Poly state

Department of Chemistry and Biochemistry Cal Poly State University San Luis Obispo, CA 93407 Email Jsimek calpoly.edu... 

Vinyl chloride is an industrial chemical produced in large amounts (10 ° Ib/year in the United States) and is used in the preparation of poly(vmyl chloride) Poly(vinyl chio ride) often called simply vinyl has many applications including siding for houses wall coverings and PVC piping... 

The production of polyester fibers leads that of all other types Annual United States production of poly ester fibers is 1 6 million tons versus 1 4 million tons for cotton and 1 0 million tons for nylon Wool and silk trail far behind at 0 04 and 0 01 million tons re spectively... 

The term polymer is derived from the Greek words poly and meros, meaning many parts. We noted in the last section that the existence of these parts was acknowledged before the nature of the interaction which held them together was known. Today we realize that ordinary covalent bonds are the intramolecular forces which keep the polymer molecule intact. In addition, the usual type of intermolecular forces—hydrogen bonds, dipole-dipole interactions, and London forces—hold assemblies of these molecules together in the bulk state. The only thing that is remarkable about these molecules is their size, but that feature is remarkable indeed. 

We shall be interested in determining the effect of electrolytes of low molecular weight on the osmotic properties of these polymer solutions. To further simplify the discussion, we shall not attempt to formulate the relationships of this section in general terms for electrolytes of different charge types-2 l, 2 2, 3 1, 3 2, and so on-but shall consider the added electrolyte to be of the 1 1 type. We also assume that these electrolytes have no effect on the state of charge of the polymer itself that is, for a polymer such as, say, poly (vinyl pyridine) in aqueous HCl or NaOH, the state of charge would depend on the pH through the water equilibrium and the reaction... 

Fig. 4. Chemistry of poly(vinyl cinnamate) negative-acting resist. Initial light absorption by the photosensitizer is followed by energy transfer to produce a pendant cinnamate group in a triplet electronic state. This combines with a second cinnamate on another polymer chain, forming a polymer—polymer...

Chlorine cannot be stored economically or moved long distances. International movements of bulk chlorine are more or less limited to movements between Canada and the United States. In 1987, chlorine moved in the form of derivatives was 3.3 million metric tons or approximately 10% of total consumption (3). Exports of ethylene dichloride, vinyl chloride monomer, poly(vinyl chloride), propylene oxide, and chlorinated solvents comprise the majority of world chlorine movement. Countries or areas with a chlorine surplus exported in the form of derivatives include Western Europe, Bra2il, USA, Saudi Arabia, and Canada. Countries with a chlorine deficit are Taiwan, Korea, Indonesia, Vene2uela, South Africa, Thailand and Japan (3). 

Lead azide is not readily dead-pressed, ie, pressed to a point where it can no longer be initiated. However, this condition is somewhat dependent on the output of the mixture used to ignite the lead azide and the degree of confinement of the system. Because lead azide is a nonconductor, it may be mixed with flaked graphite to form a conductive mix for use in low energy electric detonators. A number of different types of lead azide have been prepared to improve its handling characteristics and performance and to decrease sensitivity. In addition to the dextrinated lead azide commonly used in the United States, service lead azide, which contains a minimum of 97% lead azide and no protective colloid, is used in the United Kingdom. Other varieties include colloidal lead azide (3—4 pm), poly(vinyl alcohol)-coated lead azide, and British RE) 1333 and RE) 1343 lead azide which is precipitated in the presence of carboxymethyl cellulose (88—92). 

Vinal fibers, or poly(vinyl alcohol) fibers, are not made in the United States, but the fiber is produced commercially in Japan, Korea, and China where the generic name vinylon is used. These materials are the subject of this article (see also Vinyl polymers, vinyl alcohol polymers). 

Table 6 shows the sales estimates for principal film and sheet products for the year 1990 (14). Low density polyethylene films dominate the market in volume, followed by polystyrene and the vinyls. High density polyethylene, poly(ethylene terephthalate), and polypropylene are close in market share and complete the primary products. A number of specialty resins are used to produce 25,000—100,000 t of film or sheet, and then there are a large number of high priced, high performance materials that serve niche markets. The original clear film product, ceUophane, has faUen to about 25,000 t in the United States, with only one domestic producer. Table 7 Hsts some of the principal film and sheet material manufacturers in the United States.

Until 1990 the EPA maintained a Hst of chemicals suitable for potable water treatment ia the United States. Siace then the entire question of certification and standards has been turned over to a group of organi2ations headed by the National Sanitation Eoundation, which has issued voluntary standards. As of January 1992, standards had been issued for most of the principal inorganic products, but only for two polymers, poly(DADMAC) and Epi-DMA (epichl orohydrin dimethyl amine) polymers (78). Certifications for commercial products meeting specified standards are issued by the National Sanitation Eoundation, Underwriter Laboratories, and Risk Eocus/Versar (79). 

There is growing commercial importance and escalating scientific interest in PVDF. The World Patent database, including the United States, Hsts 678 patents that cite the term poly(vinyHdene fluoride) for the period 1963—1980 and 2052 patents for the period 1981—1992 Chemical Abstracts files covering the years 1967—1992 contain 5282 references for the same term. Thirty years ago there was only one commercial producer of PVDF in the world now there are two in the United States, two in Japan, and three in Europe. 

