Miscibility of cellulose acetate with vinyl polymers

Binary blend films of cellulose acetate (CA) with flexible syntheticpolymers including poly(vinyl acetate) (PVAc), poly(N-vinyl pyrrolidone) (PVP),and poly(N-vinyl pyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] were preparedfrommixed polymer solutions by solvent evaporation. Thermal analysis by DSC showedthat CA of any degree of substitution (DS) was not miscible with PVAc, but CAwith DS less than 2.8 was miscible with PVP to form homogeneous blends. Thestate of mixing in CA/P(VP-co-VAc) blends was affected not only by the DS of CAbut also by the VP/VAc copolymer composition. As far as CAs of DS<2.8 andP(VP-co-VAc)s with VP contents more than ca. 25 mol% were used,theCA/copolymer blends mostly showed a miscible behaviour irrespective of themixing ratio. FT-IR measurements for the miscible blends of CA/PVP andCA/P(VP-co-VAc) revealed the presence of hydrogen-bonding interactions betweenresidual hydroxyls of CA and carbonyls of N-vinyl pyrrolidone units, which maybe assumed to largely contribute to the good miscibility.     

Cellulose alkyl ester/vinyl polymer blends: effects of butyryl substitution and intramolecular copolymer composition on the miscibility

The blend miscibility of cellulose alkyl esters, mainly butyrate (CB) and acetate butyrate (CAB), with synthetic homo- and copolymers comprising N-vinyl pyrrolidone (VP) and/or vinyl acetate (VAc) units, i.e., PVP, PVAc, and P(VP-co-VAc), was examined by differential scanning calorimetry. A miscibility map for the CB/vinyl polymer systems was constructed as a function of the degree of substitution (DS) of CB and the VP fraction of the mixing component. CBs were immiscible with PVAc regardless of the DS used (2.11–2.94), but miscible or immiscible with PVP depending on whether the butyryl DS was <2.5 or >2.5. The critical value of DS≈2.5 is lower than the corresponding one (DS≈2.8) evaluated formally for cellulose acetate (CA)/PVP blend series. This lowering is ascribable to an effect of steric hindrance of the bulky butyryl substituents, leading to suppression of the hydrogen-bonding interactions, as a driving factor for miscibility attainment, between residual hydroxyls of CB and carbonyl groups of PVP. The CB/vinyl copolymer system imparted a ‘miscibility window’ in which the VP/VAc composition participated; viz., CBs of DS≈2.54–2.94 were miscible with some P(VP-co-VAc)s of 30–70Â mol% VP fractions, in spite of the immiscibility with both PVP and PVAc homopolymers. The result was interpreted in terms of another inter-component attraction derived from repulsion between the monomer ingredients constituting the vinyl copolymer component. For CAB/P(VP-co-VAc) blends, it was observed that the VP/VAc range forming such a miscibility window became further expanded, compared with the corresponding series of CB blends. Fourier transform infrared and solid-state ¹³C NMR spectroscopy revealed not only the presence or absence of the intermolecular hydrogen-bonding formation, determined according to the lower or higher DS of the cellulose ester component in the blends considered, but also a difference in the mixing scale between the polymer pairs regarded as miscible by the thermal analysis.     

Thermodynamic study of poly(N-vinyl caprolactam) hydration at temperatures close to lower critical solution temperature

The lower critical solution temperature of aqueous solutions of poly(N-vinyl caprolactam) falls in the 305–307 K range and depends on the molecular weight of the polymer. The thermodynamic functions of mixing at 298 K have been calculated from measurements of vapor pressures and heats of dissolution and dilution. Partial Gibbs energy, partial enthalpy, and partial entropy of mixing were negative over the entire range of composition. Increasing temperature resulted in a decrease in the exothermal character of mixing. Excessive heat capacity values, calculated from the dependencies of enthalpy of mixing on temperature, were positive over the entire composition range. Heat capacity of dilute solutions was measured at 298 K and partial heat capacity of poly(N-vinyl caprolactam) at infinite dilution was shown to be positive. The data obtained point out the hydrophilic and hydrophobic hydration of poly(N-vinyl caprolactam) in aqueous solutions. Hydrophobic hydration dominates at temperatures close to binodal curve. As a result, the mutual mixing of the polymer with water is decreased and phase separation takes place.     

