Polymer compatibility II. The system poly(methyl methacrylate)–poly(vinyl acetate). Preparation and impact behavior

Blends of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared by mixing the polymers in the melt and in the absence of a solvent. PMMA was the major constituent of the blend. Traces of gel permeation chromatograms showed that the starting materials retain their polymeric character after Brabender processing. Data obtained from notched Izod impact strength tests at 23°C showed that blends may exhibit values ranging from about 0.3 to 0.9 ft-lb/in. notch. Differences in mix conditions afford blends which, from a phenomenologic viewpoint, consist of a mixture of two glassy polymers or of a rubbery polymer dispersed in a glassy matrix. Micrographs of a crack pattern in companion blends consisting of PMMA/PVAc 85/15 are consistent with impact strength test results.     

Compatibility studies on blends of poly(ethylene ortho-phthalate) and poly(vinyl acetate)

Blends of poly(ethylene ortho-phthalate) (PEOP), and poly(vinyl acetate) (PVAc), appear to be compatible at all compositions, from visual examination at room temperature and differential scanning calorimetry tests. Both low- (PEOP-1) and high-molecular weight (PEOP-2) alloys with PVAc show a single composition-dependent glass transition temperature (Tg). Some blends show Tg values that are below the Tg for either of the pure polymers. Couchman's equation, with a slight modification, can be used to model Tg behavior. All PEOP-2 blends with PVAc, phase separate at high temperatures, whereas PEOP-1–PVAc blends remain miscible under the same conditions. The composition dependence of the blends refractive index shows a deviation from simple additivity rules, and a similar trend is observed in density measurements. When comparing Flory's characteristic parameters for the polymers, compatibility is predicted for PVAc–PEOP blends. In contrast, blends of PEOP and poly(methyl methacrylate) (PMMA), which has a similar chemical structure to that of PVAc are predicted to be incompatible, in agreement with experimental evidence. It is suggested that compatibility is produced because of possible specific interactions between the aromatic group of PEOP and the ester carbonyl on PVAc, which is not sterically hindered as is the corresponding moiety on PMMA.     

Thermal decomposition behavior of γ‐irradiated poly(vinyl acetate)/poly(methyl methacrylate) miscible blends

Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (T_max) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the T_max corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined T_max, which may arise from the evaporation of the solvent. The second T_max was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006     

Phase behaviour and phase separation in polymer blends of poly(methyl methacrylate) with poly(vinyl acetate)

Summary Phase behaviour and phase separation in a binary polymer blends of poly(methyl methacryate) (PMMA) with poly(vinyl acetate) (PVAc) was invistigated by cloud method and light scattering. A lower critical solution temperature (LCST) type phase diagram was found. The mixture system of PMMA/PVAc is miscible. Kinetic study on demixing at the two-phase region above the LCST was carried out by light scattering.     

Solution and solid‐state NMR investigation of poly(methyl methacrylate)/poly(vinyl pyrrolidone) blends

The development of polymer blends has become very important for the polymer industry because these blends have shown to be a successful and versatile alternative way to obtain a new polymer. In this study, binary blends formed by poly(methyl methacrylate) (PMMA) and poly(vinyl pyrrolidone) were prepared by solution casting and evaluated by solution and solid‐state NMR. Variations in the microstructure of PMMA were analyzed by ¹³C solution NMR. Solid‐state NMR promotes responses on physical interaction, homogeneity, and compatibility to use these blends to understand the behavior of the ternary blends. The NMR results led‐us to acquire information on the polymer blend microstructure and molecular dynamic behavior. From the NMR solution, it was possible to evaluate the microstructure of both polymer blend components; they were atactic. From the solid state, good compatibility between both polymer components was characterized. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 372–377, 2004     

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     

Investigation of thermal,mechanical and electrochemical properties of nanocomposites based on CuO modified poly(vinyl chloride)/poly(methyl methacrylate) blend