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

Poly(vinylchloride). Cellular poly(vinyl chloride) is prepared by many methods (108), some of which utili2e decompression processes. In all reported processes the stabili2ation process used for thermoplastics is to cool the cellular state to a temperature below its second-order transition temperature before the resia can flow and cause coUapse of the foam. 

A type of physical stabili2ation process, unique for poly(vinyl chloride) resias, is the fusion of a dispersion of plastisol resia ia a plastici2er. The viscosity of a resia—plastici2er dispersioa shows a sharp iacrease at the fusioa temperature. Ia such a system expansioa can take place at a temperature corresponding to the low viscosity the temperature can then be raised to iacrease viscosity and stabili2e the expanded state. 

Applications. Among the P—O- and P—N-substituted polymers, the fluoroalkoxy- and aryloxy-substituted polymers have so far shown the greatest commercial promise (14—16). Both poly[bis(2,2,2-trifluoroethoxy)phosphazene] [27290-40-0] and poly(diphenoxyphosphazene) [28212-48-8] are microcrystalline, thermoplastic polymers. However, when the substituent symmetry is dismpted with a randomly placed second substituent of different length, the polymers become amorphous and serve as good elastomers. Following initial development of the fluorophosphazene elastomers by the Firestone Tire and Rubber Co., both the fluoroalkoxy (EYPEL-F) and aryloxy (EYPEL-A) elastomers were manufactured by the Ethyl Corp. in the United States from the mid-1980s until 1993 (see ELASTOLffiRS,SYNTHETic-PHOSPHAZENEs). 

Applications. Polymers with small alkyl substituents, particularly (13), are ideal candidates for elastomer formulation because of quite low temperature flexibiUty, hydrolytic and chemical stabiUty, and high temperature stabiUty. The abiUty to readily incorporate other substituents (ia addition to methyl), particularly vinyl groups, should provide for conventional cure sites. In light of the biocompatibiUty of polysdoxanes and P—O- and P—N-substituted polyphosphazenes, poly(alkyl/arylphosphazenes) are also likely to be biocompatible polymers. Therefore, biomedical appHcations can also be envisaged for (3). A third potential appHcation is ia the area of soHd-state batteries. The first steps toward ionic conductivity have been observed with polymers (13) and (15) using lithium and silver salts (78). 

Vinyl-Coated Fabrics. Leather substitutes are designed to imitate the appearance of leather with its grain surface. This requirement has been accomphshed by coating substances that are capable of forming a uniform film, and was first met by plasticized poly(vinyl chloride) (PVC). A leather-like material termed vinyl-coated fabric was developed in the 1930s in the United States and Germany. Shortages of leather after World War 11 spurred the expansion of this material. 

About 35% of total U.S. LPG consumption is as chemical feedstock for petrochemicals and polymer iatermediates. The manufacture of polyethylene, polypropylene, and poly(vinyl chloride) requires huge volumes of ethylene (qv) and propylene which, ia the United States, are produced by thermal cracking/dehydrogenation of propane, butane, and ethane (see Olefin polymers Vinyl polymers). 

The most innovative photohalogenation technology developed in the latter twentieth century is that for purposes of photochlorination of poly(vinyl chloride) (PVC). More highly chlorinated products of improved thermal stabiUty, fire resistance, and rigidity are obtained. In production, the stepwise chlorination may be effected in Hquid chlorine which serves both as solvent for the polymer and reagent (46). A soHd-state process has also been devised in which a bed of microparticulate PVC is fluidized with CI2 gas and simultaneously irradiated (47). In both cases the reaction proceeds, counterintuitively, to introduce Cl exclusively at unchlorinated carbon atoms on the polymer backbone. 

Uses. Phthabc anhydride is used mainly in plasticizers, unsaturated polyesters, and alkyd resins (qv). PhthaUc plasticizers consume 54% of the phthahc anhydride in the United States (33). The plasticizers (qv) are used mainly with poly(vinyl chloride) to produce flexible sheet such as wallpaper and upholstery fabric from normally rigid polymers. The plasticizers are of two types diesters of the same monohydric alcohol such as dibutyl phthalate, or mixed esters of two monohydric alcohols. The largest-volume plasticizer is di(2-ethylhexyl) phthalate [117-81-7] which is known commercially as dioctyl phthalate (DOP) and is the base to which other plasticizers are compared. The important phthahc acid esters and thek physical properties are Hsted in Table 12. The demand for phthahc acid in plasticizers is naturally tied to the growth of the flexible poly(vinyl chloride) market which is large and has been growing steadily. 

Manufacture and Processing. Terephthalic acid and dimethyl terephthalate did not become large-volume industrial chemicals until after World War II. Imperial Chemical Industries in the United Kingdom in 1949 and Du Pont in the United States in 1953 commercialized fibers made from poly(ethylene terephthalate). Dimethyl terephthalate and ethylene glycol were the comonomers used by both companies (see Fibers, polyester). 

Work had gone on in both the United States and Europe, notably at Du Pont and ICI Ltd. in the United Kingdom, on exploring the whole series of alkylene terephthalate polymers in connection with new synthetic fibers. Poly(l,4-butylene terephthalate) (PBT) was investigated in detail, as it had very... 

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