Effect of temperature on the intrinsic viscosity of poly(ethylene glycol)/poly(vinyl pyrrolidone) blends in aqueous solutions

In this work the intrinsic viscosity of poly(ethylene glycol)/poly(vinyl pyrrolidone) blends in aqueous solutions were measured at 283.1–313.1 K. The expansion factor of polymer chain was calculated by use of the intrinsic viscosities data. The thermodynamic parameters of polymer solution (the entropy of dilution parameter, the heat of dilution parameter, theta temperature, polymer–solvent interaction parameter and second osmotic virial coefficient) were evaluated by temperature dependence of polymer chain expansion factor. The obtained thermodynamic parameters indicate that quality of water was decreased for solutions of poly(ethylene oxide), poly(vinyl pyrrolidone) and poly(ethylene oxide)/poly(vinyl pyrrolidone) blends by increasing temperature. Compatibility of poly(ethylene oxide)/poly(vinyl pyrrolidone) blends were explained in terms of difference between experimental and ideal intrinsic viscosity and solvent–polymer interaction parameter. The results indicate that the poly(ethylene glycol)/poly(vinyl pyrrolidone) blends were incompatible.     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

Conductivity and thermal behavior of proton conducting polymer electrolyte based on poly (N-vinyl pyrrolidone)

The polymer electrolytes based on poly N-vinyl pyrrolidone (PVP) and ammonium thiocyanate (NH₄SCN) with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The shift in T_g values and the melting temperatures of the PVP-NH₄SCN electrolytes shown by DSC thermo-grams indicate an interaction between the polymer and the salt. The dependence of T_g and conductivity upon salt concentration have been discussed. The conductivity analysis shows that the 20 mol% ammonium thiocyanate doped polymer electrolyte exhibit high ionic conductivity and it has been found to be 1.7 × 10⁻⁴ S cm⁻¹, at room temperature. The conductivity values follow the Arrhenius equation and the activation energy for 20 mol% ammonium thiocyanate doped polymer electrolyte has been found to be 0.52 eV.     

DSC Studies of Thermally Induced Phase Separation of Hydrogen Bonded Polymer Blends

The thermally induced phase separation behavior of hydrogen bonded polymer blends, poly(n-hexyl methacrylate) (PHMA) blended with poly(styrene-co-vinyl phenol) (STVPh) random copolymers having various vinyl phenol contents, was studied by temperature modulated differential scanning calorimetry (TMDSC).The enthalpy of phase separation was determined to be about 0.5 cal g^–1 for one of the blends. A phase diagram was constructed from the TMDSC data for one of the blends. The kinetics of phase separation was studied by determining the phase compositions from the glass transition temperatures of quenched samples after phase separation. Subsequently, the phase separated samples were annealed at temperatures below the phase boundary to observe the return to the homogeneous state.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation of polymeric nanocapsules by radiation induced miniemulsion polymerization

In this research, polystyrene (PSt) nanocapsules with liquid cores were prepared by ⁶⁰Co γ-ray radiation induced miniemulsion polymerization, in which N-vinyl pyrrolidone (NVP) was used as the polar monomer. The characterization of polymer was carried out by ¹H NMR. It was verified that during polymerization, graft copolymerization between poly (pyrrolidone) (PVP) and PSt had taken place instead of random copolymerization. The interfacial tension between polymer and water was reduced because of the grafting reaction that had occurred, which was helpful to form nanocapsules. The influence of the ratio of St to NVP, the type and amount of the surfactant and the monomer/dodocane ratio on the particle morphology was studied by TEM. Finally, the releasing process of the synthesized nanoparticles was monitored by UV-vis measurement.     

