Physical gelation of cellulose acetate propionate solutions mediated by metal carbonyl complexes

The weak physical gelation of cellulose acetate propionate-butyl butyrate solutions as a result of the in-situ decomposition of iron pentacarbonyl complexes was explored. Viscometry and infrared spectroscopy were used to monitor the iron pentacarbonyl decomposition reaction progress and its effect on viscosity. Changes in viscosity in of the cellulosic fluids in general and gelation in particular were found to be dependent upon the environment in which the Fe(CO)₅ decompositions occurred. Systems under inert atmospheres exhibited a marked increase in viscosity, while systems under oxidative atmospheres exhibited a general decrease in viscosity. We propose a hypothesis that explains the dependence of the viscosity of these cellulosic fluids as a function of the environmental conditions during the precursor decomposition. Under nitrogen atmospheres, zero-valent nanoparticles with highly reactive surfaces are synthesized, which form weak, transient bonds with the cellulosic polymer. The iron particles, under these circumstances, serve as weak bridges between adjacent polymer chains. Conversely, the primary particles synthesized under an oxidative atmosphere are metal oxides, which are less attractive to the polymer chain and, therefore, do not yield such bridges. This work demonstrates the capability to apply a simple method to control the viscosity of cellulose ester fluids.     

Viscometric behavior of concentrated cellulose acetate solutions

The viscometric behavior of concentrated cellulose acetate solutions in a variety of solvent and mixed solvent systems has been studied. Rapid increases in solution viscosity with increase in cellulose acetate concentration are apparently related to polymer nonsphericity and the tendency of molecules to experience extensive nonhydrodynamic interactions. By employing a well-defined polymer solution theory in conjunction with an empirically determined calibration curve, accurate predictions of concentrated cellulose acetate solution viscosities are possible.     

A light-scattering and membrane formation study on concentrated cellulose acetate solutions

An improved explanation of the mechanism of the porous membrane formation with asymmetric structure has been proposed. It emerged from the correlation of the results obtained by the light-scattering measurements of the ternary membrane casting solutions and by the reverse osmosis and ultrafiltration testing of the asymmetric membranes prepared from these solutions. The results of anisotropic light-scattering measurements indicated the extent of supermolecular structurization of the casting solution which affected the porous structure formation in the membrane surface region. The variation of the casting solution composition and, particularly, the role of the CA/F ratio, the formamide content, and their influence on the asymmetric membrane properties were investigated and explained using the improved concept of the membrane-making mechanism.     

Structure,nonisothermal crystallization behavior,and thermal property study of poly(trimethylene terephthalate)/cellulose acetate butyrate blends

Poly(trimethylene terephthalate) (PTT)/cellulose acetate butyrate (CAB) blends were prepared by melting blending through a co‐rotating twin screw extruder. The structures of PTT/CAB blends were characterized by scanning electron microscope (SEM) and Fourier transform infrared (FTIR) spectra, and the results showed that CAB phase dispersed homogeneously in the PTT matrix and there existed evident phase interface between PTT and CAB. The nonisothermal crystallization behavior was investigated by differential scanning calorimetry (DSC) and was described with modified Avrami equation of Jeziorny and Mo equation, respectively. The results indicated that the half crystallization time (t_{1/ 2}) is much shorter, the nonisothermal crystallization kinetic rate constant (Z_c) is bigger at a given cooling rate, the cooling rate [F_z(T)] is smaller at a given relative crystallinity (X _t) of PTT/CAB blends than those of PTT, which proved that the addition of CAB improved the crystallization of PTT and made PTT crystallize more perfect and faster than pure PTT. In addition, thermogravimetric analysis (TGA) curves of PTT and PTT/CAB blends showed that effects of CAB content on the thermal decomposition of PTT/CAB blends were little. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Viscometric behavior of ternary concentrated solutions of hydroxypropyl cellulose and ethyl cellulose in m-cresol

The shear viscosity of blend solutions of hydroxypropyl cellulose (HPC) and ethyl cellulose (EC) in m-cresol (both HPC/m-cresol and EC/m-cresol systems form lyotropic liquid crystals) was determined by cone-plate-type and capillary-type viscometers. The textures for the same systems at rest and undergoing shear were also observed with a polarized microscope. At shear rate of 1 s^?1, viscosity exhibited a maximum and a minimum with respect to temperature, and this suggested that the phase of the matrix dominated the viscometric behavior of the ternary systems; the blend composition dependence of the viscosity was not additive, and this suggested that HPC and EC were immiscible. At relatively high shear stress, the blend composition dependence of the viscosity greatly depended on the total polymer concentration of the solutions and was quite different from that at low shear rate; the texture of the anisotropic solutions was also different from that at low shear rate. Our findings suggested that the dependence of viscosity on shear and concentration for pure HPC solution was different from that for pure EC solution.     

