Cellulose permeability

Polymer Plasticizer. Nylon, cellulose, and cellulose esters can be plasticized using sulfolane to improve flexibiUty and to increase elongation of the polymer (130,131). More importantly, sulfolane is a preferred plasticizer for the synthesis of cellulose hoUow fibers, which are used as permeabiUty membranes in reverse osmosis (qv) cells (131—133) (see Hollow-FIBERMEMBRANEs). In the preparation of the hoUow fibers, a molten mixture of sulfolane and cellulose triacetate is extmded through a die to form the hoUow fiber. The sulfolane is subsequently extracted from the fiber with water to give a permeable, plasticizer-free, hoUow fiber. 

Barrier Layers. Depending on composition, barrier layers can function simply as spatial separators or they can provide specified time delays by swelling at controlled rates or undergoing reactions such as hydrolysis or dissolution. Suitable barrier materials include cellulose esters and water-permeable polymers such as gelatin and poly(vinyl alcohol) (see Barrier polymers). 

FIG. 22-76 Constant -cost lines as a function of permeability and selectivity for CO2/CH4, Cellulose-acetate membrane mscf is one thousand standard cubic feet, CouHesy VP R. Grace.)... 

Most of the above can be made into plastic films - primarily used for wrapping. Film properties vary widely from permeable for food to impermeable to preserve dryness. Paper, treated or untreated, has been used for many years as a covering film, but has low strength when wet and is difficult to make transparent. In the 1920s, the transparency of cellophane revolutionized wrap. It is regenerated cellulose, like viscose rayon, except it is extruded in sheet instead of fiber, unfortunately it is sensitive to water and humidity. 

While it would be difficult to enumerate all of the efforts in the area of implants where plastics are involved, some of the significant ones are (1) the implanted pacemaker, (2) the surgical prosthesis devices to replace lost limbs, (3) the use of plastic tubing to support damaged blood vessels, and (4) the work with the portable artificial kidney. The kidney application illustrates an area where more than the mechanical characteristics of the plastics are used. The kidney machine consists of large areas of a semi-permeable membrane, a cellulosic material in some machines, where the kidney toxins are removed from the body fluids by dialysis based on the semi-permeable characteristics of the plastic membrane. A number of other plastics are continually under study for use in this area, but the basic unit is a device to circulate the body fluid through the dialysis device to separate toxic substances from the blood. The mechanical aspects of the problem are minor but do involve supports for the large amount of membrane required. 

Cellulosic plastics are usually used for the membrane, but any water vapor permeable material is a good possibility, provided the film has good mechanical properties. 

Water Permeation and Solute Separation through the Membrane. The measurements of water permeability of the 67 membranes prepared under different conditions were carried out by using an Amicon Diaflo Cell (effective membrane area, 13.9 cm2) under a pressure of 3 kg/cm2 at 25 °C. Some results are listed in Table 1067. It is apparent that much higher water absorption and permeability than the cellulosic membrane are characteristic of the 67 membranes prepared by both the casting polymerization and conventional casting. 

The exceptional ability of PCL to form blends with many other polymers has stimulated a large amount of research. The subject has been reviewed a number of times (7,8). To date, the potential of such blends for drug delivery has been largely unexploited. The permeability of blends of PCL with cellulose propionate, cellulose... 

Polymer blends have been categorized as (1) compatible, exhibiting only a single Tg, (2) mechanically compatible, exhibiting the Tg values of each component but with superior mechanical properties, and (3) incompatible, exhibiting the unenhanced properties of phase-separated materials (8). Based on the mechanical properties, it has been suggested that PCL-cellulose acetate butyrate blends are compatible (8). Dynamic mechanical measurements of the Tg of PCL-polylactic acid blends indicate that the compatability may depend on the ratios employed (65). Both of these blends have been used to control the permeability of delivery systems (vide infra). 

The membrane is critically important in osomometry. Selection of a membrane involves reconciliation of high permeability toward the solvent with virtual impermeability to the smallest polymer molecules present in the sample. Membranes of cellulose are most widely used. Commercially Regenerated cellulose film is a common source. The undried gel cellophane film is often preferred, but the dry film may be swollen in water (or in aqueous solutions of caustic or zinc chloride ) to satisfactory porosity. Useful cellulose membranes may also be prepared by denitration of nitrocellulose films/ and special advantages have been claimed for bacterial cellulose films. The water in the swollen membrane in any case may be replaced by a succession of miscible organic solvents ending with the one in which osmotic measurements are to be made. Membranes of varying porosity may be... 

