Solution properties of cellulose triacetate. I. Fractional precipitation

Using petroleum ether as a precipitant and chloroform–acetone mixture as solvent, six fractions of cellulose triacetate were obtained by fractional precipitation. The molecular weight of each fraction was obtained from osmotic pressure measurements carried out on chloroform solutions. It was shown that virtual nonfractionability of cellulose triacetate with regard to molecular weight occurred in this system. This behavior was also observed in attempts to fractionate it from tetrachloroethane or acetic acid solutions. These results are explained by the hypothesis that specific polymer–solvent interaction takes place due to hydrogen bonding.     

Synthesis and properties of poly(ester urethanes) based on cellulose triacetate

Segmented poly(ester urethanes) were synthesized from oligomeric cellulose triacetate diols, poly(caprolactone)diols, and 1,6-hexamethylene diisocyanate. The effects of the molecular mass and structure of soft and hard segments of poly(ester urethanes) on their thermal behavior, mechanical properties, and degradation in aqueous solutions of a phosphate buffer were studied by DSC and IR spectroscopy. The combination of soft segments derived from poly(caprolactone)diols with M = (1.0–3.5) × 10³, hard segments based on depolymerized cellulose triacetate with M = (2–4) × 10³, and 1,6-hexamethylene diisocyanate makes it possible to synthesize poly(ester urethanes) with excellent mechanical characteristics. The degree of crystallinity of these polymers increases with a decrease in the molecular mass of the depolymerized cellulose triacetate block in the hard segment. As the soft segment lengthens, phase separation between domains of soft and hard segments becomes more pronounced. Upon incorporation of poly(ethylene glycol) blocks into the soft segments of poly(ester urethanes), their hydrophobicity is enhanced and biodegradability is accelerated.     

5.4 Properties and applications of cellulose triacetate film

The CTA film can be characterized by e.g. its relatively high moisture regain, significantly low birefringence, and moderate mechanical strength. Having been commercialized more than fifty years ago, it has been widely used as photographic film, protective film for polarizing plate, and optical compensation film for liquid crystal display (LCD). The photographic film application exploits the optical isotropy and unique physical properties of the CTA film. In the application of the CTA film to protective film for polarizing plate, its low in-plane birefringence is of particular importance. In the optical compensation to enhance the viewing angle of LCD, the CTA film, because of its moderate retardation in thickness direction (Rth), serves as an element of compensator as well as a base film. Considering the growth of the LCD market, the demand for CTA film is believed to be further expanding.     

Adsorption of cellulose triacetate on calcium silicate

Adsorption of cellulose triacetate from its chloroform solution on calcium silicate has been studied. The adsorption follows first order kinetics. The adsorption data are adequately described by the Langmuir isotherm indicating that the adsorbed polymer molecules behave as rigid molecules in the adsorbed state. An attempt has been made to fractionate cellulose triacetate employing the adsorption technique.     

The structure of electron beam-modified cellulose triacetate

The structure, relaxation, and surface properties of cellulose triacetate (CTA) fibers and films modified by electron-beam irradiation in the absorbed dose range of D = 0−1000 kGy have been studied. The relation of the glass transition and melting temperatures of the irradiated CTA samples with the local density and the fractal dimensionality of the macrochain has been revealed. It has been shown that the radiation-chemical processes associated with the rupture of acetal bonds and the hydrolysis of CTA acetate groups predetermine the change in the structural and relaxation characteristics of the irradiated samples, as well as a nonmonotonic form of the dependence of the density and the surface energy of the films upon the absorbed dose near the threshold value of D = 75 kGy.     

Optical anisotropy in solution-cast film of cellulose triacetate

The out-of-plane birefringence and its wavelength dispersion are studied employing solution-cast films of cellulose triacetate (CTA). In solution-cast process, CTA molecules are induced to align in the film plane. Although refractive index is the lowest in the oriented direction for the CTA films stretched more than 110 %, refractive index is found to be the lowest in the normal direction for the unstretched cast film. Attenuated total reflection measurements reveal that in-plane alignment of the acetyl group which provides strong polarizability anisotropy is responsible for the phenomenon. Furthermore, the out-of-plane birefringence is found to increase with increasing wavelength, i.e. extraordinary wavelength dispersion, whereas a stretched CTA film shows ordinary wavelength dispersion. The level of the out-of-plane birefringence in cast films depends on the preparation conditions, which is predictable considering the evaporation rate. Moreover, it is demonstrated for the first time that the out-of-plane birefringence and its wavelength dispersion can be modified by addition of a certain plasticizer such as tricresyl phosphate (TCP). During the evaporation, TCP molecules orient in the film plane accompanying the orientation of CTA chains by intermolecular orientation correlation, called nematic interaction. This technique will widen the scope of material design of retardation films because there are numerous liquid compounds having strong polarizability anisotropy.     