IR laser-induced decomposition of poly(vinyl chloride-co-vinyl acetate): Control of products by irradiation conditions

IR laser-induced, ablative decomposition of poly(vinyl chloride-co-vinyl acetate) was examined under different irradiation conditions and its volatile and solid products were characterized by mass spectroscopy, infrared spectroscopy, Raman spectroscopy and UV spectroscopy and EDX-measurements. The laser decomposition of the copolymer, compared with that of poly(vinyl acetate) and poly(vinyl chloride), is revealed to be a more efficient process leading to solid films with the proportion of Cl- and CH₃C(O)O-groups controlled by irradiation conditions.     

Study of some properties of poly(N-vinyl imidazole) partially quaternized with n-butyl bromide aqueous solutions

This paper presents a study of the properties of aqueous solutions of poly(N-vinyl imidazole) quaternized with n-butyl bromide (PVIQ3). The influence of the temperature and polymer concentration on refractive index, electrical conductivity and surface tension was studied. The critical micelar concentration of PVIQ3 in aqueous solution was determined and correlated with the polymer solubility in water.All the PVIQ3 aqueous solutions properties were compared with those of poly(N-vinyl imidazole) (PNVI) and the influence of the quaternization process on the polymer properties was evidenced.     

Cellulose propionate/poly(N-vinyl pyrrolidone-co-vinyl acetate) blends: dependence of the miscibility on propionyl DS and copolymer composition

Blend miscibility of cellulose propionate (CP) with synthetic copolymers comprising N-vinyl pyrrolidone (VP) and vinyl acetate (VAc) units was examined, and a data map was constructed as a function of the degree of substitution (DS) of CP and the VP fraction in the copolymer component. Results of differential scanning calorimetry and Fourier transform infrared measurements indicated that the pairing of CP/P(VP-co-VAc) formed a miscible or immiscible blend system according to the balance in effectiveness of the following factors: (1) hydrogen bonding between residual hydroxyls of CP and VP carbonyls of P(VP-co-VAc); (2) steric hindrance of propionyl side-groups to the interaction specified in (1); (3) intramolecular repulsion between the two units constituting the vinyl copolymer; and, additionally, (4) structural affinity between two segmental moieties involving the propionyl group and VAc unit, respectively. The factor 3 inducing intercomponent attraction is responsible for the appearance of a so-called “miscibility window” in the miscibility map, and the factor 4 substantially expands the miscible region whole, wider relative to those in the maps for the corresponding blend series based on cellulose acetate and butyrate. In further refined estimation by dynamic mechanical analysis and T _1ρ ^H quantification in solid-state ¹³C NMR, it was found that the miscible blends of hydrogen-bonding type (using CPs of DS < 2.7) were completely homogeneous on a scale within a few nanometers, whereas the polymer pairs situated in the window region (using CPs of DS > 2.7) formed blends exhibiting a somewhat larger size of heterogeneity (ca. 5–20 nm).     

Mechanical properties and morphology of epoxy/poly(vinyl acetate)/poly(4-vinyl phenol) brominated system

Diglycidyl ether of bisfenol-A (DGEBA)/poly(vinyl acetate) (PVAc)/poly(4-vinyl phenol) brominated (PVPhBr) ternary blends cured with 4,4’-diaminodiphenylmethane (DDM) were investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). Homogeneous (DGEBA+DDM)/PVPhBr networks with a unique T _g are generated. Ternary blends (DGEBA+DDM)/PVAc/PVPhBr are initially miscible and phase separate upon curing arising two T _gs that correspond to a PVAc-rich phase and to epoxy network phase. Increasing the PVPhBr content the T _gof the PVAc phase move to higher temperatures as a consequence of the PVAc-PVPhBr interactions. Different morphologies are generated as a function of the blend composition.     

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one‐pot process from mixtures of monomers. Herein we report the use of O₂ as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co^III?R [Salen=N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine; R=alkyl] to the ring‐opening copolymerization (ROCOP) of CO₂/epoxides. Critical to this process is unprecedented monooxygen insertion into the Co?C bond, as rationalized by DFT calculations, leading to the formation of (Salen)Co^III?O?R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)‐b‐polycarbonate could be obtained by ROCOP of CO₂/epoxides with preactivation of (Salen)Co end‐capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)‐b‐poly(methyl acrylate)‐b‐polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt‐mediated sequential polymerization with an O₂‐triggered switch in a one‐pot process.     

Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole,poly(<Emphasis Type="Italic">N</Emphasis>-methylpyrrole) and polypyrrole derivatives functionalized by titanocene centers,in dry non-aqueous solutions

We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH₂)₃NC₄H₄; Tc=CpCpTiCl₂; Cp=C₅H₅; Cp=C₅H₄] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl^–-containing solutions have shown that the p(Tc3Py) matrix is very sensitive to the presence of Cl^– ions in all the above solvents, namely that it was subjected to electrochemical degradation at potentials above 0.1 V vs. a Ag/0.01 M Ag⁺ in AN reference electrode. Degradation of the p(Tc3Py) matrix was also observed in chloride-free DMF+TBAPF₆ solutions. Addition of chloride ions to the AN solution containing pyrrole, N-methylpyrrole or Tc3Py inhibits the deposition of the polymer films. On the other hand, we have found that PPy and p(N-MePy) matrices after their deposition in chloride-free AN solutions show much more stable redox responses in contact with chloride and/or DMF solutions. Possible mechanisms of these effects are discussed.Abbreviations AN acetonitrile - Cp cyclopentadienyl - DMF N,N-dimethylformamide - N-MePy N-methylpyrrole - p(N-MePy) poly(N-methylpyrrole) - PPy polypyrrole - p(Tc3Py) poly[Tc(CH₂)₃NC₄H₄] - Py pyrrole - Tc titanocene=bis(cyclopentadienyl)titanium dichloride, Cp₂TiCl₂, or its radical CpCpTiCl₂ (Cp=C₅H₄) - Tc3Py titanocene-propyl-pyrrole, Tc(CH₂)₃NC₄H₄ - THF tetrahydrofuran Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

Dynamics studies on thermoresponsive poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) hydrogel in tetrahydrofuran/water mixtures

The properties of thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel in tetrahydrofuran/H₂O mixtures were studied. Scanning electron microscopic (SEM) images demonstrate that the hydrogel changes from homogeneous to heterogeneous microstructure upon the addition of tetrahydrofuran to water. This heterogeneous PNIPAAm hydrogel in the mixture solvent exhibits a very slow response rate at temperatures above its lower critical solution temperature. The decreased response rate is attributed to the formation of special ternary complexes including the polymer and the two solvents in the tetrahydrofuran/H₂O mixture. Factors controlling the thermoresponse rate are discussed further and several suggestions are provided for designing and developing fast-response PNIPAAm hydrogels in the future.     

Preparation of a novel polymer gel electrolyte based on N-methyl-quinoline iodide and its application in quasi-solid-state dye-sensitized solar cell

Using poly(acrylonitrile-co-styrene) as polymer host, 1,2-propanediol carbonate, dimethyl carbonate and ethylene carbonate as mixture solvent, N-methyl-quinoline iodide and iodine as the source of I⁻/I₃ ⁻, a novel polymer gel electrolyte with ionic conductivity of 5.12 × 10⁻³ S· cm⁻¹ at 25°C was prepared by sol-gel and hydrothermal methods. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell was fabricated. The solar cell possess better long-term stability and light-to-electrical energy conversion efficiency of 4.04% under irradiation of 100 mW· cm⁻². The influences of polymer host, solvent, N-methyl-quinoline iodide and temperature on ionic conductivity of the polymer gel electrolyte and the performance of the dye-sensitized solar cell was discussed.     

