Poly(ethylene oxide)/poly(methyl methacrylate) blends: Influence of tacticity of poly(methyl methacrylate) on blend structure and miscibility

The influence of different configurations of poly(methyl methacrylate) on the miscibility and superstructure of poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA) blends was examined using small-angle X-ray scattering and differential scanning calorimetry. The blends prepared by solution casting were isothermally crystallized at 48°C. The miscibility, the melting behaviour, the glass transition temperature and the structural parameters of the blends were strongly dependent on the tacticity and blend composition. The small-angle X-ray intensity profiles were analysed using a recently developed methodology. For the poly(ethylene oxide)/atactic poly(methyl methacrylate) (PEO/APMMA) and poly(ethylene oxide)/syndiotactic poly(methyl methacrylate) (PEO/SPMMA) blends, the long period and the amorphous and transition region thicknesses increased with increase of PMMA content, whereas for the poly(ethylene oxide)/isotactic poly(methyl methacrylate) (PEO/IPMMA) blends they are independent of composition. The structural properties of the blends were attributed to the presence of non-crystallizable material in the interlamellar or interfibrillar regions, depending on PMMA tacticity. From the glass transition and melting temperatures, it has been supposed that one homogeneous amorphous phase is present in the case of PEO/APMMA and PEO/SPMMA blends and that the PEO/IPMMA amorphous system is phase-separated. The free-volume contribution to the energy of mixing for the various tactic PMMAs is hypothesized to be responsible for the difference in mixing behaviour.     

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.     

Blends of poly(ethylene oxide) and poly(4-vinylphenol-co-2-hydroxyethyl methacrylate): thermal analysis, morphological behaviour and specific interactions

DSC and optical microscopy were used to determine the miscibility and crystallinity of blends of poly(ethylene oxide) (PEO) with poly(4-vinylphenol-co-2-hydroxyethyl methacrylate) (PVPh-HEM). A single glass transition temperature was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherullites is observed, as PVPh-HEM is added. FTIR was used to probe the intermolecular specific interactions of the blends and the miscibility of the blend is mainly attributed to PVPh-HEM/PEO intermolecular interactions via hydrogen bonding.     

Miscibility and mechanical properties of an amine‐cured epoxy resin blended with poly(ethylene oxide)

Blends composed of diaminodiphenylmethane bisphenol‐A epoxy resin and poly(ethylene oxide) (PEO) were prepared via in situ curing reaction of epoxy in the presence of PEO. The miscibility of the blends before and after curing was established by thermal (differential scanning calorimetry, DSC), microstructural (atomic force microscopy) and dynamic mechanical analysis. Fourier transform infrared spectroscopy indicated that the OH groups developed through cure reactions interact by hydrogen bonding with PEO. After crystallinity analysis by DSC, the interaction parameter was determined through the depression of the equilibrium melting temperature. Mechanical properties of the miscible blends do not show any significant change, although improvement of fracture toughness has been observed with respect to the matrix properties. Copyright © 2006 Society of Chemical Industry     

Poly(ethylene oxide)–polyelectrolyte blends: viscometric and thermal analysis behaviour

The miscibility of binary poly(ethylene oxide) (PEO) and sodium poly(4‐styrene sulphonate) (PSS) or [3,6]‐ionene (ION) systems, was analysed in aqueous solutions and in the solid state by viscometry and thermal analysis, respectively. Both techniques indicate partial miscibility of PEO–PSS and immiscibility of PEO–ION blends. In water solution, the partial miscibility of the PEO–PSS system is probably due to the counterion Na⁺ which can partially provide the driving force association in a similar manner to that observed for PEO–surfactant systems. In blend films, the PEO–polyelectrolyte interaction is also analysed in terms of the effect on the PEO crystallization observed through optical microscopy, and the results indicate compatibility between the components in the PEO–PSS system. © 2000 Society of Chemical Industry     

Gas chromatographic determination of the interaction parameter of poly(ethylene oxide)/poly(methyl methacrylate) blends

