Equilibrium constants and the prediction of miscibility windows for polymer blends containing poly(tetrafluoroethylene-alt-vinyl alcohol)

Theoretical calculations of miscibility windows for binary polymer blends in which one component is an essentially alternating copolymer of tetrafluoroethylene and vinyl alcohol (FVOH) are reported. FVOH has an inherently low solubility parameter [≈ 6.2 (cal. cm^?3)^0.5] that is outside the range commonly encountered in miscible polymer blends and thus represents a stringent test of the predictive capabilities of an association model we have used in previous work. The application of this model requires that we determine dimensionless equilibrium constants describing the self-association of a model compound 3,4-pentafluorobutan-2-ol (PFB) at 25°C from infrared spectroscopic data. Analogous equilibrium constants for FVOH were scaled from those of PFB by taking into account differences in the molar volume of the model and the specific repeat of the copolymer (see M. M. Coleman, J. F. Graf, and P. C. Painter: Specific Interactions and the Miscibility of Polymer Blends, Technomic, Lancaster, PA, 1991). Equilibrium constants describing the inter-association of FVOH with ester type carbonyl groups were obtained from spectroscopic studies of miscible blends with poly(ethyl methacrylate). These equilibrium constant values were then used to calculate theoretical miscibility windows for the complete range of blends of FVOH with polymethacrylates, ethylene-co-methyl acrylate, styrene-co-methyl acrylate, and ethylene-co-vinyl acetate copolymers. Experimental results performed in our laboratories confirm the general validity of the predicted miscibility windows. © 1993 John Wiley & Sons, Inc.     

Miscibility of Halogen-containing Polymethacrylates with Various Poly(alkyl acrylate)s

The miscibility behavior of a series of halogen-containing polymethacrylates with poly(methyl acrylate), poly(ethyl acrylate), poly(n-propyl acrylate) and poly(n-butyl acrylate) was investigated by differential scanning calorimetry and for lower critical solution temperature (LCST) behavior. Poly(chloromethyl methacrylate), poly(1-chloroethyl methacrylate), poly(2-chloroethyl methacrylate), poly(2,2-dichloroethyl methacrylate), poly(2,2,2-trichloroethyl methacrylate), poly(2-fluoroethyl methacrylate) and poly(1,3-difluoroisopropyl methacrylate) are miscible with some of the poly(alkyl acrylate)s. Most of the miscible blends show LCST behavior. However, poly(3-choloropropyl methacrylate), poly(3-fluoropropyl methacrylate), poly(4-fluorobutyl methacrylate), poly(1,1,1,3,3,3-hexafluoroisopropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate) are immiscible with any of the poly(alkyl acrylate)s studied. © 1997 John Wiley & Sons, Ltd.     

Synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl) methyl methacrylate‐co‐ethyl acrylate] by incorporation of carbon dioxide into epoxide polymer and the miscibility behavior of its blends with poly(methyl methacrylate) or poly(vinyl chloride)

This study was related to the investigation of the chemical fixation of carbon dioxide to a copolymer bearing epoxide and the application of the cyclic carbonate group containing copolymer‐to‐polymer blends. In the synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl) methyl methacrylate‐co‐ethyl acrylate] [poly(DOMA‐co‐EA)] from poly(glycidyl methacrylate‐co‐ethyl acrylate) [poly(GMA‐co‐EA)] and CO₂, quaternary ammonium salts showed good catalytic activity. The films of poly(DOMA‐co‐EA) with poly(methyl methacrylate) (PMMA) or poly(vinyl chloride) (PVC) blends were cast from N,N′‐dimethylformamide solution. The miscibility of the blends of poly(DOMA‐co‐EA) with PMMA or PVC have been investigated both by DSC and visual inspection of the blends. The optical clarity test and DSC analysis showed that poly(DOMA‐co‐EA) containing blends were miscible over the whole composition range. The miscibility behaviors were discussed in terms of Fourier transform infrared spectra and interaction parameters based on the binary interaction model. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1472–1480, 2001     

Miscibility maps for copolymer - copolymer blends: A comparison of theoretical predictions to experimental studies of poly(styrene-co-vinyl phenol) blends with poly(ethylene-co-methyl acrylate)

We report the results of theoretical and experimental studies of random amorphous styrene-co-vinyl phenol (STVPh) copolymer blends with ethylene-co-methyl acrylate (EMA). This work is a natural extension to our recently reported studies of the phase behavior of analogous STVPh blends with an homologous series of poly(n-alkyl methacrylate) homopolymers, where we employed an association model together with parameters obtained from studies of miscible homopolymer blends. Here we emphasize that there is no conceptual difference between the average chemical repeat of a random copolymer and that of an analogous repeat unit of a homopolymer containing the same number and type of functional groups. The theoretically calculated miscibility maps for STVPh - EMA copolymer blends are in outstanding agreement with experiment.     