Preparation and characterization of nifedipine-loaded cellulose acetate butyrate based microspheres and their controlled release behavior

Eudragit L100/cellulose acetate butyrate blend microspheres were prepared by solvent evaporation technique using poly(vinyl alcohol) as an emulsifying agent nifedipine (NFD) was successfully loaded into these microspheres. The effect of experimental variables such as ratio of blend ratio on NFD encapsulation efficiency, release rate, size, and morphology of the microspheres has been investigated. Scanning electron micrographs indicated the formation of spherical microspheres. Mean particle size of the microspheres has been measured by the laser light scattering technique ranged between 100 and 120 μm. NFD was successfully encapsulated up to 80% in the polymeric matrices. In vitro dissolution experiments performed in pH 7.4 buffer medium indicated a controlled release of NFD from the blend microspheres up to 12 h.     

A comparative analysis of the preparation of cellulose acetate butyrate and the characteristics of applying in pearlescent coating film

Polymer Bulletin - A simple, green, and efficient mechanical activation-assisted esterification (MAE) technology was developed for the preparation of cellulose acetate butyrate (CAB), which was...     

The permeation behavior of metal complex solutions through cellulose acetate membranes

Transport phenomena of several kinds of metal complexes were investigated with cellulose acetate membranes annealed at 65°–76°C. In reverse osmosis experiments, the rejections of metal complexes involving organic sequestering agents such as EDTA or citric acid were much higher than those of the corresponding metal ions. While, in the case of metal complexes involving small inorganic ligands such as NH₃ or SCN^-, their rejections did not necessarily increase with the increase in the coordination numbers of the metal ions. To more precisely understand such transport behaviors, the distribution and the diffusion coefficients of metal complexes were obtained by desorption-rate measurements with dense cellulose acetate membranes. The results revealed that the distribution of a metal ion to the membrane was largely depended on the coexisting ligands. Attempts were also made to explain the distribution coefficient from the microscopic point of view by using Glueckauf's equation.     

醋酸丁酸纤维素与聚丙烯酸乙酯共混体系的研究

通过差热分析和拉伸试验研究了醋酸丁酸纤维素CAB－35－1与聚丙烯酸乙酯（PEA）物理共混、半一互穿网络共混体系的相容性和力学性能，并用扫描电镜观察了共混物的形态。     

Dispersion and properties of cellulose nanowhiskers and layered silicates in cellulose acetate butyrate nanocomposites

The aim of this work was to develop well dispersed nanocomposites, in a non water soluble polymer using a non aqueous, low polarity solvent as a dispersion medium. The nanoreinforcements were cellulose whiskers and layered silicates (LSs) and matrix was cellulose acetate butyrate (CAB). Before nanocomposite processing, a homogenizer was used in combination with sonification to achieve full dispersion of the nanoreinforcements in a medium of low polarity (ethanol). After processing, the cellulose nanowhiskers (CNW) showed flow birefringence in both ethanol and dissolved CAB, which indicated well dispersed whiskers. The microscopy studies indicated that the processing was successful for both nanocomposites. The CNW showed a homogeneous dispersion on nanoscale. The LS nanocomposite contained areas with lower degree of dispersion and separation of the LS sheets and formed mainly an intercalated structure. The produced materials were completely transparent, which indicated good dispersion. Transparency measurements also indicated that the nanocomposite containing CNW showed similar performance as the pure CAB. Dynamic mechanical thermal analysis (DMTA) showed improved storage modulus for a wide temperature range for both nanocomposites compared with the pure CAB matrix. This study indicated that CNW have a potential application in transparent nanocomposites based on fully renewable resources. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