Hydroxypropylguar gum gel can be crosslinked with borates [1227], ti-tanates, or zirconates. Borate-crosslinked fluids and linear hydroxyethyl-cellulose gels are the most commonly used fluids for high-permeability fracture treatments. This is for use for hydraulic fracturing fluid under high-temperature and high-shear stress. 

The predominant RO membranes used in water applications include cellulose polymers, thin film oomposites (TFCs) consisting of aromatic polyamides, and crosslinked polyetherurea. Cellulosic membranes are formed by immersion casting of 30 to 40 percent polymer lacquers on a web immersed in water. These lacquers include cellulose acetate, triacetate, and acetate-butyrate. TFCs are formed by interfacial polymerization that involves coating a microporous membrane substrate with an aqueous prepolymer solution and immersing in a water-immiscible solvent containing a reactant [Petersen, J. Memhr. Sol., 83, 81 (1993)]. The Dow FilmTec FT-30 membrane developed by Cadotte uses 1-3 diaminobenzene prepolymer crosslinked with 1-3 and 1-4 benzenedicarboxylic acid chlorides. These membranes have NaCl retention and water permeability claims. 

Ghosh [548] used cellulose nitrate microporous filters (500 pm thick) as scaffold material to deposit octanol into the pores and then under controlled pressure conditions, displace some of the oil in the pores with water, creating a membrane with parallel oil and water pathways. This was thought to serve as a possible model for some of the properties of the outermost layer of skin, the stratum comeum. The relative proportions of the two types of channel could be controlled, and the properties of 5-10% water pore content were studied. Ibuprofen (lipophilic) and antipyr-ine (hydrophilic) were model drugs used. When the filter was filled entirely with water, the measured permeability of antipyrine was 69 (in 10 6 cm/s) when 90% of the pores were filled with octanol, the permeability decreased to 33 95% octanol content further decreased permeability to 23, and fully octanol-filled filters indicated 0.9 as the permeability. 

An infrequently used method (in pharmaceutical research) for determining the UWL permeability involves measuring transport of molecules across a high-porosity microfilter that is not coated by a lipid. The molecules are able to diffuse freely in the water channels of the microfilter. The filter barrier prevents convective mixing between the donor and acceptor sides, and an UWL forms on each sides of the microfilter. Camenisch et al. [546] measured the effective permeabilities of a series of drug molecules in 96-well microtiter plate-filterplate (Millipore GVHP mixed cellulose ester, 0.22 pm pore) sandwich where the filters were not coated by a lipid. The permeabilities were nearly the same for all the molecules, as shown in Fig. 7.8a. Our analysis of their data, Fig. 7.8b, indicates / aq = 460 pm (sandwich stirred at 150 rpm). We have been able to confirm similar results in our laboratory with different microfilters, using the lipid-free method. 

Controlling fluid loss loss is particularly important in the case of the expensive high density brine completion fluids. While copolymers and terpolymers of vinyl monomers such as sodium poly(2-acrylamido-2-methylpropanesulfonate-co-N,N-dimethylacrylamide-coacrylic acid) has been used (H)), hydroxyethyl cellulose is the most commonly used fluid loss additive (11). It is difficult to get most polymers to hydrate in these brines (which may contain less than 50% wt. water). The treatment of HEC particle surfaces with aldehydes such as glyoxal can delay hydration until the HEC particles are well dispersed (12). Slurries in low viscosity oils (13) and alcohols have been used to disperse HEC particles prior to their addition to high density brines. This and the use of hot brines has been found to aid HEC dissolution. Wetting agents such as sulfosuccinate diesters have been found to result in increased permeability in cores invaded by high density brines (14). 

This technique has been applied to the concentration of organochlorine and organophosphorus insecticide [7,8] and various ethers, glycols amines, nitriles, hydrocarbons, and chlorinated hydrocarbons. Although this work was concerned with drinking water, it is a useful technique which may have application in seawater analysis. Cellulose acetate [9], ethyl cellulose acetate [6], and crosslinked polyethyleneinine [8] have been used as semi-permeable membranes. 

In Table 3, the membranes of capsules 2,7,8, and 10 are quite dense and have low permeability. In Table 4, capsule entries 2 and 4 are again relatively impermeable and are probably unsuitable for xenogeneic cell encapsulation. By comparison the alginate/cellulose sulfate//polydimethylene-co-guanidine/calcium chloride capsules seem to offer the most suitable MWCO (approximately 100 kD). This type of capsule is photographed in Fig. 2, with... 

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