Poly pressure

Figure C2.1.8. Reduced osmotic pressure V l(RTc as a function of the polymer weight concentration for solutions of poly(a-metliylstyrene) in toluene at 25 °C. The molecular weight of poly(a-metliylstyrene) varies...

The ethylene glycol liberated by reaction (5.L) is removed by lowering the pressure or purging with an inert gas. Because the ethylene glycol produced by reaction (5.L) is removed, proper stoichiometry is assured by proceeding via the intermediate, bis(2-hydroxyethyl) terephthalate otherwise the excess glycol used initially would have a deleterious effect on the degree of polymerization. Poly(ethylene terephthalate) is more familiar by some of its trade names Mylar as a film and Dacron, Kodel, or Terylene as fibers it is also known by the acronym PET. 

The phenomena we discuss, phase separation and osmotic pressure, are developed with particular attention to their applications in polymer characterization. Phase separation can be used to fractionate poly disperse polymer specimens into samples in which the molecular weight distribution is more narrow. Osmostic pressure experiments can be used to provide absolute values for the number average molecular weight of a polymer. Alternative methods for both fractionation and molecular weight determination exist, but the methods discussed in this chapter occupy a place of prominence among the alternatives, both historically and in contemporary practice. 

First, we consider the experimental aspects of osmometry. The semiperme-able membrane is the basis for an osmotic pressure experiment and is probably its most troublesome feature in practice. The membrane material must display the required selectivity in permeability-passing solvent and retaining solute-but a membrane that works for one system may not work for another. A wide variety of materials have been used as membranes, with cellophane, poly (vinyl alcohol), polyurethanes, and various animal membranes as typical examples. The membrane must be thin enough for the solvent to pass at a reasonable rate, yet sturdy enough to withstand the pressure difference which can be... 

The solute molecular weight enters the van t Hoff equation as the factor of proportionality between the number of solute particles that the osmotic pressure counts and the mass of solute which is known from the preparation of the solution. The molecular weight that is obtained from measurements on poly disperse systems is a number average quantity. 

Table 9.3 lists the intrinsic viscosity for a number of poly(caprolactam) samples of different molecular weight. The M values listed are number average figures based on both end group analysis and osmotic pressure experiments. Tlie values of [r ] were measured in w-cresol at 25°C. In the following example we consider the evaluation of the Mark-Houwink coefficients from these data. 

Another widely used overlay adhesive is the contact type. These specialized adhesives, in the same group as mbber cement, may be of the solvent-base or water-base types. They are often used to bond overlays such as wood veneer, vinyl (poly(vinyl chloride)) films, or high pressure laminates such as countertop overlays. 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

This principle is illustrated in Figure 10 (45). Water adsorption at low pressures is markedly reduced on a poly(vinyhdene chloride)-based activated carbon after removal of surface oxygenated groups by degassing at 1000°C. Following this treatment, water adsorption is dominated by capillary condensation in mesopores, and the si2e of the adsorption-desorption hysteresis loop increases, because the pore volume previously occupied by water at the lower pressures now remains empty until the water pressure reaches pressures 0.3 to 0.4 times the vapor pressure) at which capillary condensation can occur. 

Dry chlorine has a great affinity for absorbing moisture, and wet chlorine is extremely corrosive, attacking most common materials except HasteUoy C, titanium, and tantalum. These metals are protected from attack by the acids formed by chlorine hydrolysis because of surface oxide films on the metal. Tantalum is the preferred constmction material for service with wet and dry chlorine. Wet chlorine gas is handled under pressure using fiberglass-reinforced plastics. Rubber-lined steel is suitable for wet chlorine gas handling up to 100°C. At low pressures and low temperatures PVC, chlorinated PVC, and reinforced polyester resins are also used. Polytetrafluoroethylene (PTFE), poly(vinyhdene fluoride) (PVDE), and... 

The beater additive process starts with a very dilute aqueous slurry of fibrous nitrocellulose, kraft process woodpulp, and a stabilizer such as diphenylamine in a felting tank. A solution of resin such as poly(vinyl acetate) is added to the slurry of these components. The next step, felting, involves use of a fine metal screen in the shape of the inner dimensions of the final molded part. The screen is lowered into the slurry. A vacuum is appHed which causes the fibrous materials to be deposited on the form. The form is pulled out after a required thickness of felt is deposited, and the wet, low density felt removed from the form. The felt is then molded in a matched metal mold by the appHcation of heat and pressure which serves to remove moisture, set the resin, and press the fibers into near final shape (180—182). 

In 1954 the surface fluorination of polyethylene sheets by using a soHd CO2 cooled heat sink was patented (44). Later patents covered the fluorination of PVC (45) and polyethylene bottles (46). Studies of surface fluorination of polymer films have been reported (47). The fluorination of polyethylene powder was described (48) as a fiery intense reaction, which was finally controlled by dilution with an inert gas at reduced pressures. Direct fluorination of polymers was achieved in 1970 (8,49). More recently, surface fluorinations of poly(vinyl fluoride), polycarbonates, polystyrene, and poly(methyl methacrylate), and the surface fluorination of containers have been described (50,51). Partially fluorinated poly(ethylene terephthalate) and polyamides such as nylon have excellent soil release properties as well as high wettabiUty (52,53). The most advanced direct fluorination technology in the area of single-compound synthesis and synthesis of high performance fluids is currently practiced by 3M Co. of St. Paul, Minnesota, and by Exfluor Research Corp. of Austin, Texas. 

Extmsion processes have been used to produce high and low density flexible cellular poly(vinyl chloride). A decomposable blowiag ageat is usually bleaded with the compouad prior to extmsioa. The compouaded resia is thea fed to an extmder where it is melted under pressure and forced out of an orifice iato the atmosphere. After extmsion iato the desired shape, the cellular material is cooled to stabili2e it and is removed by a belt. 

Manufacture. The manufacture of 1,4-cyclohexanedimethanol can be accompHshed by the catalytic reduction under pressure of dimethyl terephthalate ia a methanol solution (47,65). This glycol also may be prepared by the depolymerization and catalytic reduction of linear polyesters that have alkylene terephthalates as primary constituents. Poly(ethylene terephthalate) may be hydrogenated ia the presence of methanol under pressure and heat to give good yields of the glycol (see Polyesters) (66,67). 

Poly(alkylene glycol)s have a number of characteristics that make them desirable as lubricants. Compared to petroleum lubricants, they have lower pour points, a higher viscosity index, and a wider range of solubilities including water, compatibility with elastomers, less tendency to form tar and sludge, and lower vapor pressure (35). 

Membrane Sep r tion. The separation of components ofhquid milk products can be accompHshed with semipermeable membranes by either ultrafiltration (qv) or hyperfiltration, also called reverse osmosis (qv) (30). With ultrafiltration (UF) the membrane selectively prevents the passage of large molecules such as protein. In reverse osmosis (RO) different small, low molecular weight molecules are separated. Both procedures require that pressure be maintained and that the energy needed is a cost item. The materials from which the membranes are made are similar for both processes and include cellulose acetate, poly(vinyl chloride), poly(vinyHdene diduoride), nylon, and polyamide (see AFembrane technology). Membranes are commonly used for the concentration of whey and milk for cheesemaking (31). For example, membranes with 100 and 200 p.m are used to obtain a 4 1 reduction of skimmed milk. 

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