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.     

Miscibility of poly(tetrahydrofurfuryl methacrylate) and poly(tetrahydropyranyl-2-methacrylate) with some chlorine-containing polymers

The miscibility of poly(tetrahydrofurfuryl methacrylate) (PTHFMA) and poly(tetrahydropyranyl-2-methacrylate) (PTHPMA) with some chlorine-containing polymers was studied by differential scanning calorimetry (DSC). PTHPMA was found to be miscible with poly(vinyl chloride) (PVC), polyepichlorohydrin (PECH), and a vinylidene chloride/vinyl chloride copolymer [P (VDC/VC)] and only partially miscible with an epichlorohydrin/ethylene oxide copolymer [P (ECH/EO)]. PTHFMA was shown to be miscible with PECH and P(VDC/VC), but its miscibility with P(ECH/EO) is composition-dependent. Information about interactions between components in PTHFMA/P (VDC/VC) and PTHPMA/P(VDC/VC) blends was estimated from melting-point depression. The interaction parameters B were found to be ?1.7 and ?3.6 J/cm³ for PTHFMA/P(VDC/VC) and PTHPMA/P(VDC/VC) blend systems, respectively. The miscibility behavior of PTHFMA and PTHPMA is compared to that of poly(cyclohexyl methacrylate).     

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.     

Comparison of Poly(Ethylene Oxide) Melt Crystallization in Blend and Block Copolymer Systems with Poly (Methyl Methacrylate) and Poly (Tert-Butyl Methacrylate)

DSC investigations are reported for a broad assortment of blends and copolymers of the immiscible poly(ethylene oxide) (PEO)/poly(tert-butyl) methacrylate) (PTBMA) system. Contrary to expectations, the PEO crystallization and melting behavior of the copolymer system is similar to that of the PEO/poly(methyl methacrylate) (PMMA) copolymer system (which is usually considered to be miscible in the melt). This is discussed with the concept of a UCST-type granulated demixing in the latter. In both systems the crystallization is rather sensitive to the block structure, even for comparable molecular weights and compositions. This indicates some importance of DSC as an additional tool in copolymer characterization. Free PEO ends favor the crystallization in all cases.     

DSC and DMTA characterization of ternary blends

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

Miscibility 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.     

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.     

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     

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     

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.     

Casting solvent effect on crystallization behavior and morphology of poly(ethylene oxide)/poly(methyl methacrylate)

Poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends were prepared by casting from either chloroform or benzene solvents. After casting from solvents, all samples used in this study were preheated to 100°C and held for 10 min. Then, the solvent effect on the crystallization behavior and thermodynamic properties were studied by differential scanning calorimeter (DSC). Also, the morphology of spherulite of casting film was studied by polarized optical microscope. From the DSC and polarizing optical microscopy (POM) results, it was found that PEO/PMMA was miscible in the molten state no matter which casting solvent was used. However, the crystallization of PEO in the chloroform‐cast blend was more easily suppressed than it was in the benzene‐cast blend. Relatively, the chloroform‐cast blend showed the greater melting‐point depressing of PEO crystals. Also, the spherulite of chloroform‐cast film showed a coarser birefringence. It was supposed that the chloroform‐cast blend had more homogeneous morphology. It is fair to say that polymer blends, cast from solvent, are not necessarily in equilibrium. However, the benzene‐cast blends still were not in equilibrium even after preheating at 100°C for 10 min. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1627–1636, 2000     

Poly(hydroxyether sulfone) and its blends with poly(ethylene oxide): miscibility, phase behavior and hydrogen bonding interactions

Poly(hydroxyether sulfone) (PHES) was synthesized through polycondensation of bisphenol S with epichlorohydrin. It was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy and differential scanning calorimetry (DSC). The miscibility in the blends of PHES with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PHES/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed single, composition-dependent glass transition temperatures (T_gs), indicating that the blends are miscible in amorphous state. At elevated temperatures, the PHES/PEO blends underwent phase separation. The phase behavior was investigated by optical microscope and the cloud point curve was determined. A typical lower critical solution temperature behavior was observed in the moderate temperature range for this blend system. FTIR studies indicate that there are the competitive hydrogen bonding interactions upon adding PEO to the system, which was involved with the intramolecular and intermolecular hydrogen bonding interactions, i.e. -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO between PHES and PEO. In terms of the infrared spectroscopic investigation, it is judged that from weak to strong the strength of the hydrogen bonding interactions is in the following order: -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO.     

Melt blending of polylactide and poly(methyl methacrylate): Thermal and mechanical properties and phase morphology characterization

Blends of polylactide with poly(methyl methacrylate), PLA/PMMA, were prepared by a semi‐industrial twin screw extruder and afterwards were injection molded. Blends were studied using different techniques as Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Mechanical Analysis (DMA), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and mechanical properties by means of tensile and impact tests, were also studied. This work helped better understanding of apparently contradictory results reported in the literature for PLA/PMMA blends prepared by melt compounding. DSC first heating scan and DMA results showed partially miscible blends, whereas the second DSC heating scan showed miscible blends. For miscible blends, T_g values were predicted using Gordon‐Taylor equation. On the other hand, Small and Van Krevelen approaches were used to estimate the solubility parameters of neat PLA and neat PMMA, and Flory‐Huggins interaction parameter was calculated from solubility parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42677.     