Inverse gas chromatography (IGC) has been used to investigate thermodynamic miscibility of a molten poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blend. Toluene, benzene, and chloroform have been employed as probes in pure and mixed stationary phases of these polymers. Experimental measurements have been taken over a narrow range of temperatures because of the high PMMA glass transition temperature as well as the degradation of the PEO. The interaction parameter χ₂₃ determined at 150°C is slightly negative and dependent on the interacting probe, as has been also noted in previous chromatographic studies on polymer-polymer miscibility. The last section is devoted to a model calculation, using Flory's equation of state theory. Different χ₂₃-concentration curves have been simulated, with the interaction energy parameter X₂₃ as an adjustable parameter.     

Tacticity effects on the miscibility behavior of poly(methyl methacrylate)/poly(ethylene oxide-b-dimethylsiloxane-b-ethylene oxide) blends

The miscibility of a triblock copolymer poly(ethylene oxide)-poly(dimethylsiloxane)-poly(ethylene oxide) with syndiotactic and isotactic poly(methylmethacrylate) wasstudied. Although isotactic poly(methyl methacrylate) (PMMA) was miscible with poly(ethylene oxide) (PEO) in the pure state, it was immiscible with the PEO end blocks in the copolymer. In comparison, the syndiotactic poly(methyl methacrylate) (sPMMA) was miscible with the PEO blocks as indicated by melting point depression, decrease in crystallinity, and slower rate of spherulite growth of PEO. When blends of the triblock copolymer were cooled to low temperatures, the poly(dimethylsiloxane) (PDMS) middle block which resided in the interlamellar region of PEO spherulites also crystallized; the development of PDMS crystals was clearly suppressed at high sPMMA contents.On leave from Union Chemical Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan     

The study of poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyrene)/poly(ethylene oxide) blends

Different hydroxyl content poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyene) [PS(OH)‐X] copolymers were synthesized and blends with 2,2,6,6‐tetramrthyl‐piperdine‐1‐oxyl end spin‐labeled PEO [SLPEO] were prepared. The miscibility behavior of all the blends was predicted by comparing the critical miscible polymer–polymer interaction parameter (χ_crit) with the polymer–polymer interaction parameter (χ). The micro heterogeneity, chain motion, and hydrogen bonding interaction of the blends were investigated by the ESR spin label method. Two spectral components with different rates of motion were observed in the ESR composite spectra of all the blends, indicating the existence of microheterogeneity at the molecular level. According to the variations of ESR spectral parameters T_a, T_d, ΔT, T_50G and τ_c, with the increasing hydroxyl content in blends, it was shown that the extent of miscibility was progressively enhanced due to the controllable hydrogen bonding interaction between the hydroxyl in PS(OH) and the ether oxygen in PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2312–2317, 2004     

Miscibility in blends of linear and branched poly(ethylene oxide) with methacrylate derivative random copolymers and estimation of segmental χ parameters

Miscibility in the blends of poly(ethylene oxide) (PEO) with n-hexyl methacrylate-methyl methacrylate random copolymers (HMA-MMA) and 2-ethylhexyl methacrylate-MMA random copolymers (EHMA-MMA) was evaluated using glass transition and light scattering methods. EHMA-MMA was more miscible with PEO than HMA-MMA. Both blends of PEO with HMA-MMA and EHMA-MMA showed UCST-type miscibility although homopolymer blends PEO/PMMA were predicted to be of LCST-type. This was attributed to an increase in the exchange enthalpy with increasing HMA or EHMA composition in the random copolymer. From the copolymer composition dependence of miscibility the segmental χ parameters of HMA/MMA, EHMA/MMA, EO/HMA and EO/EHMA were estimated using the Flory-Huggins theory extended to random copolymer systems. Miscibility in the blends of branched PEO with HMA-MMA whose HMA copolymer composition was 0.16 was compared with that in the linear PEO blends. The former blends were more miscible with HMA-MMA than the latter one by about 35 °C at the maximum cloud point temperature.     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