Miscible blends of amorphous polymers

Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH₂/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.     

Blends of styrene/maleic anhydride copolymers with polymethacrylates

The phase behavior of a series of styrene/maleic anhydride (SMA) copolymers with various polyacrylate and polymethacrylate homopolymers has been investigated using various techniques. None of the polyacrylates are miscible with SMA copolymers. Poly (methyl methacrylate) (PMMA) poly(ethyl methacrylate) (PEMA) and poly(n-propyl methacrylate) (PnPMA), are miscible with these copolymers over a certain range of maleic anhydride contents; whereas, the higher methacrylates apparently have no region of miscibility. For PEMA and PnPMA, the miscibility windows extend through 0% MA; hence, polystyrene is miscible with these polymethacrylates although the lower critical solution temperature is quite low. The exothermic heat of mixing styrene and ester analogs found here supports the observed miscibility of polystyrene with ethyl, n-propyl, and cyclohexyl (reported elsewhere) methacrylates. Lattice fluid interaction parameters for styrene-methacrylate obtained from the cloud points of these blends agree quite well with the Flory—Huggins parameters obtained from copolymer miscibility windows.     

Liquid chromatography of polymer mixtures applying a combination of exclusion and full adsorption mechanisms. 5. Six-component blends of chemically similar polymers

The separation of six-component blends of chemically similar homopolymers utilising the full adsorption-desorption (FAD) process is presented. The main advantage of the FAD approach over other methods represents the successive and independent size- exclusion chromatography (SEC) characterisation of all blend components. The method is based on the full adsorption and retention of all n or n−1 components of the polymer blend from an adsorption promoting liquid (ADSORLI) in a small FAD column. Nonadsorbed macromolecules are forwarded directly into SEC for molecular characterisation. Next, appropriate displacers are successively applied to the FAD column to selectively release preadsorbed blend constituents into the on-line SEC column. Dynamic integral desorption isotherms for single constituents, as well as for polymer blends to be analysed, allow identification of optimal displacer compositions to release just one kind of macromolecule. Model polymer blends containing polystyrene (PS), poly(lauryl methacrylate), poly(butyl methacrylate), poly(ethyl methacrylate), poly(methyl methacrylate) and poly(ethylene oxide) (PEO) or, alternatively, PS, poly(2-ethylhexyl acrylate), poly(butyl acrylate), poly(ethyl acrylate), poly(methyl acrylate) and PEO of similar molar masses can be separated and characterised in one multistep run using nonporous silica FAD packing, toluene as an ADSORLI and its mixtures with a desorption promoting liquid such as ethyl acetate, tetrahydrofuran or dimetylformamide to form displacers with appropriate desorption strength. Received: 9 September 1998 Accepted in revised form: 16 November 1998     

Compatibility and thermodynamic interaction in random copolymer blends

Some random copolymer blends have been found to be miscible in a certain range of copolymer composition even though any combinations of their corresponding homopolymers are not miscible. The opposite case may exist. These two types of miscibility behaviors have been called miscibility and immiscibility windows, respectively. Such two miscibility behaviors were discussed by application of the equation-of-state theory to copolymer systems. The equation-of-state theory gives two kinds of temperature dependences of the interaction parameter X: (a) a U-shaped curve which is always positive regardless of temperature and (b) a function increasing monotonically from negative to positive values. Infinite molecular weight polymer blends are immiscible over all the temperature in the case (a), while in the case (b) two polymers are miscible below a temperature at which X=0. Applying the equation-of-state theory to random copolymer blends in which miscibility changes with the copolymer composition at a certain temperature to be immiscible → miscible → immiscible, two types of dependences of the temperature-X curve can be obtained: (1) (a) → (b) → (a) dependent on the copolymer composition and (2) (b) regardless of the copolymer composition. For the blends in which miscibility changes with the copolymer composition to be miscible → immiscible → miscible, there can be two types: (3) (b) → (a) → (b) and (4) (b) regardless of the copolymer composition. It may be concluded that socalled miscibility and immiscibility windows should be defined by the types (1) and (3), respectively. The equation-of-state theory for random copolymer systems was applied to the real systems. The blends of poly(vinyl acetate-co-vinyl chloride) and poly(ethylene-co-vinyl acetate) were of the type (1), while it was suggested that the blends of poly(vinyl acetate-co-vinyl chloride) and poly(isobutyl methacrylate-co- butyl methacrylate) may be of the type (4) though this system behaved like an immiscibility window at a certain temperature.     

