Densely grafting copolymers of ethyl cellulose through atom transfer radical polymerization

Densely grafting copolymers of ethyl cellulose with polystyrene and poly(methyl methacrylate) were synthesized through atom transfer radical polymerization (ATRP). First, the residual hydroxyl groups on the ethyl cellulose reacted with 2‐bromoisobutyrylbromide to yield 2‐bromoisobutyryloxy groups, known to be an efficient initiator for ATRP. Subsequently, the functional ethyl cellulose was used as a macroinitiator in the ATRP of methyl methacrylate and styrene in toluene in conjunction with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a catalyst system. The molecular weight of the graft copolymers increased without any trace of the macroinitiator, and the polydispersity was narrow. The molecular weight of the side chains increased with the monomer conversion. A kinetic study indicated that the polymerization was first‐order. The morphology of the densely grafted copolymer in solution was characterized through laser light scattering. The individual densely grafted copolymer molecules were observed through atomic force microscopy, which confirmed the synthesis of the densely grafted copolymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4099–4108, 2005     

Characteristics of thin cellulose ester films spin-coated from acetone and ethyl acetate solutions

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Sorption and diffusion of oxygen in plasticized ethyl cellulose films of varying degrees of substitution

Plasticized films cast from ethyl cellulose were examined to evaluate the effect of the degree of substitution, DS, and the plasticizer content on the sorption and diffusion of oxygen. Sorption and permeation measurements were performed over a temperature range of 25–65°C on three different types of ethyl cellulose in the DS range 1.7–2.5 that had been plasticized with organic esters of comparatively low molecular weight. Sorption coefficients were determined by the pressure decay method, and permeability coefficients were measured independently according to ASTM D-1434-66. The diffusion coefficients were calculated assuming Fickian transport, and were compared to the values directly obtained from the evaluation of the sorption kinetics. The permeability coefficient indicates that there is a significant improvement of the barrier properties of the materials when the DS is reduced and when the plasticizer content is at the absolute minimum required. It was found that the variation in the magnitude of the permeability coefficient is related to the value of the diffusion coefficient, which is governed by the chemical composition of the mixtures. In contrast, the solubility of oxygen was determined by the physical state of the polymer matrix and increased rapidly at temperatures significantly below the glass transition temperature. Using an ergodic model, the diffusion coefficients obtained were related to the size distribution of microvoids in the materials and relative values for the diffusion coefficient were computed as a function of DS and temperature. The model calculates the concentration (number per volume) of voids that are large enough to be occupied by a penetrant molecule. It was assumed that the unoccupied volume fraction as a function of the cohesive energy density follows a Boltzmann distribution. The cohesive energy density and the unoccupied volume fraction of the polymer-plasticizer mixtures were calculated by fitting the Simha-Somcynsky equation of state to pressure-volume-temperature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 639–653, 1997     

Properties of solutions and films of blends of ethyl cellulose with polyvinylpyrrolidone and Poviargol

Viscosity properties of dilute and concentrated ethanol solutions of blends of ethyl cellulose with polyvinylpyrrolidone and Poviargol bactericidal formulation (silver metal nanoparticles stabilized with polyvinylpyrrolidone) were studied. The physicomechanical and thermomechanical properties of films prepared from solutions of the polymer blends were determined. Experiments on solvent vapor sorption showed that ethyl cellulose is incompatible with polyvinylpyrrolidone and Poviargol in the solid state in the entire composition range examined.     

Preparation and properties of silicon- and titanium-containing hybrid nanocomposite films based on ethyl cellulose

