Mixed cellulose esters

Since this early work, a very large range of organic acids has been used to prepare cellulose esters, mixed esters, and ethw esters (Rouse, 1965). A typical example of considerable commercial importance is the acetylation of cellulose. As in aU esterifications of macromolecular materials, the accessibility of the hydroxyl groups to the esterilying acid is of prime importance. Reaction (11.1) represents complete esterification, a process that is probably never fuUy achieved. The identification of the esterified products is, therefore, dependent not only on the content of acetyl groups but also on the location of these groups on the macromolecular backbone. Both factors are affected by the method of preparation and the esterification conditions. 

Cotton linters or wood pulp are nitrated using mixed acid followed by treatment with hot acidified water, pulping, neutralization, and washing. The finished product is blended for uniformity to a required nitrogen content. The controlling factors in the nitration process are the rates of diffusion of the acid into the fibers and of water out of the fibers, the composition of mixed acid, and the temperature (see Cellulose esters, inorganic esters). 

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

Mixed cellulose esters containing the dicarboxylate moiety, eg, cellulose acetate phthalate, have commercially useful properties such as alkaline solubihty and excellent film-forming characteristics. These esters can be prepared by the reaction of hydrolyzed cellulose acetate with a dicarboxyhc anhydride in a pyridine or, preferably, an acetic acid solvent with sodium acetate catalyst. Cellulose acetate phthalate [9004-38-0] for pharmaceutical and photographic uses is produced commercially via the acetic acid—sodium acetate method. 

The price of cellulose ester flake has generally increased with inflation and as of mid-1987 was estimated at ca 3.64— 4.71/kg for cellulose diacetate molding resin and from ca 4.16— 4.71/kg for the mixed esters molding resins depending on purity and the number of propionyl or butyryl esters (4). 

From 1946 to mid-1987, Farbenfabriken Bayer AG in Germany was the European producer of cellulose acetate, cellulose acetate butyrate (CAB), and cellulose acetate propionate (CAP) before closing its faciUties. Bayer s exit from the cellulose acetate mixed esters business leaves Eastman Chemical Co. in the United States as the sole producer of CAB/CAP resins. 

Determining the degree of substitution using standard proton nmr refles on the integral ratio between the ceUulosic ring protons ( i 5.0-2.96) and the ester alkyl protons ( i 1.26 for butyryl and propionyl and i 2.06 for acetyl methyl groups). This simple procedure is used extensively to determine the extent of esterification and is currently the fastest, easiest way for determining the DS of mixed cellulose esters. 

Mixing cellulose esters in nonpolar hydrocarbons, such as toluene or xylene, may result in static electricity buildup that can cause a flash fire or explosion. When adding cellulose esters to any flammable Hquid, an inert gas atmosphere should be maintained within the vessel (132). This risk may be reduced by the use of conductive solvents in combination with the hydrocarbon or by use of an antistatic additive. Protective clothing and devices should be provided. 

Cellulose esters, especially acetate propionate and acetate butyrate mixed esters, have found limited use in a wide variety of specialty appHcations such as in nonfogging optical sheeting (171), low profile additives to improve the surface characteristics of sheet-molding (SMC) compounds and hulk-molding (BMC) compounds (172,173), and controlled dmg release via encapsulation (174). 

Collect asbestos on a special, 0.8 micrometer pore size, 25 mm diameter mixed cellulose ester filter, using a back-up pad. 

The primary OH group can be selectively blocked by the bulky triphenyl-methyl (trityl) moiety, followed by esterification at the secondary OH groups and removal of the protecting trityl group. Thus 2,3-di-O-acetyl cellulose has been obtained by this procedure. Moreover, regioselectively substituted mixed cellulose esters, acetate/propionate, were prepared by subsequent acy-... 

MCEF Mixed cellulose ester membranes filter... 

SRM 1876b is intended for use in evaluating transmission electron microscopy (TEM) techniques used to identify and count chrysotile fibers. This SRM consists of sections of mixed-cellulose-ester filters containing chrysotile fibers deposited by an aerosol generator. 

RM 8411 consists of a section of collapsed mixed-cellulose-ester filters with a high concentration (138 fibers/o.oi mm) of chrysotile and a medium concentration (43 fibers/o.oi mm) of amosite. It is intended for use in evaluating the technique used to identify and count asbestos fibers by TEM. 

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. 

Another potentially important fermentation is that producing butyric acid. The process is used industrially on only a small scale at present and details have not been disclosed. Many derivatives of butyric acid are used industrially the benzyl, methyl, octyl and terpenyl esters are used in the perfumery and essence trade and amyl butyrate, bornyl and isobornyl butyrates have been described as plasticizers for cellulose esters. Moreover vinyl butyrate is a possible ingredient of polymerizable materials. The mixed acetic and butyric acid esters of polysaccharides are also coming into favor. Cellulose acetate butyrate is marketed as an ingredient of lacquer and is less inflammable than the pure acetate. Dextran (see below) acetate butyrate may have similar uses. 

Sampling and Analytical Precision and Accuracy. The accuracy of results obtained from a sampling and analytical method are determined by comparison with an independent method. The aerosols of phosphoric and sulfuric acids were collected on mixed cellulose ester filters (14 ) and analyzed by ion chromatography. Table V shows the collection efficiency of the 7-mm O.D./700-mg silica gel collection tubes with respect to the results obtained from filter samples, and the precision obtained from calculation of the pooled relative standard deviation. 

Filter Methods. The filters most commonly used were mixed-cellulose ester (MCE), glass fiber (GF), and polytetrafluoroethyl-ene (PTFE). Glass fiber and PTFE filters were used almost... 

The first of the set is chlordane (Figure 2). In this case chlordane was collected primarily on the mixed-cellulose ester filter with about 10% collected on the sorbent. If the sampling device was only tested over the proposed sampling period, one hour in this case, vapor collected on the sorbent may not have been detected. Hence, extended sampling periods are necessary to realistically test collection efficiency of the individual sampling media in the train. Also, at higher temperatures and lower chlordane concentration, the fraction collected on the sorbent may be substantially increased. 

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