Iodine-Transfer Polymerization (ITP) of Ethylene and Copolymerization with Vinyl Acetate

Controlled radical polymerization of ethylene using different commercially available, cheap, and non-toxic iodo alkyls is performed by iodine transfer polymerization (ITP) under mild conditions (≤100 °C and ≤200 bar). The formed well-defined iodo end-capped polyethylene (PE−I) species is very stable upon storage. Narrow molar-mass distributions (dispersities around 1.6) were obtained up to number average molar masses of 7300 g mol⁻¹. The ethylene copolymerization by ITP (ITcoP) with vinyl acetate allowed to form a broad range of poly(ethylene-co-vinyl acetate) (EVA) containing from 0 to 85 mol % of VAc unit. In addition, EVA-b-PE block copolymers or EVA-b-EVA gradient block copolymers with different content of VAc in the blocks were obtained for the first time using ITP. Finally, reactivity trends were explored by a theoretical mechanistic study. This highly versatile synthetic platform provides a straightforward access to a diverse range of well-defined PE based polymer materials.     

Interpolymer complexation and thermal behaviour of poly(styrene-co-maleic acid)/poly(vinyl pyrrolidone) mixtures

Polymer complexation between poly(styrene-co-maleic acid), (SMA28) and (SMA50) containing 28 and 50 mol% of maleic acid and poly(vinyl pyrrolidone) (PVP), has been investigated by differential scanning calorimeter (DSC), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). All results showed that the ideal complex composition of SMA28/PVP and SMA50/PVP leads, respectively, to 2:1 and 1:1 mole ratio of interacting components.For the investigated systems, the T_g versus composition curve does not follow any of the usual proposed models for polymer blends. Withal, a new model proposed by Cowie et al. is used to fit the T_g data and it is found to reproduce the experimental results more closely. According to n and q obtained values, it seems reasonable to conclude that the inter-associated hydrogen bonds dominate in SMA28/PVP (2:1) complexes. This effect is corroborated by the FTIR study as evidenced by the high displacement of the specific bands and ionic interactions have been clearly identified. Finally, a thermogravimetric study shows that ionic interactions increase the thermal stability of these complexes.     

Aspects of Living Radical Polymerization Mediated by Cobalt Porphyrin Complexes

Living radical polymerization (LRP) of methyl acrylate (MA), acrylic acid (AA), and vinyl acetate (VAc) mediated by cobalt(II) porphyrin complexes ((TMP)Co^II·, (TMPS)Co^II·) are reported. The polymeric products with relatively low polydispersity and controlled number average molecular weight (M_n) based on one polymer chain per cobalt complex demonstrate the living characters of the polymerization process. The formation of block copolymers of poly(methyl acrylate)‐b‐poly(vinyl acetate) (PMA‐b‐PVAc) and poly(methyl acrylate)‐b‐poly(vinyl pyrrolidone) (PMA‐b‐PVP) demonstrate another important feature of LRP and extend the application of cobalt porphyrin mediated radical polymerization to a wider array of functionalized monomers. Kinetic studies using ¹H NMR to follow the formation of orGano‐cobalt complexes reveal that two mechanisms, reversible termination (RT) and degenerative transfer (DT), occur during the polymerization process. MA and VAc polymerization mediated by cobalt porphyrin complexes are used to illustrate the properties of these two LRP pathways and evaluate the kinetic and thermodynamic properties for several of the central reactions.     

Fast responsive poly(<Emphasis Type="Italic">N,N</Emphasis>-diethylacrylamide) hydrogels with interconnected microspheres and bi-continuous structures

We prepared thermo-responsive polymer hydrogels by γ-ray irradiation of aqueous solutions of N, N-diethylacrylamide at different temperatures below and above its lower critical solution temperature (LCST). Poly(N, N-diethylacrylamide) gel had a transparent and homogeneous structure when the radiation-induced polymerization and crosslinking were carried out below the LCST (25 °C) of the polymer. On the other hand, cloudy and heterogeneous gels were formed at temperatures above the LCST of the polymer (>35 °C). From environmental scanning electron microscopy observations, the gels prepared at 35 and 40 °C were seen to show sponge-like bi-continuous porous structures, while those prepared at 50 °C showed a porous structure consisting of interconnected microspheres. For temperature changes between 10 and 40 °C, gels with porous structures showed rapid volume transitions on a time scale of about a minute, not only for shrinking but also for swelling processes, which is in remarkable contrast to the porous poly(N-isopropylacrylamide) hydrogels.