Nanocomposite hybrid films containing silicon and titanium compounds in the polymer matrix are prepared through the sol-gel method via the hydrolytic polycondensation of Si and Ti alkoxides (tetraethoxysilane and titanium tetrabutoxide) in the THF solution of a hydrophobic polymer, ethyl cellulose. Their structure and properties are studied with the use of a complex of physicochemical methods. During the hydrolysis of tetraethoxysilane and the subsequent polycondensation of the reaction products, silicon atoms are incorporated into the polymer and form -O-Si-O-bonds involving hydroxyl groups of ethyl cellulose. In the sol-gel method, titanium alkoxide yields nanosized particles of titanium dioxide that play the role of fillers in the polymer matrix. Titanium-containing films show solubility in THF and, after prolonged contact with the solvent, precipitate titanium dioxide from the solution. Hybrid films containing silicon are insoluble owing to the formation of a chemical network between polymer molecules and Si-OH groups of the products of hydrolysis of silicon alkoxide, as confirmed by the IR data. It is shown that the amounts and types of alkoxides and the diameters of the structures formed in the polymer matrix via the sol-gel procedure affect the hydrophilicity levels of ethyl cellulose hybrid films and their abilities to swell in water and aqueous solutions of organic dyes (brilliant blue and methylene blue). Ethyl cellulose hybrid films are hydrophilic, and they facilitate the removal of dye molecules from aqueous solutions. The best properties are featured by the films containing nanosized particles of titanium dioxide in the polymer matrix.     

Synthesis of graft copolymer of ethyl cellulose through living polymerization and its self-assembly

Copolymers of ethyl cellulose (EC) with polystyrene (PSt) were synthesized through atom transfer radical polymerization (ATRP). The molecular weight of graft copolymers increased without any trace of the EC macro-initiator, and the polydispersity of the side chains was low. The molecular weight of the side chains increased with the monomer conversion. Kinetic study indicated that the polymerization was first order. The micelle characteristics of the graft copolymer in acetone were investigated using dynamic light scattering (DLS), atom force microscopy (AFM) and transmission electron microscopy (TEM). With increasing the concentration, micelles were gradually formed from the solution. The TEM and AFM images indicated that the micelles had spherical shape and showed core-shell structure.     

Fabrication and characterization of a biocompatible hybrid film based on silver nanoparticle/ethyl cellulose polymer

Cellulose - This work deals with a green route to fabricate a biocompatible hybrid film composed of silver nanoparticles (AgNPs) and ethyl cellulose (EC). The hybrid film (AgNP/EC), with a...     

Pervaporation of alcohols through highly permeable PIM-1 polymer films

Polycondensation material PIM-1 has attracted the attention of researchers owing to its high transport parameters in gas separation and a high free volume. The pervaporation characteristics of PIM-1 have been systematically studied. Lower aliphatic alcohols (CH₃OH, C₂H₅OH, and n-C₄H₉OH) and water were selected as objects of research. The rates of mass transfer for individual components at various temperatures have been estimated, and for the ethanol-water binary mixture, the process of separation has been examined. The films based on the polymer under study exhibit the properties of organophilic membranes and are characterized by high permeability with respect to alcohols. The apparent activation energy of permeability is low. This behavior is common for pervaporation membranes based on glassy polymers with a high free volume. The parameters of separation for the water-alcohol mixture surpass corresponding values for typical organophilic membranes based on PDMS. These parameters are commensurable with the values observed for membranes based on poly(trimethylsilylpropyne). At the same time, PIM-1 does not demonstrate a rapid decrease in permeability in the course of time.     

Honeycomb micropatterning of proteins on polymer films through the inverse microemulsion approach

Here we report the rapid and convenient patterning of proteins on porous polymer film using the inverse microemulsion approach. Following this method, proteins, which were dissolved in water, were transferred into dichloromethane solution of polymers through the formation of inverse microemulsion by mixing the two solutions. The protein-containing microemulsion droplets accumulated automatically into large and stable ones on the surface of organic solution casting on solid substrates, and formed tightly packed microemulsion droplet arrays driven by surface tension. With the evaporation of organic solvent and water, the microemulsion droplet arrays, which act as the template, turn to honeycomb patterned pores bearing proteins in them. The formed protein patterns can be locally applied for the detection of other proteins through specific recognition. The generality and reproducibility for the formation of BSA/PS microporous film and protein patterning by using different polymers and solvents were demonstrated by investigating surfactant addition, polymer and solvent types, and casting volume on the morphology of the microporous films. A preliminary mechanism for the protein patterning is discussed based on the analysis of the experimental results.     

