Cellulose acetate polymers properties

MOO Moore, W.R. and Tidswell, B.M., Thermo namic properties of solutions of cellulose derivatives. 1. Dilute solutions of secondary cellulose acetate, /. Polym. Sci., 27,459,1958. 

There is finally a group of commercial biodegradable polymers, the blends of polymers from different origins. They have been formulated so that they offer interesting properties, limiting the amount of costly materials in their composition. In this family fall blends of starch with aliphatic polyesters, polylactic acid, polycaprolactone, polyvinylalcohol or cellulose acetate. The properties of starch (low cost material) are improved by the controlled addition of other more costly biopolymers. They will be described in section 1.2.1. 

Cellulose acetate Loeb-Sourirajan reverse osmosis membranes were introduced commercially in the 1960s. Since then, many other polymers have been made into asymmetric membranes in attempts to improve membrane properties. In the reverse osmosis area, these attempts have had limited success, the only significant example being Du Font s polyamide membrane. For gas separation and ultrafUtration, a number of membranes with useful properties have been made. However, the early work on asymmetric membranes has spawned numerous other techniques in which a microporous membrane is used as a support to carry another thin, dense separating layer. 

Other blends such as polyhydroxyalkanoates (PHA) with cellulose acetate (208), PHA with polycaprolactone (209), poly(lactic acid) with poly(ethylene glycol) (210), chitosan and cellulose (211), poly(lactic acid) with inorganic fillers (212), and PHA and aUphatic polyesters with inorganics (213) are receiving attention. The different blending compositions seem to be limited only by the number of polymers available and the compatibiUty of the components. The latter blends, with all natural or biodegradable components, appear to afford the best approach for future research as property balance and biodegradabihty is attempted. Starch and additives have been evaluated ia detail from the perspective of stmcture and compatibiUty with starch (214). 

Although the prime function of plasticisers in cellulose acetate is to bring the processing temperature of the compound below the polymer decomposition temperature, it has additional values. An increase in the plasticiser content will reduce the melt viscosity at a given temperature and simplify processing. The physical properties of the finished product will be modified, increasing toughness... 

Where transparency is required, a range of polymers is available. Polystyrene is the least expensive but polymethylmethacrylate has an outstanding high light transmission combined with excellent weathering properties. Also to be considered are the polycarbonates, glass-clear polyamides, SAN, butadiene-styrene block copolymers, MBS polymers, plasticised PVC, ionomers and cellulose esters such as cellulose acetate. 

Cellulosic They are tough, transparent, hard or flexible natural polymers made from plant cellulose feedstock. With exposure to light, heat, weather and aging, they tend to dry out, deform, embrittle and lose gloss. Molding applications include tool handles, control knobs, eyeglass frames. Extrusion uses include blister packaging, toys, holiday decorations, etc. Cellulosic types, each with their specialty properties, include cellulose acetates (CAs), cellulose acetate butyrates (CABs), cellulose nitrates (CNs), cellulose propionate (CAPs), and ethyl celluloses (EC). 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

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). 

All polymers utilized in this investigation have been listed in Table 2, along with their supplier and the concentration range over which they were tested. Polymers were either used as received or purified by filtration through a 0.22 or 0.45-pm MiUipore cellulose acetate membrane. For aseptic applications autoclaving was carried out for 20 min at a temperature of 121 °C. Qualitative properties of each polymer are listed in Table 3. For polymers supplied as solutions, dialysis was carried out in membranes (Spectrum Medical Industries, Houston, TX) with a MWCO of 10,000 daltons. 

Plasticizers are used in the polymer industry to improve flexibility, workability, and general handling properties. Dibutyl sebacate and phthalates, such as dibutyl phthalate, diethyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, and diphenyl-2-ethylhexyl phosphate, serve widely as plasticizers in vinylidene chloride copolymers, nitrocellulose-coated regenerated cellulose film, and cellulose acetate (Castle et ah, 1988a). In PVC, di(2-ethylhexyl)... 

Nature has long used reactions such as these to produce interesting solids such as cotton (seed pod), hemp (grass), and silk (cocoons for worms while they develop into moths) as fibers that we can strand into rope or weave into cloth. Chemists discovered in the early twentieth century that cellulose could be hydrolyzed with acetic acid to form cellulose acetate and then repolymerized into Rayon, which has properties similar to cotton. They then searched for manmade monomers with which to tailor properties as replacements for rope and sdk. In the 1930s chemists at DuPont and at ICl found that polyamides and polyesters had properties that could replace each of these. [Linear polyolefins do not seem to form in nature as do condensation polymers. This is probably because the organometaUic catalysts are extremely sensitive to traces of H2O, CO, and other contaminants. This is an example where we can create materials in the laboratory that are not found in nature.]... 

Weldons, J. D., and V. Stannett Some properties of isolated graft copolymers of cellulose acetate and styrene. Polymer preprint A.C.S. Meeting, Detroit, Michigan April 1965. 

Tn the last decades many attempts have been made to obtain attractive - materials by intimate mixing of two polymers with opposite or complementary properties. For example, the impact resistance of brittle polystyrene is increased by mixing with a rubber the wettability of polyacrylonitrile fiber is increased by mixing with hydrophilic saponified cellulose acetate, and the inconvenient flat-spotting of nylon-reinforced tires is suppressed by mixing stiffer polyester fibrils into the nylon fibers. In practically all cases these products acquire their final shape via the liquid state. Thus, the viscous properties of these liquid mixtures are important. 

H.K. Lonsdale, U. Merten and R.L. Riley, Transport Properties of Cellulose Acetate Osmotic Membranes, J. Appl. Polym. Sci. 9, 1341 (1965). 

During the 1960s and 1970s the Office of Saline Water sponsored development of noncellulosic reverse osmosis membranes. Many polymers were evaluated as Loeb-Sourirajan membranes but few matched the properties of cellulose acetate. Following the development of interfacial composite membranes by Cadotte, this line of research was abandoned by most commercial membrane producers. 

The salt form of the polymer may also play a role in determining the performance of the formulation. Kane et al. [32] found that cellulose acetate phthalate was more effective than cellulose acetate trimellitate in controlling the dissolution of sulfothiazole-sodium tablets with cellulose acetate. The enteric properties of hydroxypropylmethylcellulose phthalate (HPMCP) were found to depend on the solubility of the drug that was coated. 

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