The preparation of binary polymer blend nanocomposites with different nanomaterials is a relatively new approach to achieve desired physical, thermal, mechanical, and electrochemical properties because it has the collective effects of both polymer blending and fillers. Transition metal oxides constitute a large class among those fillers because the precursors for metal oxides are abundantly available. However, very few studies have been accomplished on incorporating transition metal oxides into binary polymer blends. In this project, cuprous oxide (CuO) nanoparticles (NPs) with a crystallite size of 24.95 nm were incorporated into poly(vinyl chloride)/poly(methyl methacrylate) (PVC/PMMA) blend, and thin films of the nanocomposites were obtained through a solution casting technique. Scanning electron microscopy, X‐ray diffraction, universal testing machine testing, thermogravimetric analysis, and cyclic voltammetry were used to study morphological, crystalline, mechanical, thermal, and electrochemical properties of the nanocomposites. Scanning electron micrographs showed that the blend was completely miscible and CuO NPs were well dispersed within the matrix. Mechanical properties greatly improved with each wt% addition of CuO NPs. Thermogravimetric analysis thermograms revealed a two‐stage degradation for neat PVC/PMMA blend and CuO/PVC/PMMA. Cyclic voltammetry results indicated a free electron transfer in neat blend that further improved with the incorporation of increasing percentage of CuO NPs. J. VINYL ADDIT. TECHNOL., 23:80–85, 2017. © 2015 Society of Plastics Engineers     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Physical aging in poly(methyl methacrylate) / poly(styrene-co-acrylonitrile) blends. I. Stress relaxation

An investigation was carried out on the effect of physical aging on viscoelastic properties of compatible polymer blends. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of six different ratios of PMMA and SAN were physically aged at different times and temperatures and then subjected to stress–relaxation tests at small strains. It was found that the shape of the stress-relaxation curve does not change with a change in blend composition, aging temperature, or aging time. A single “master curve” is presented, to which all data may be fit using 0.408 for the exponential parameter of the Williams-Watts equation. In creating the master curve, all data are shifted horizontally in time only. For a given set of experimental conditions, the relaxation time τ may be expressed in terms of blend composition, aging temperature, and aging time.     

A nonradiative energy transfer fluorescence spectroscopy study of poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility of poly(vinyl chloride)/atactic poly(methyl methacrylate (PVC/a-PMMA) blends was investigated by nonradiative energy transfer fluorescence spectroscopy using naphthalene-labeled PVC (PVC-N) with anthracene-labeled PMMA (PMMA-A), or anthracene-labeled PVC (PVC-A) with carbazole-labeled PMMA (PMMA-C). The two sets of results indicate an increase in energy transfer efficiency, corresponding to an increase in blend miscibility, as the PVC concentration increases and, more importantly, demonstrate that the same information about blend miscibility can be obtained using different donor-acceptor chromophore pairs and by changing the polymer to which the donor or the acceptor is attached. The effect of the tacticity of PMMA on its miscibility with PVC was also investigated using PMMA-C and PVC-A labeled polymers. The results confirm that PVC/a-PMMA blends are more miscible than PVC/i-PMMA blends over a large range of compositions.     

Crystallization behavior and mechanical properties of poly(ethylene oxide)/poly(L‐lactide)/poly(vinyl acetate) blends

Poly(vinyl acetate) (PVAc) was added to the crystalline blends of poly(ethylene oxide) (PEO) and poly(L ‐lactide) (PLLA) (40/60) of higher molecular weights, whereas diblock and triblock poly(ethylene glycol)–poly(L ‐lactide) copolymers were added to the same blend of moderate molecular weights. The crystallization rate of PLLA of the blend containing PVAc was reduced, as evidenced by X‐ray diffraction measurement. A ringed spherulite morphology of PLLA was observed in the PEO/PLLA/PVAc blend, attributed to the presence of twisted lamellae, and the morphology was affected by the amount of PVAc. A steady increase in the elongation at break in the solution blend with an increase in the PVAc content was observed. The melting behavior of PLLA and PEO in the PEO/PLLA/block copolymer blends was not greatly affected by the block copolymer, and the average size of the dispersed PEO domain was not significantly changed by the block copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3618–3626, 2001     