Effect of immobilizing adsorption on mass transport through polymer films

The Freundlich isotherm used in place of the Langmuir isotherm to describe the adsorption mode in the dual sorption theory of glassy polymer—gas systems. Time-lag expressions have been derived and compared with the available corresponding results for the Langmuir case. In the case of large and moderate values of the upstream boundary activity a₀, the value of the time-lag function L^a)(l) calculated with the proposed model is close to that calculated by Paul for the Langmuir isotherm. In the case of small values of a₀, the L^a(l) values predicted by Paul and the proposed model are different and the difference increases when the value of a₀ decreases. The ability of the present model to represent systems exhibiting positive deviations from Henry's law is also described.     

Thermal study of ethyl cellulose coating films used for modified release (MR) dosage forms

The aim of our research was to investigate the effect of the length of the polymer chain and the concentration of triethyl citrate used as a plasticizer on the thermal stability of the film structure in the case of two ethyl cellulose films (EC 10 and EC 45) used for preparing MR dosage forms. The influence of storage time was studied by monitoring the changes in the thermoanalytical parameters and by performing TG–MS examinations. It was found that the decomposition of the plasticizer from the arising film structure is retarded and a more homogeneous sample, therefore a better film can be prepared from EC 45. Mass spectrography performed as a coupled technique also proved that the films stayed stable until approximately 200 °C. Based on the above results, the composition prepared from EC 45 polymer with 5% triethyl citrate as plasticizer is recommended for making MR dosage forms.     

Transport of solutes through calix[4]pyrrole-containing cellulose acetate films

Films of cellulose acetate containing different concentrations of meso-octamethyl-porphyrinogen (calix[4]pyrrole) were prepared and characterized using UV-vis and FTIR spectroscopy, DSC and SEM. Incorporation of calix[4]pyrrole into cellulose acetate leads to a decrease in the degree of hydrophilicity of the polymeric matrix. However, a slight increase in the percentage of water uptake of the polymer is found with an increase of the initial amount of calix[4]pyrrole in the composite composition. This effect can be related to the plasticizing effect that the calix[4]pyrrole provokes in the cellulose acetate. A comparative study of transport parameters of oxygen and some non-associated electrolytes (sodium, copper(II) and nickel chlorides) was carried out. The diffusion coefficients of molecular oxygen through cellulose acetate films decrease with an increase of the concentration of calix[4]pyrrole in the composite films. The transport (diffusion and permeation) of the above mentioned electrolytes through a set of composite films shows a decrease of permeability and diffusion coefficients with an increase of calix[4]pyrrole concentration. Such behaviour is typical of systems where interactions between the polymer and diffusing species occur. However, from the analysis of the distribution coefficient, it was found that those interactions are only dependent on the calix[4]pyrrole content for 2:1 electrolytes.     

Mechanical enhancement of cellulose nanofibril (CNF) films through the addition of water-soluble polymers

Cellulose - In this work, water-soluble polymers were screened through solution casting and polyvinyl alcohol (PVA) and poly(2-ethyl-2-oxazoline) (PEOX) were found as reinforcement agents for...     

Viscometric behavior of mesomorphic ethyl cellulose solution in chloroform

A simple modification of the viscometer used to determine the viscosity of concentrated solutions is described which permits the ready measurement of viscosity versus shear rate behavior above room temperature. Basic experimental viscometry was performed on the ethyl cellulose–chloroform system using a B-type (Brookfield-like) rotating-cylinder viscometer. Data are compared with theoretical predictions. The flow curves exhibit yield stress at low shear rate. The yield stress is dependent on concentration and temperature. The viscosity versus concentration curves show typical mesomorphic behavior. The concentration dependences of viscosity and yield stress are similar. The critical concentration increases with temperature. In the single-phase region (isotropic or anisotropic state) the viscosity decreases with temperature and the apparent activation energy (E_a) for flow is positive, but in the biphasic range the viscosity increases with temperature and E_a is negative. The experimental results for the critical concentration appear to agree with Flory's theory of rodlike molecules when the ratio of persistence length to diameter of the chain is taken as the aspect ratio.     