Spectroscopic Ellipsometry for Characterization of Thin Films of Polymer Blends

Morphology, composition, miscibility, interdiffusion, and interactions at interfaces are important quantities of polymer blends. Many of these parameters can be probed with spectroscopic ellipsometry. Ellipsometry in the visible spectral range is very suitable for determination of thicknesses and the high frequency refractive indices of thin organic films. However the spectral contrast is low for many polymers in comparison to infrared spectroscopic ellipsometry (IRSE) where specific contributions of the molecular vibrations are probed. In the presented study the infrared optical constants of a double layer (206.6 nm in total) of poly(n-butyl methacrylate) (PnBMA) and poly(vinyl chloride) (PVC) and of the films of the single compounds have been determined with optical simulations using layer models. The multiple layer model served for simulation of the ellipsometric spectra taken after an annealing induced mixing process in a polymeric double layer. The ellipsometric spectra of a not completely mixed sample could be fitted in a three-layer model, in which a mixed interphase in between the two layers of the polymers is formed due to interdiffusion.     

Characterization of the interaction energies for polystyrene blends with various methacrylate polymers

The binary interaction energies between styrene and various methacrylates were determined from newly examined phase boundaries with lattice–fluid theory. Because the blends of polystyrene (PS) and poly(cyclohexylmethacrylate) (PCHMA) were only miscible at high molecular weights when the blends were prepared by solution casting from tetrahydrofuran, we examined the miscibility of other blends by changing the molecular weights of PS or methacrylate polymers. On the basis of the phase‐separation temperature caused by the lower critical solution temperature, the miscibility of PS with the various methacrylates appeared to be in the order PCHMA > poly(n‐propyl‐methacrylate) (PnPMA) > poly(ethyl methacrylate) (PEMA) > poly(n‐butyl‐methacrylate) (PnBMA) > poly(iso‐butyl‐methacrylate) > poly(methyl methacrylate) (PMMA) > poly(tert‐butyl methacrylate), and the branching of butylmethacrylate appeared to decrease the miscibility with PS. The interaction energies between PS with various methacrylates obtained from phase boundaries with lattice–fluid theory reached minimum value corresponding to the styrene/n‐propylmethacrylate interaction. They were in the order PnPMA < PEMA < PCHMA < PnBMA < PMMA. The difference in the order of miscibility and interaction energies might be attributed to the terms related to the compressibility. The phase‐separation temperatures calculated with the interaction energies obtained here indicated that the PS/PEMA and PS/PnPMA blends at high molecular weights were miscible, whereas the PS/PnBMA blends were immiscible at high molecular weights. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2666–2677, 2000     

Phase behavior of tetramethylpolycarbonate blends with styrene‐based methacrylate copolymers and their interaction energies

The miscibility of tetramethylpolycarbonate (TMPC) blends with styrenic copolymers containing various methacrylates was examined, and the interaction energies between TMPC and methacrylate were evaluated from the phase‐separation temperatures of TMPC/copolymer blends with lattice‐fluid theory combined with a binary interaction model. TMPC formed miscible blends with styrenic copolymers containing less than a certain amount of methacrylate, and these miscible blends always exhibited lower critical solution temperature (LCST)‐type phase behavior. The phase‐separation temperatures of TMPC blends with copolymers such as poly(styrene‐co‐methyl methacrylate), poly(styrene‐co‐ethyl methacrylate), poly(styrene‐co‐n‐propyl methacrylate), and poly(styrene‐co‐phenyl methacrylate) increase with methacrylate content, go through a maximum, and decrease, whereas those of TMPC blends with poly(styrene‐co‐n‐butyl methacrylate) and poly(styrene‐co‐cyclohexyl methacrylate) always decrease. The calculated interaction energy for a copolymer–TMPC pair is negative and increases with the methacrylate content in the copolymer. This would seem to contradict the prediction of the binary interaction model, that systems with more favorable energetic interactions have higher LCSTs. A detailed inspection of lattice‐fluid theory was performed to explain such phase behavior. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1288–1297, 2002     