CPMAS 13C NMR and X-ray studies of cellooligosaccharide acetates as a model for cellulose triacetate

A series of crystalline oligomers from α-D -cellobiose octaacetate through α-D -cellohexaose eicosaacetate were prepared by homogeneous acetylation of the corresponding cellooligosaccharides and characterized by cross-polarization and magic angle sample spinning (CPMAS) carbon-13 nuclear magnetic resonance (¹³C NMR) spectroscopy and X-ray analysis to obtain the structural models of cellulose triacetate (CTA) in the solid state. Progressing toward the hexamer, the NMR spectral features of the oligomers, in comparison with two allomorphs of CTA I and CTA II, gradually approached those of CTA I. Specifically, chemical shifts of both the hexamer and pentamer were in agreement with those of CTA I. In addition, X-ray diffraction patterns of the oligomers established that the crystalline pentamer and hexamer had a CTA I lattice despite recrystallization from ethylacetate-n-hexane. Therefore, we conclude that the pentamer and hexamer are useful models for the CTA I structure. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4100–4107, 1999     

Solution properties and chain conformation characteristics of cellulose tricarbanilate

Fractions of two cellulose tricarbanilate samples were characterized by light-scattering (weight-average molecular weight, second virial coefficient, mean-square radius of gyration), gel permeation chromatography (polydispersity index), and viscometry (intrinsic viscosity) in tetrahydrofuran and acetone. The intrinsic viscosity data were analyzed in terms of the theory developed for the continuous wormlike cylinder model, and the chain parameters (Kuhn statistical segment length λ^?1, chain diameter d, and shift factor M_L) were evaluated. The molecular-weight dependence of the mean-square radius of gyration in tetrahydrofuran was calculated for the Kratky—Porod chain model and compared with the experimental results. Data on the intrinsic viscosity and radii of gyration for other solvents at temperatures from 0 to 100°C were analyzed in the same way, and the effects of solvent and temperature on the statistical segment length were evaluated. Polymer—solvent interaction parameters were estimated from the second virial coefficients.     

Acetylation of cellulose I and II studied by limiting viscosity and X-ray diffraction

When cellulose triacetates and some hydrolyzed acetates are boiled in 2.5N hydrochloric acid there is no residue. Under the same conditions cellulose is hydrolyzed, and a residue is obtained with a limiting viscosity that is related to the average length of the cellulose crystallites. These findings are combined to develop a method for studying the progress of acetylation through the amorphous portion of cellulose and into the crystallites, and to investigate the relative reactivities of cellulose I and cellulose II. Acetates were made from cotton and wood cellulose by a “fibrous” (heterogeneous) esterification involving sulfoacetic acid or perchloric acid catalyst in acetic acid-acetic anhydride; the final acetyl contents (10–41%) were attained by stopping the reaction at various points short of the triester (rather than by hydrolyzing a triester). When these acetates were boiled in 2.5N HCI they did not disappear completely, and the residues were cellulose I, indicating that cellulose acetate had been removed. With increasing acetyl the yield of residue decreased, and beyond about 33% acetyl the viscosity and x-ray measurements showed that the length and width of the crystallites decreased. However, when a nonsolvent such as toluene was added to the acetylation medium, the limiting viscosity did not change over the same acetyl range (up to 40%). Samples of varying acetyl values were taken during a regular acetylation of cotton linters in a mixer with sulfuric acid catalyst. X-ray studies of the residues obtained by boiling the acetates in 2.5N HCI revealed the presence of unreacted cellulose I even after 40% acetyl had been reached. This explains why the manufacture of cellulose esters from cellulose I requires complete esterification before they are hydrolyzed to the desired acetyl level. It was shown that there is a distinct difference between the acetylation reactivity of cellulose I and cellulose II. This indicates the importance of avoiding cellulose II formation during the refinement of cellulose for the manufacture of cellulose acetate in a process involving activation with acetic acid.     