Design,synthesis, and characterization of a combined main-chain/side-chain liquid-crystalline polymer based on ethyl cellulose

A novel combined main-chain/side-chain liquid-crystalline polymer based on an ethyl cellulose main chain containing azobenzene mesogens (AzoEC) was successfully synthesized. Molecular characterization of the resulting polymers with different degrees of substitution (DS) was performed with proton nuclear magnetic resonance (¹H NMR), Fourier-transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Thermal stability was investigated by thermogravimetric analysis (TGA). The phase transitions and liquid-crystalline behavior of these polymers were investigated by differential-scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The results indicate that DS has substantial effect on the liquid-crystalline behavior of these polymers. AzoEC with low DS only shows the cholesteric phase similar to ethyl cellulose (EC). However, when DS increases to a specific value, AzoEC begins to show fascinating supramolecular structures. The supramolecular structure of AzoEC with maximum DS consisted of a large-scale ordered lamellar structure formed by EC main chains and a small-scale ordered structure formed by azobenzene mesogens.     

Water in polymer membranes. Part III : Water sorption and pore volume in cellulose acetate films

Changes in waveguide properties of several cellulose acetate membranes and one polyimide membrane were measured as a function of their exposure to varying levels of relative humidity. The volume fraction of water in the films and the occupied pore volumes were determined from refractive index and thickness changes. The dependence of the refractive index on water absorption is related to a competition between two processes: one of filling pores with no film expansion and one of “free expansion” where the film expands to completely accommodate the added water volume. The term “pore” is taken to mean a volume with molecular and not macroscopic dimensions. The hydration properties of these dense cellulose acetate membranes were affected by degree of acetylation, casting temperatures and annealing treatments. Annealing CA398 membranes at 180°C decreased film water concentration by reducing the amount of free expansion. Annealed CA398 membranes that were tested in a reverse osmosis cell were found to have high salt rejection compared to unannealed films. The hydration characteristics of a polyimide membrane are compared to cellulose acetate membranes.     

Reactive, multifunctional polymer films through thermal cross-linking of orthogonal click groups

The ability to produce robust and functional cross-linked materials from soluble and processable organic polymers is dependent upon facile chemistries for both reinforcing the structure through cross-linking and for subsequent decoration with active functional groups. Generally, covalent cross-linking of polymeric assemblies is brought about by the application of heat or light to generate highly reactive groups from stable precursors placed along the chains that undergo coupling or grafting reactions. Typically, these strategies suffer from a general lack of control of the cross-linking chemistry as well as the fleeting nature of the reactive species that precludes secondary chemistry. We have addressed both of these issues using orthogonal chemistries to effect both cross-linking and subsequent functionalization of polymer films by mild heating, which results in exacting control of the cross-link density as well as the density of the residual stable functional groups available for subsequent, stepwise functionalization. This methodology is exploited to develop a strategy for the independent and orthogonal triple-functionalization of cross-linked polymer thin-films through microcontact printing.     

Photoactive additives for cross-linking polymer films: Inhibition of dewetting in thin polymer films

In this report, we describe a versatile photochemical method for cross-linking polymer films and demonstrate that this method can be used to inhibit thin polymer films from dewetting. A bifunctional photoactive molecule featuring two benzophenone chromophores capable of abstracting hydrogen atoms from various donors, including C-H groups, is mixed into PS films. Upon exposure to UV light, the bis-benzophenone molecule cross-links the chains presumably by hydrogen abstraction followed by radical recombination. Photoinduced cross-linking is characterized by infrared spectroscopy and gel permeation chromatography. Optical and atomic force microscopy images show that photocrosslinked polystyrene (PS) thin films resist dewetting when heated above the glass transition temperature or exposed to solvent vapor. PS films are inhibited from dewetting on both solid and liquid substrates. The effectiveness of the method to inhibit dewetting is studied as a function of the ratio of cross-linker to macromolecule, duration of exposure to UV light, film thickness, the driving force for dewetting, and the thermodynamic nature of the substrate.