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     

Synthesis and Characterization of Block-Graft Copolymers [poly(epichlorohydrin-<Emphasis Type="Italic">b</Emphasis>-styrene)-<Emphasis Type="Italic">g</Emphasis>-poly(methyl methacrylate)] by Combination of Activated Monomer Polymerization,NMP and ATRP

Summary Synthesis of block-graft copolymers, namely poly(epichlorohydrin-b-styrene)-g-poly(methyl methacrylate) (PECH-b-St)-g-PMMA) by combination of Activated Monomer (AM), Nitroxide Mediated Polymerization (NMP) and Atom Transfer Radical Polymerization (ATRP) methods was described. For this purpose, first epichlorohydrin (ECH) was polymerized by using BF₃THF complex in the presence of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl-1-oxy (HTEMPO) via AM mechanism. The resulting stable radical terminated polymer was subsequently used as a counter radical in the NMP of styrene (St) initiated by benzoyl peroxide to yield block copolymers of ECH and St. Finally, the ATRP of methyl methacrylate (MMA) by using chloromethyl groups of the PECH segment as initiating sites resulted in the formation of (PECH-b-St)-g-PMMA). The structures of the intermediate polymers at various stages were characterized by ¹H-NMR spectral investigations. The thermal behavior and surface morphology of the copolymers were also investigated by DSC and AFM measurements.     

Crystallization, melting and morphology of PEO in PEO/MWNT-g-PMMA blends

The dispersion of multi-walled carbon nanotubes (MWNTs) in crystalline poly(ethylene oxide) (PEO) is significantly improved by grafting with poly(methyl methacrylate) (PMMA) on surface of MWNTs via emulsion reactions. The synthesized MWNTs-g-PMMA is soluble in solvents that can dissolve PMMA and is well dispersed in PEO. The effects of the MWNTs-g-PMMA on PEO crystallization and its use as a reinforcement for PEO are investigated using DMA, DSC, POM, and SAXS. DMA data show that the PEO/MWNTs-g-PMMA blends containing up to 30 wt% MWNTs-g-PMMA are compatible. DSC data show the crystallization of PEO is enhanced by the MWNTs-g-PMMA, accompanying with a decreased thickness of crystal layers and an increased thickness of amorphous layers of the PEO lamellar stacks, in combination with SAXS data.     

Determining multiple component glass transition temperatures in miscible polymer blends: Comparison of fluorescence spectroscopy and differential scanning calorimetry

Fluorescence spectroscopy is used to measure component glass transition temperatures (T_gs) in miscible blends of pyrene-labeled poly(methyl methacrylate) (MPy-labeled PMMA) with poly(ethylene oxide) (PEO) or poly(vinyl chloride) (PVC) over a broad composition range. Component T_gs determined for PMMA blended with PEO can be described by the same value of self-concentration (0.60) determined previously (Lodge et al. J Polym Sci Part B: Polym Phys 2006; 44:756–763) using differential scanning calorimetry (DSC), indicating that fluorescence and DSC report a similar strength of component T_g perturbations. Blends of PMMA with PVC are also characterized via MPy-labeled PMMA fluorescence, demonstrating for the first time that both binary blend component T_gs can be determined from the temperature dependence of the fluorescence of a pyrenyl dye attached to a single blend component. This special sensitivity of the pyrenyl dye label to both component T_gs is hypothesized to derive from the solvatochromic nature of the dye, which in turn implies that the dye fluorescence may be sensitive to local stiffness or modulus in the blend. Because of the close proximity of the T_gs of neat PMMA and neat PVC, DSC is unable to clearly resolve the two component T_gs in these blends. Thus, fluorescence provides information unattainable by DSC and is a powerful new tool for investigating component T_gs in miscible blends.     

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.     

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     

New liquid crystalline columnar poly(epichlorohydrin‐co‐ethylene oxide) derivatives leading to biomimetic ion channels

A new family of liquid crystalline columnar polyethers was obtained by modification of Poly(epichlorohydrin‐co‐ethylene oxide) (P(ECH‐co‐EO)) with the dendron 3,4,5‐tris[4‐(n‐dodecan‐1‐yloxy)benzyloxy]benzoate, under different conditions. The highest modification degree that we could achieve was 69%. The copolymers were fully characterized by ¹H and ¹³C nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD). All copolymers exhibited liquid‐crystalline columnar behavior whose range of stability depended on the modification degree. X‐ray diffraction experiments on oriented samples showed that the dendrons are approximately perpendicular to the column axis and that their average number per unit cell ranged from 5 to 6. The formation of a stable columnar mesophase in the polyether should determine the presence of a continuous ion channel along the column axis. Therefore, these copolymers are suitable candidates for the preparation of membranes for small cation transport, in agreement with the results that we obtained by using poly(oxy‐1‐chloro methylethylene) (PECH) modified with the same dendron. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers