a component of a blend has in its miscibility level was observed in a series of blends of phenoxy (Ph) with poly(methacrylates). Thus, while the Ph/poly(methyl methacrylate) blends are miscible and the Ph/poly(ethyl methacrylate) blends partially miscible, Ph/poly(butyl methacrylate) blends were almost fully immiscible. The observed miscibility of Ph/poly(butylmethyl methacrylate) indicates that the change in a component of a miscible blend of some pendant units that give rise to miscibility, by those from a different second component, which give rise to immiscibility is less important. The observed decrease in the strength of the β secondary transition of Ph was clearly related to the miscibility level of the blends. The negative effects on properties of a very low molecular weight material can be overcame by blending with a miscible second component, rendering the overall molecular weight of the blend above the critical value. The change in the nature of the side chain, apart from the negative effect on fracture properties such as ductility, also had considerable effect on the short‐term mechanical properties such as modulus of elasticity and yield stress. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2978–2986, 2000     

Polymer blends containing poly(vinylidene fluoride). Part III: Polymers containing ester,ketone, or ether groups

To further investigate the nature of the specific interaction leading to the miscibility of poly(vinylidene fluoride), PVF₂, with certain oxygen containing polymers, blends of PVF₂ with poly(ε-caprolactone), PCL, with poly(vinyl methyl ether), PVME, and with poly(vinyl methyl ketone), PVMK, were prepared. PVMK/PVF₂ blends were found to be miscible while blends of PVME/PVF₂ and PCL/PVF₂ were found not to be miscible. These results show that the specific interaction with PVF₂ involves mainly the carbonyl group rather than the entire ester group. The relative effectiveness of having this group in the chain or pendant to it is not yet resolved.     

Compatibilization of thermosetting-thermoplastic polymer blends

Polymer blends of thermosetting and thermoplastic polymers were developed by properly mixing them in the presence of compatibilizers. Two compatibilizers that are structurally and chemically similar to thermosetting and thermoplastic polymers and a compatibilizer that does not have such similarity were synthesized. Polymer blends of phenol formaldehydepoly(methyl methacrylate) and phenol formaldehyde-polystyrene were prepared by using the compatibilizers, poly(phenol formal dehyde-s-triazine-methyl methacrylate), P(PF-g-MMA), poly(phenol formaldehyde-s-triazine-styrene), P(PF-g-S), and poly (cinnamaldehyde-co-oxy propylene oxy isophthaloyl-cooxy propylene oxy fumaroyl), P(C-g-E). The effects of molecular weight and quantity of the copolymer on the compatibility of the polymer were examined. The optimum compatibility which leads to superior tensile properties of the present blends was observed with P(PF-g-MMA) and P(PF-g-S) copolymers. The superior properties were also found to occur only in the range of the optimum molecular weight and quantity of the copolymer present in the blend. The polymer blends were analyzed by differential scanning calorimetry (DSC) and Electron Microscopy. DSC scans of P(PF-g-MMA) and P(PF-g-S) copolymer blends showed a single T_g whereas the scans of P(Cg-E) copolymer blends showed an additional T_g for unblended thermoplastic fractions. The electron microscopy studies also revealed good compatibility in P(PF-g-MMA) and P(PF-g-S) copolymer blends in which the unblended thermoplastic fractions are negligibly less. The UV-vacuum and heat resistance of the P(PF-g-MMA) and P(PF-g-S) copolymer blends were found to be good.