Physical aging in the mechanical properties of miscible polymer blends

Changes in mechanical properties during isothermal physical aging were investigated for three miscible blends: polystyrene (PS)/poly(2,6-dimethyl 1,4-phenylene oxide) (PPO), PS/poly(vinylmethylether) (PVME), and poly(methylmethacrylate) (PMMA)/poly(ethyleneoxide) (PEO). The kinetics of stress relaxation was investigated for the blend, dilute in one component, and compared with that of the neat major component at equal temperature distances, Tg-T, from the midpoint glass transition temperature. It is demonstrated that for all three blends, the mean stress relaxation time (τ) does not scale with Tg-T. For PS/PPO and PS/PVME blends, the stress relaxation rates are faster compared to neat PS; for PMMA/PEO, they are slower than for neat PMMA. Two effects appear to be important in contributing to this discrepancy. First, addition of the second component produces a change in the packing density of the blend: less dense for PS/PPO and PS/PVME; more dense for PMMA/PEO. Comparison of average free volume hole sizes and fractional free volumes measured via orthopositronium annihilation lifetime measurements for all three blends versus the pure constituents are qualitatively consistent with this interpretation. Second, because of the presence of concentration fluctuations in the blend, it is expected that the initial stress decay is dominated by regions enriched in the more mobile component. From observations of the change in width of the stress relaxation time distribution, this effect appears to be particularly significant in the PS/PVME blend. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 483–496, 1997     

New method of determining miscibility in binary polymer blends through hydrodynamic interaction: The free volume approach

A new method has been developed to determine the probability of miscibility in binary polymer blends through hydrodynamic interaction. This is achieved by the measurement of the free volume content in blends of carefully selected systems—styrene acrylonitrile (SAN)/poly(methyl methacrylate) (PMMA), PMMA/poly(vinyl chloride) (PVC), and PVC/polystyrene (PS)—with positron annihilation lifetime spectroscopy. The free volume content can predict the miscible/immiscible nature of the blends but provides no information on the extent of miscibility for different compositions of the blends. We have generalized a model used to understand the viscometric behavior of polymer/solvent systems to polymer/polymer systems through the free volume approach. This model provides two important parameters: a geometric factor (γ) and a hydrodynamic interaction parameter (α). γ depends on the molecular architecture, whereas α accounts for the excess friction at the interface between the constituents of the blend, and we propose that α can serve as a precursor to miscibility in a system and indicate which composition produces a high probability of miscibility. The efficacy of this proposition has been checked with measured free volume data for the three blend systems. The SAN/PMMA system produces a maximum α value of ?209 at 20% PMMA; PVC/PMMA produces a maximum α value of ?57 at 10% PMMA. Interestingly, for the PS/PVC system, α is close to zero throughout the entire concentration range. Therefore, we infer that α is perhaps an appropriate parameter for determining the composition‐dependent probability of miscibility in binary blend systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatibilizing effects of poly(styrene-graft-ethylene oxide) in blends of polystyrene and butyl acrylate polymers

The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (T_g) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a T_g reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc.     

Correlation between interactions, miscibility, and spherulite growth in crystalline/crystalline blends of poly(ethylene oxide) and polyesters

Crystalline/crystalline blend systems of poly(ethylene oxide) (PEO) and a homologous series of polyesters, from poly(ethylene adipate) to poly(hexamethylene sebacate), of different CH₂/CO ratios (from 3.0 to 7.0) were examined. Correlation between interactions, miscibility, and spherulite growth rate was discussed. Owing to proximity of blend constituents' T_g's, the miscibility in the crystalline/crystalline blends was mainly justified by thermodynamic and kinetic evidence extracted from characterization of the PEO crystals grown from mixtures of PEO and polyesters at melt state. By overcoming experimental difficulty in assessing the phase behavior of two crystalline polymers with closely spaced T_g's, this work has further extended the range of polyesters that can be miscible with PEO. The interaction parameters (χ₁₂) for miscible blends of PEO with polyesters [poly(ethylene adipate), poly(propylene adipate), poly(butylene adipate), and poly(ethylene azelate) with CH₂/CO = 3.0-4.5] are all negative but the values vary with the polyester structures, with a maximum for the blend of PEO/poly(propylene adipate) (CH₂/CO = 3.5). The values of interactions are apparently dependent on the structures of the polyester constituent in the blends; interaction strength for the miscible PEO/polyester systems correlate in the same trend with the PEO crystal growth rates in the blends.     