Fabrication of cellulose triacetate/graphene oxide porous membrane

Cellulose triacetate (AC)/graphene oxide (GO) porous membranes were successfully fabricated by combining ultrasonication and phase inversion method. The structures and morphologies of the resultant composite membranes were investigated by X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy, respectively. Microscopic and X‐ray diffraction measurements revealed that GO sheets were uniformly dispersed within the AC matrix. The pore size and structure were modulated by changing GO concentration from 0.25 to 1 wt%. Membrane thermal properties were also studied. Among all tested membranes, the most favorable GO amount was 1 wt%, giving Td_3% of 274°C, which represents a 22°C enhancement compared with AC. Conversely, the membranes showed improved barrier properties against water and ethanol. The decrease of both ethanol and water fluxes was assigned to the stabilization of composite membrane structure, as a result of GO progressive addition. Bovine serum albumin rejection assay indicated an increasing from 78% in the case of CA membrane to 99% in the case of CA/GO 1 wt% of the rejection degree after 90 min. Copyright © 2015 John Wiley & Sons, Ltd.     

Morphological studies of liquid-crystalline cellulose derivatives. II. Hydroxypropyl cellulose films prepared from liquid-crystalline aqueous solutions

A morphological study of hydroxypropyl cellulose (HPC) was performed on solid films prepared by casting from a liquid-crystalline aqueous solution at rest or under shear. Electron microscopic observations reveal that many round particles composed of stacked disks are densely packed in the interior of a quiescently cast HPC film, while on the film surface formation of fibrous textures is also noted. Shear-deformed HPC films exhibit some interesting morphological features according to the shearing conditions. It is found by electron microscopy that the originally round particles become more and more elongated as shear stress increases. The resulting rodlike fibrillar entities are considerably aligned in the shear direction (SD), but form a banded structure with periodic discontinuities of molecular orientation distribution along the SD. A new mechanism of structural transformation is proposed in order to interpret these results.     

Dose rate dependence of cellulose triacetate dosimeter and radiochromic film dosimeter

The doses of γ-rays and electron beams were evaluated by Fricke dosimetry and the responses of cellulose triacetate dosimeter (CTA) and radiochromic film dosimeter (RCF) to the two types of radiations were compared to investigate their dose rate dependence. Both the change in absorbance at 280 nm of CTA and that in absorbance at 510 nm of RCF caused by γ-irradiation were larger than those by electron-irradiation, when the dosimeters were irradiated to the same dose. The results in this study suggest that the responses of CTA and RCF are dependent upon dose rate.     

Solution properties of cellulose tris(3,5-dimethyl-phenylcarbamate)

The dilute-solution behavior and liquid crystal formation of cellulose tris(3,5-dimethylphenylcarbamate) (CTDC) in 1-methyl-2-pyrrolidone (NMP) at 25°C are discussed by summarizing our recent studies, and its molecular characteristics are compared with those of cellulose tris(phenylcarbamate) (CTC) in the same solvent. The molecular weight dependences of optical anisotropy factor, radius of gyration, intrinsic viscosity ([η]), and isotropic-cholesteric phase boundary concentration for CTDC are explained consistently by current theories based on the wormlike chain. An analysis of the newly measured [η] for CTC shows that the backbone conformation and chain stiffness are substantially the same for the two cellulose derivatives in NMP. However, a distinct difference in optical anisotropy is found and briefly discussed in relation to the higher optical resolution capacity of CTDC than that of CTC in chromatographic separation of racemic compounds.     

Mechanism of facilitated saccharide transport through plasticized cellulose triacetate membranes

Mechanistic insight is gained for saccharide transport through plasticized cellulose triacetate (CTA) membranes containing lipophilic ion-pair transport carriers. The molecular structures of the different membrane components are systematically varied and diagnostic transport characteristics such as saccharide–carrier diffusion constant and saccharide extraction constant are determined. The observed percolation thresholds support a jumping mechanism, however, the diffusion constants are found to decrease as the size of the saccharide, carrier cation, and carrier anion increase, indicating that the rate-limiting step in the transport process involves diffusion of a complex comprised of all three components. The data is reconciled in terms of mobile-site jumping mechanism where the saccharide is relayed along a sequence of ion-pair carriers that are locally mobile. In an attempt to improve saccharide selectivity, calix-[4]-arene dicarboxylates were evaluated as potential ditopic transport carriers. This produced no major change in saccharide extraction constants.