研究环氧树脂聚酰亚胺树脂凝胶行为的新方法

为了优化双组分环氧树脂和PMR型聚酰亚胺树脂的固化工艺,选用DMA圆盘压缩夹具,采用等温模式分别测定了这2种树脂的凝胶行为,给出了其凝胶动力学数学模型,计算了树脂的凝胶活化能为75.68 kJ/g。在聚酰亚胺树脂凝胶实验结果的基础上,推测该聚酰亚胺体系在310℃前后可能存在不同的固化反应机理。     

Deterioration behavior of cellulose acetate films in acidic or basic aqueous solutions

The deterioration behavior of cellulose acetate (CA) films (degree of substitution = 2.5) was examined in hydrochloric acid (HCl) and sodium hydroxide (NaOH) solutions of various concentrations to determine acid and base catalytic effects in heterogeneous systems at room temperature. With concentrations of 0.5N HCl and 0.01N NaOH and higher, the physical properties of the films changed. The films, recovered after 1–10 days of immersion, were slightly opaque and rubbery from swelling in the solutions before drying. They became brittle and shrank when they dried. For HCl immersion, the weight change of a film depended on the HCl concentration and the immersion time. With 6.0N HCl, the film shape was broken, and a fine powder was deposited in the solution with a recovery of 53.8 wt %. The infrared spectrum of this deposit indicated that it was completely deacetylated cellulose. For NaOH immersion, although the weight change depended on the NaOH concentration, the weight loss reached 40–50% within the first 24 h, and it was constant with respect to the immersion time and base concentration in 0.5N NaOH or NaOH of a higher concentration. The infrared and gel permeation chromatography analyses showed that this deterioration mainly depended on the deacetylation of CA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3354–3361, 2004     

A study on reproducibility of cellulose acetate membranes

The variation in flux and rejection of replicate cellulose acetate membranes is measured within a membrane sheet as well as between membranes. Although the casting conditions were carefully controlled and various influences were studied. the source of variation in replicates was not identified. It is shown that the cause of variation is not due to hand or machine casting technique, casting solution composition, heat treatment, dust, overall film thickness or pressure history.     

Synthesis and characterization of interpenetrating networks from polycarbonate and cellulose acetate butyrate

Polycarbonates (PC) are currently used for organic optical glass; nevertheless they show a poor impact resistance which may be increased by combination with cellulose acetate butyrate (CAB) into a PC/CAB interpenetrating polymer network (IPN), without altering the material transparency as we show here. A series of rigid IPNs based on an aliphatic polycarbonate and CAB was prepared through in situ polymerization techniques. The kinetics of the formation of two networks in the IPNs were studied by FTIR spectroscopy. Effects of the CAB cross-linking and weight proportions of the two components in the IPNs were investigated by dynamic mechanical thermal analysis.     

The effect of plasticizer and cellulose nanowhisker content on the dispersion and properties of cellulose acetate butyrate nanocomposites

We studied the effects of plasticizer and cellulose nanowhisker content on the dispersion and properties of cellulose acetate butyrate (CAB)‐based bionanocomposites. The cellulose nanowhiskers in an aqueous medium were solvent‐exchanged to nonaqueous polar solvent (acetone) and used for nanocomposite processing by solution casting. The plasticized and unplasticized nanocomposites with 5 and 10 wt % cellulose nanowhisker content were prepared. Atomic force microscopy indicated nanoscale dispersion of whiskers in the CAB matrix. The dynamic mechanical analysis showed an increase in storage modulus with addition of cellulose nanowhiskers, especially above the glassy‐rubbery transition region. Thermogravimetric analysis showed an improvement in thermal stability with increased whisker content for both unplasticized and plasticized nanocomposites. The plasticized nanocomposites showed better transparency than the unplasticized composites, indicating a better dispersion of cellulose nanowhiskers in CAB, in the presence of a plasticizer. The dynamic mechanical properties and thermal stability increased, whereas transparency decreased with increased CNW content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A comparative study of the thermal decomposition of cellulose and cellulose triacetate

Conclusions A comparative study has been made of the thermal decomposition of cellulose and of cellulose acetates having various degrees of polymerization, and also of specimens regenerated from nonaqueous solutions.The effect of the solvent on reducing the effective energy of activation of thermal decomposition on transition from the starting samples of cellulose and its derivatives to specimens regenerated from nonaqueous solutions has been revealed.It has been found that the degree of polymerization exerts no significant effect on the temperature of thermal decomposition.Translated from Khimicheskie Volokna, No. 4, pp. 28–29, July–August, 1986.