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 study in the blends of novel poly (styrene-co-4-vinylphenyldimethylsilanol) and poly (n-butyl methacrylate)

The miscibility of poly (styrene-co-4-vinylphenyldimethylsilanol) (ST-VPDMS) and poly (n-butyl methacrylate) (PBMA) blends has been investigated by means of DSC and FT-IR spectroscopy. It was found that miscible blends were formed only for the copolymers containing 9–34 mol % 4-vinylphenyldimethylsilanol (VPDMS). The glass transition behavior of the miscible blends was analyzed by recently proposed equations in terms of the physical meaning of the fitting parameters. The results of FT-IR study were found to be fully consistent with the observation of the miscibility window obtained from glass transition temperature measurements. Quantitative information concerning intermolecular hydrogen bond interaction in the carbonyl stretching vibration region of the miscible blends was obtained by curve-fitting method. © 1994 John Wiley & Sons, Inc.     

Miscibility as a function of copolymer composition in blends of a random copolymer and a homopolymer

Random copolymers of n-butyl acrylate (BA) and cyclohexyl acrylate (CHA) were synthesized by solution polymerization in cyclohexane. Blends of polystyrene with the poly(CHA-stat-BA) copolymers were prepared by solvent casting and coprecipitation. The miscibility of the blends was characterized by means of differential scanning calorimetry. While blends with a low content of CHA in the copolymer showed two characteristic glass-transition temperatures of the corresponding blend components, those with a CHA content higher than 70% presented good compatibility. Phase separation of the miscible blends took place after annealing at 200 °C for 1 h, which implies an upper miscibility gap (lower critical solution temperature).     

Blends of alkylated comb-like polyacrylates with copolymers with a controlled ethylene-vinyl acetate composition

The thermodynamic and morphological behaviors of poly(octadecyl acrylate) (PODA) with flexible ethylene-co-vinyl acetate copolymer (EVA) with a controlled amount of vinyl acetate units in the copolymer were investigated over the entire composition region by thermal analysis, Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, optical microscopy, and light scattering. Thermal analysis revealed that the EVA portion interferes with the side chain crystallization of PODA, as the number of crystallized methylene units in PODA was calculated from the heat of fusion of the paraffinic side chain crystals. The hexagonal packing of side chains was also confirmed by FTIR and x-ray diffraction. Optical microscope studies showed a homogeneous melt state beyond the melting temperature of EVA, but clearly showed two phases over the whole range of composition in EVA20, EVA40, and EVA50/PODA blends after the side chain crystallization of PODA. Light scattering showed the single circular halo as the evidence of phase separation when the samples were cooled to below the crystallization temperature. The changes in crystallization cannot be accounted for by the miscibility, because liquid-liquid phase separation competes with crystallization. © 1996 John Wiley & Sons, Inc.     

Δχ effects on the miscibility of polymer blends

The Δχ effect on the miscibility of polymer blends prepared by solution-casting has been investigated using the mixture of poly(methyl methacrylate)(PMMA) with poly(vinyl acetate) (PVAc). The PMMA/PVAc blends have been prepared by casting from eleven different solutions. The Δχ effect of the solution–cast PMMA/PVAc blends was discussed in terms of Hansen's specified solubility parameters. It was found that the miscibility of the blends could be defined mainly by the solubility parameter contributed by the hydrogen–bonding of a solvent.     

Miscibility and crystallization behavior in blends of poly(methyl methacrylate) and poly(vinylidene fluoride): Effect of star‐like topology of poly(methyl methacrylate) chain