On the deformation of poly(methyl methacrylate) poly(ethylene oxide) blends: A molecular characterization by small-angle neutron scattering

The deformation behavior of miscible amorphous/amorphous PMMA/PEO poly(methyl methacrylate)/poly(ethylene oxide) blends was compared with that of pure PMMA. Small-angle neutron scattering experiments were performed on labeled systems made of PEO + D-PMMA + HPMMA. Characteristic molecular parameters such as radius of gyration, Rg, molecular weight, M_w, and interaction parameter, X, were extracted from the coherent scattering cross sections, Molecular anisotropy was measured on the solid state coextruded samples, and the observed drawing efficiency is compared with, the results of shrinkage tests. In the case of PMMA/PEO blends, anomalous scattering behavior precludes any quantitative Interpretation of the scattering patterns, but revealed important structural changes upon drawing, namely a deformation-induced phase separation.     

Miscibility and phase behavior in thermosetting blends of polybenzoxazine and poly(ethylene oxide)

Thermosetting polymer blends composed of polybenzoxazine (PBA-a) and poly(ethylene oxide) (PEO) were prepared via in situ curing reaction of benzoxazine (BA-a) in the presence of PEO, which started from the initially homogeneous mixtures of BA-a and PEO. Before curing, the BA-a/PEO blends displayed the single and composition-dependant glass transition temperatures (T_g's) in the entire blend composition, and the equilibrium melting point depression was also observed in the blends. It is judged that the BA-a/PEO blends are completely miscible. The miscibility was mainly ascribed to the contribution of entropy to mixing free energy since the molecular weight of BA-a is rather low. However, phase separation occurred after curing reaction at the elevated temperature, which was confirmed by differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM). It was expected that the PBA-a/PEO blends would be miscible since PBA-a possesses a great number of phenolic hydroxyls in the molecular backbone, which are potential to form the intermolecular hydrogen bonding interactions with oxygen atoms of PEO and thus would fulfill the miscibility of the blends. To interpret the experimental results, we investigated the variable temperature Fourier transform infrared spectroscopy (FTIR) of the blends via model compound. The FTIR results indicate that the phenolic hydroxyl groups could not form the efficient intermolecular hydrogen bonding interactions at the elevated temperatures (e.g. the curing temperatures), i.e. the phenolic hydroxyl groups existed mainly in the non-associated form in the system. Therefore, the decrease of the mixing entropy still dominates the phase behavior of thermosetting blends at the elevated temperature.     

Blends containing polymers of epichlorohydrin and ethylene oxide. II. Polyacrylates

The phase behavior of blends of various polyacrylate homopolymers and two commercial ethyl acrylate (EA) and n-butyl acrylate (nBA) copolymers with polyepichlorohydrin (PECH), poly(ethylene oxide) (PEO), and a copolymer of epichlorohydrin and ethylene oxide [P(ECH/EO)] was examined using differential scanning calorimetry and optical indications of phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Poly(methylacrylate) (PMA) was shown to be miscible with PECH, PEO, and P(ECH/EO) while only PECH was found to be miscible with the higher polyacrylates: poly(ethyl acrylate), EA copolymer, poly(n-propyl acrylate), and nBA copolymer. However, even PECH was found to be only partially miscible with poly(n-butyl acrylate). In general, glass transitions observed by DSC for blends were not as broad as those found in corresponding polymethacrylate blends. 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 polyacrylates decreases with increasing size of the alkyl group. The commercial copolymers seem to interact more exothermically with PECH than the corresponding homopolymers. The interaction with PMA is apparently larger for PECH than for PEO or for P(ECH/EO). Interactions for the latter two are about the same. The apparently exothermic interactions between ECH and EO units are not sufficiently strong to preclude miscibility of P(ECH/EO) with PMA. As for the polymethacrylates, it is clear that the chlorine moeity of PECH is needed for miscibility with higher polyacrylates.     