Phase behavior and properties of poly(methyl methacrylate)/poly(vinyl acetate) blends prepared via in situ polymerization

Polymer blends composed of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared via radical-initiated polymerization of methyl methacrylate (MMA) in the presence of PVAc. Differential scanning calorimetry and dynamic mechanical analysis were employed to investigate the miscibility and phase behavior of the blends. The PMMA/PVAc blends of in situ polymerization were found to be phase separated and exhibited a two-phase structure, although some chain transferring reaction between the components occurred. The phase separation resulted from the solvent effect of MMA during the in situ polymerization, which was confirmed by the investigation of phase behavior based on solution cast blending. Solubility analysis of the polymerized blends indicated that some chain transferring reaction between the components occurred during the polymerization. An abrupt increase in gel content from 21.2 to 72.4 wt % was observed when the inclusion of PVAc increased from 30 to 40 wt %, and the gel component consisted of the component polymers as shown by infrared spectroscopy studies. The thermogravimetric analysis study indicated that the inclusion of a small amount of PVAc gives rise to a marked stabilization effect on the thermal stability. The PMMA/PVAc blends exhibited increased notched impact properties with the inclusion of 5 wt % PVAc. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 675–684, 1998     

Blends of poly[3,3-bis(chloromethyl)oxetane] with poly(vinyl acetate). I. Thermal and mechanical properties

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T_g). The T_g of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a β-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations. © 1992 John Wiley & Sons, Inc.     

Effect of nanoclay on the morphology and properties of poly(methyl methacrylate)/high‐density polyethylene blends

The effect of nanoclay on the morphology and properties of poly(methyl methacrylate) (PMMA)/high‐density polyethylene (HDPE) blends was studied. A scanning electron microscopy study of the PMMA/HDPE (70/30 w/w) blends with nanoclay indicated a reduction in the average domain sizes of the dispersed HDPE phase and, hence, a better extent of mixing compared to that of the blends without any nanoclay. An X‐ray diffraction study and transmission electron microscopy revealed the localization of intercalated nanoclay in the PMMA matrix of the PMMA/HDPE (70/30 w/w) blend. However, the same effect of clay was not observed in the PMMA/HDPE (30/70 w/w) blend when HDPE became the matrix. In the PMMA/HDPE (30/70 w/w) blend, the addition of nanoclay increased the domain size of the dispersed PMMA domains by preferential location of the clays inside the PMMA domains. The addition of polyethylene‐grafted maleic anhydride in both compositions of the PMMA/HDPE blend effectively reduced the domain size of the disperse phases in the blend. However, the presence of clay increased the tensile strength and storage modulus of the PMMA/HDPE blends in both blend compositions. Thus, in the PMMA/HDPE blend, the clay platelets acted as a effective compatibilizer as long as they were dispersed mainly in the matrix phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology of phase separated blends of poly(cyclohexyl methacrylate) with poly(vinyl acetate)

Blends of poly(vinyl acetate) (PVAc) and poly(cyclohexyl methacrylate) (PCHMA) labeled by copolymerization with 4‐methacryloylamine‐4′‐nitrostilbene (Sb), with (1‐pyrenylmethyl)methacrylate (Py) or with 3‐(methacryloylamine)propyl‐N‐carbazole (Cbz), were prepared by casting dilute solutions in tetrahydrofurane (THF) or chloroform onto silanized glass plates. The resulting films were studied by epifluorescence microscopy, microfluorescence spectroscopy, DSC and optical microscopy. Epifluorescence micrography probes the chemical composition of the different regions in phase separated blends, with black areas corresponding to PVAc rich regions and colored areas corresponding to labeled PCHMA rich regions. The technique also visualizes primary and secondary morphologies, which depend on the composition of the polymer blend and on the casting solvent. Mixtures containing 80 wt % PCHMA show, in general, a bicontinuous primary morphology suggesting a spinodal demixing mechanism. Solvent effects are particularly relevant for 50% and 20% PCHMA samples showing morphologies composed of PCHMA rich domains, in a matrix of solvent‐dependent compositions. Samples cast from chloroform are more homogeneous and the matrix is always highly fluorescent. In contrast, the domains of samples cast from THF are heterogeneous in size and shape and the matrix is non‐fluorescent, being thus formed by nearly pure PVAc. Small voids are formed in the polymer‐air interface. They are submicrometric for THF cast films and disappear with annealing at 122°C. For chloroform cast samples they are much less frequent and appear well ordered, forming a mostly hexatic two dimensional network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1284–1290, 2003     