A tetraarmed star‐shaped poly(methyl methacrylate) (s‐PMMA) was synthesized via atom transfer radical polymerization with 2‐bromoisobutyryl pentaerythritol as the initiator. For comparison, a linear PMMA with the identical molecular weight (l‐PMMA) was also prepared. The blends of the two PMMA samples with poly (vinylidene fluoride) (PVDF) were prepared to investigate the effect of macromolecular topological structure on miscibility and crystallization behavior of the binary blends. The behavior of single and composition‐dependent glass transition temperatures was found for the blends of s‐PMMA with PVDF, indicating that the s‐PMMA is miscible with PVDF in the amorphous state just like l‐PMMA. The miscibility was further evidenced by the depression of equilibrium melting points. It is found that the blends of s‐PMMA and PVDF displayed the larger k value of Gordon–Taylor equation than the blends of l‐PMMA and PVDF blends. According to the depression of equilibrium melting points, the intermolecular parameters for the two blends were estimated. It is noted that the s‐PMMA/PVDF blends displayed the lower interaction parameter than l‐PMMA/PVDF blends. The isothermal crystallization kinetics shows that the crystallization of PVDF in the blends containing s‐PMMA is faster than that in the blends containing the linear PMMA. The surface‐folding free energy of PVDF chains in the blends containing s‐PMMA is significantly lower than those in the blends containing l‐PMMA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2580–2593, 2007     

Thermal degradation of poly(alkyl acrylates). II. Primary esters: Ethyl,n-propyl,n-butyl,and 2-ethylhexyl

Quantitative analyses of the products of thermal degradation of poly(ethyl acrylate), poly(n-propyl acrylate), poly(n-butyl acrylate) and poly(2-ethylhexyl acrylate) have been made, principally by the combined application of GLC and mass and infrared spectroscopy. Data are recorded in mass balance tables. The major gaseous products are carbon dioxide and the olefin corresponding to the ester group. The minor gaseous products include the corresponding alkane, the alkane/olefin ratio being of the order of 10^?2–10^?3, and traces of carbon monoxide and hydrogen. The alcohol corresponding to the alkyl group is the major liquid product but there are also traces of monomer and the corresponding methacrylate. Alcohol production exhibits autocatalytic properties. The chain fragment fractions of the products are colored yellow and have average chain lengths of 3.2, 3.3, 3.6, and 5.6 for the ethyl, n-propyl, n-butyl and 2-ethylhexyl esters, respectively. The infrared spectra are similar to those of the parent polymers but with well defined differences. Insolubility develops in the ethyl, n-propyl, and n-butyl esters, but the residual material from poly(2-ethylhexyl acrylate) remains soluble even at very advanced stages of degradation. All of these products and reaction characteristics are accounted for in terms of radical reactions with a unique initiation step.     

Investigating polymer blend miscibility with forward recoil spectrometry

We tested forward recoil spectrometry (FRES) as a method to determine miscibility by measuring coexistence compositions in binary polymer blends. In this study, equilibrium phase compositions were determined for a compositionally symmetric poly(styrene‐ran‐methyl methacrylate) random copolymer (S_0.49‐r‐MMA) and two homopolymers, deuterated polystyrene (dPS) and deuterated poly(methyl methacrylate) (dPMMA). Sample preparation, film dewetting, and beam damage were addressed, and the results for these polymer blends were in good agreement with those obtained through other experimental techniques. Deuteration had a strong effect on the miscibility of the dPS/S_0.49‐r‐MMA and dPMMA/S_0.49‐r‐MMA blends, to the extent that the asymmetric miscibility observed separately for the PS/S_0.49‐r‐MMA and PMMA/S_0.49‐r‐MMA blends was not found. Although this deuteration effect may limit the applicability of FRES for some polymer systems, the accuracy with which phase compositions can be determined with FRES makes it an attractive alternative to other less quantitative methods for investigating blend miscibility. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1547–1552, 2000     

Miscibility of poly(styrene‐co‐butyl acrylate) with poly(ethyl methacrylate): Existence of both UCST and LCST

A miscible homopolymer–copolymer pair viz., poly(ethyl methacrylate) (PEMA)–poly(styrene‐co‐butyl acrylate) (SBA) is reported. The miscibility has been studied using differential scanning calorimetry. While 1 : 1 (w/w) blends with SBA containing 23 and 34 wt % styrene (ST) become miscible only above 225 and 185 °C respectively indicating existence of UCST, those with SBA containing 63 wt % ST is miscible at the lowest mixing temperature (i.e., T_g's) but become immiscible when heated at ca 250 °C indicating the existence of LCST. Miscibility for blends with SBA of still higher ST content could not be determined by this method because of the closeness of the T_g's of the components. The miscibility window at 230 °C refers to the two copolymer compositions of which one with the lower ST content is near the UCST, while the other with the higher ST content is near the LCST. Using these compositions and the mean field theory binary interaction parameters between the monomer residues have been calculated. The values are χ_ST‐BA = 0.087 and χ_EMA‐BA = 0.013 at 230 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 369–375, 2000