Processable aromatic polyesters based on bisphenol derived from cashew nut shell liquid: synthesis and characterization

The miscibility of chitosan/poly(ethylene oxide) (CS/PEO) blends was investigated by a combination of experiment and molecular simulation. Results from X-ray diffraction (WAXD) and thermal analysis (DSC) suggest that the maximum miscibility was seen at the PEO weight fraction (w _PEO) =0.2; the optimum stoichiometric ratio for CS and PEO functional groups. The change in vibrational frequencies from infrared spectra was attributed to the specific interaction between PEO ether oxygen with the amino and hydroxyl groups of CS. Radial distribution functions (RDF) from MD simulation suggest that all CS functional groups (NH₂, C3-OH, and C6-OH) can interact with PEO ether groups for which NH₂ has the highest activity. For CS hydroxyl groups, a more significant contribution of C6-OH rather than C3-OH groups that interact with PEO ether oxygen was observed. The interaction parameter (χ) determined from MD simulation was in good agreement with that of the DSC experiment (χ_CS-PEO?=?-0.21). Based on a comparison between χ and χ _critical , CS/PEO blend was predicted to be miscible for w _PEO <0.58 with a maximum at w _PEO =0.2. In addition, the order parameter from the mesoscale simulation was employed to monitor the phase separation in these blends. From MesoDyn simulation, the miscibility was decreased with increasing PEO content, and miscible CS/PEO blends were obtained only with w _PEO <0.58, in good agreement with MD simulation and experiment.     

Ionomeric blends of poly(ethylene oxide) with poly(styrene‐co‐maleic anhydride) ionomer: Miscibility,crystallization, and melting behavior

The miscibility and crystallization behavior of poly(ethylene oxide) (PEO) and poly(styrene‐co‐maleic anhydride) ionomer (SMAI) blends were studied by the dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). This study has demonstrated that the presence of ion–dipole interactions enhances the miscibility of otherwise immiscible polymers in the PEO and high molecular weight poly(styrene‐co‐maleic anhydride) (SMA). The effect of ion–dipole interactions on enhancing miscibility is confirmed by the presence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of the PEO component. The equilibrium melting temperature of PEO in the blends are obtained using Hoffman‐Weeks plots. The interaction energy density, β, is calculated from these data using the Nishi‐Wang equation. The results suggest that PEO and SMAI blends are thermodynamically miscible in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1–7, 2000     

MesoDyn modeling study of the phase morphologies of miktoarm poly(ethylene oxide)‐b‐poly(methyl methacrylate) copolymers doped with nanoparticles

Earlier studies have shown that poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blocks are compatible at 270 and 298 K, and that their Flory–Huggins interaction parameters have the same blending ratio dependence at both temperatures. At a much higher temperature (400 K), the behavior of PEO/PMMA blends is strikingly different as both components become incompatible, while the Flory–Huggins parameters are low. Here we investigate the effect of doping with nanoparticles on the degree of incompatibility of twelve miktoarm PEO‐b‐PMMA copolymers at 400 K. Since PEO tends to be semicrystalline and long chains aggregate easily, PEO‐rich and long‐chain copolymer blends feature the highest degree of incompatibility for all nanoparticle arrangements and present cubic phase morphologies. In addition, the largest nanoparticles can reinforce the microscopic phase separation of all PEO‐b‐PMMA copolymers. This shows that the main factor affecting the phase morphology is the size of the nanoparticles. Also, only the asymmetric Da3‐type PEO‐rich copolymers show a hexagonal cylindrical phase morphology, which illustrates the effect induced by the nanoparticles on the microscopic phase separation changes of the PEO‐b‐PMMA copolymers. These induced effects are also related to the composition and molecular architecture of the copolymers. © 2013 Society of Chemical Industry