Effect of cholesteryl additive on poly(ethyl methacrylated)–poly(vinyl acetate) blend

Three different compositions (9 : 1, 7 : 3, and 1 : 1) of poly(ethyl methacrylate) (PEMA) and poly(vinyl acetate) (PVAc) are chosen to check the miscibility of a polymer pair. The 9 : 1 and 7 : 3 PEMA-PVAc blends are immiscible and have shown two distinct loss peaks in dynamic mechanical analysis (DMA) studies, while 1 : 1 PEMA-PVAc has shown a single loss peak. Immiscible composition 7 : 3 PEMA-PVAc is selected to study the effect of cholesteryl additives on the miscibility of the polymers. The additives chosen for the present studies are cholesteryl chloride, cholesteryl caprylate, and cholesteryl laurate. The DMA studies showed that all the additives caused a merging of the two loss peaks into one. X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) studies of the blend and blend with additive samples are utilized to get further information. The FTIR studies do not show any detectable change. The SEM micrographs of the blend and cholesteryl additive systems show a single-phase ordered structure, and XRD data studies indicate the presence of small crystallites.     

Nanocomposites based on vermiculite clay and ternary blend of poly(L‐lactic acid), poly(methyl methacrylate), and poly(ethylene oxide)

Vermiculite (VMT) as clay was introduced into a ternary polymer blend composed of poly(L ‐lactic acid) (PLLA), poly(methyl methacrylate) (PMMA), and poly(ethylene oxide) (PEO), whose ternary miscibility was proven within low certain contents of PMMA and PEO in PLLA. VMT was incorporated to the ternary polymer blend as matrix after proper organic modification on the clay. The organically modified vermiculite (OVMT) shows good interaction and acceptable dispersion in the ternary polymer matrix without altering the crystal structures of PLLA/PEO constituents. The effect of OVMT addition was then analyzed in isothermal crystallization by using the Avrami kinetic analysis, and the addition of OVMT is evident in altering nucleation process of the polymer blend as well as the crystal perfection. The activation energy is much lowered by the addition of OVMT, as evident from the analysis; the overall crystallization kinetic rates are increased with the incorporation of OVMT. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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 separation of poly (methyl methacrylate) / poly (styrene-co-acrylonitrile) blends in the presence of silica nanoparticles

The effects of silica nanoparticles on the phase separation of poly (methyl methacrylate)/poly (styrene-co-acrylonitrile) (PMMA/SAN) blends are studied by the rheological method. The binodal temperatures of near-critical compositions were obtained by the gel-like behavior during spinodal decomposition, which is a character of polymer blends with co-continuous morphology. The shifted Cole–Cole plot method was introduced to determine the binodal temperatures of off-critical compositions based on the appearance of shoulder-like transition in the terminal regime of blends with droplet morphology. Such method is found also applicable in nanoparticle filled polymer blends. Moreover, a new method to determine the spinodal temperature from Fredrickson-Larson mean field theory was suggested, where the concentration fluctuation's contribution to the storage modulus is used instead of the whole dynamic moduli. This method was also successfully extended to nanoparticle filled polymer blend. The influences of the concentration and the average diameter of silica particles on the phase separation temperature were studied. It was found that the small amount of the silica nanoparticles in PMMA/SAN blends will significantly change the phase diagram, which is related to the selective location of silica in PMMA. The comparisons with thermodynamic theory of particle-filled polymer blends are also discussed.     

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.