Poly special

It is not the purpose of this book to discuss in detail the contributions of NMR spectroscopy to the determination of molecular structure. This is a specialized field in itself and a great deal has been written on the subject. In this section we shall consider only the application of NMR to the elucidation of stereoregularity in polymers. Numerous other applications of this powerful technique have also been made in polymer chemistry, including the study of positional and geometrical isomerism (Sec. 1.6), copolymers (Sec. 7.7), and helix-coil transitions (Sec. 1.11). We shall also make no attempt to compare the NMR spectra of various different polymers instead, we shall examine only the NMR spectra of different poly (methyl methacrylate) preparations to illustrate the capabilities of the method, using the first system that was investigated by this technique as the example. 

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. 

In conventional tenter orientation, the sequence of steps is as described above (MD—TD). In some cases it is advantageous to reverse the draw order (TD—MD) or to use multiple draw steps, eg, MD—TD—MD. These other techniques are used to produce "tensilized" films, where the MD tensile properties are enhanced by further stretching. The films are generally unbalanced in properties and in extreme cases may be fibrillated to give fiber-like elements for special textile appHcations. Tensilized poly(ethylene terephthalate) is a common substrate for audio and video magnetic tape and thermal transfer tape. 

Poly(vinyl fluoride) is available from Du Pont both as a resia and as transparent and pigmented films under the trademark Tedlar PVF film. Films are available ia nonoriented and oriented grade ia several tensile modifications and thicknesses, with either adherable or nonadherable release-grade surfaces. The 1992 prices ranged from 30 to 70/kg, vs 24 to 62/kg ia 1988. Prices for specially tailored films were significantly higher. 

Because lactic acid has both hydroxyl and carboxyl functional groups, it undergoes iatramolecular or self-esterificatioa and forms linear polyesters, lactoyUactic acid (4) and higher poly(lactic acid)s, or the cycUc dimer 3,6-dimethyl-/)-dioxane-2,5-dione [95-96-5] (dilactide) (5). Whereas the linear polyesters, lactoyUactic acid and poly(lactic acid)s, are produced under typical condensation conditions such as by removal of water ia the preseace of acidic catalysts, the formation of dilactide with high yield and selectivity requires the use of special catalysts which are primarily weakly basic. The use of tin and ziac oxides and organostaimates and -titanates has been reported (6,21,22). 

The newer open-ceU foams, based on polyimides (qv), polyben2imida2oles, polypyrones, polyureas, polyphenylquinoxalines, and phenoHc resins (qv), produce less smoke, are more fire resistant and can be used at higher temperatures. These materials are more expensive and used only for special appHcations including aircraft and marine vessels. Rigid poly(vinyl chloride) (PVC) foams are available in small quantities mainly for use in composite panels and piping appHcations (see Elame retardants Heat-RESISTANTPOLYA rs). 

The even-numbered carbon alpha olefins (a-olefins) from through C q are especially useful. For example, the C, C, and Cg olefins impart tear resistance and other desirable properties to linear low and high density polyethylene the C, Cg, and C q compounds offer special properties to plasticizers used in flexible poly(vinyl chloride). Linear C q olefins and others provide premium value synthetic lubricants linear 145 olefins are used in... 

The in situ process is simpler because it requires less material handling (35) however, this process has been used only for resole resins. When phenol is used, the reaction system is initially one-phase alkylated phenols and bisphenol A present special problems. As the reaction with formaldehyde progresses at 80—100°C, the resin becomes water-insoluble and phase separation takes place. Catalysts such as hexa produce an early phase separation, whereas NaOH-based resins retain water solubiUty to a higher molecular weight. If the reaction medium contains a protective coUoid at phase separation, a resin-in-water dispersion forms. Alternatively, the protective coUoid can be added later in the reaction sequence, in which case the reaction mass may temporarily be a water-in-resin dispersion. The protective coUoid serves to assist particle formation and stabUizes the final particles against coalescence. Some examples of protective coUoids are poly(vinyl alcohol), gum arabic, and hydroxyethjlceUulose. 

Phthahc anhydride (1) is the commercial form of phthaUc acid (2). The worldwide production capacity for the anhydride was ca 3.5 x 10 metric tons ia 1993, and it was used ia the manufacture of plasticizers (qv), unsaturated polyesters, and alkyd resins (qv) (see Polyesters, unsaturated). Sales of terephthahc acid (3) and its dimethyl ester are by far the largest of any of the benzenepolycarboxyhc acids 14.3 x 10 t were produced in 1993. This is 80% of the total toimage of ah. commercial forms of the benzenepolycarboxyhc acids. Terephthahc acid is used almost exclusively for the manufacture of poly(ethylene terephthalate), which then is formed into textiles, films, containers, and molded articles. Isophthahc acid (4) and trimehitic anhydride (5) are commercial products, but their worldwide production capacities are an order of magnitude smaller than for terephthahc acid and its dimethyl ester. Isophthahc acid is used primarily in the production of unsaturated polyesters and as a comonomer in saturated polyesters. Trimehitic anhydride is used mainly to make esters for high performance poly(vinyl chloride) plasticizers. Trimesic acid (6), pyromehitic dianhydride (7), and hernimehitic acid (8) have specialized commercial apphcations. The rest of the benzenepolycarboxyhc acids are not available commercially. 

The packaging (qv) requirements for shipping and storage of thermoplastic resins depend on the moisture that can be absorbed by the resin and its effect when the material is heated to processing temperatures. Excess moisture may result in undesirable degradation during melt processing and inferior properties. Condensation polymers such as nylons and polyesters need to be specially predried to very low moisture levels (3,4), ie, less than 0.2% for nylon-6,6 and as low as 0.005% for poly(ethylene terephthalate) which hydrolyzes faster. 

Aqueous Solution Viscosity. A special solution preparation method is used for one type of measurement of aqueous solution viscosity (96). The appropriate amount of poly(ethylene oxide) resin is dispersed in 125 mL of anhydrous isopropyl alcohol by vigorous stirring. Because the resin is insoluble in anhydrous isopropyl alcohol, a slurry forms and the alcohol wets the resin particles. An appropriate amount of water is added and stirring is slowed to about 100 rpm to avoid shear degradation of the polymer. In Table 4, the nominal resin concentration reported is based on the amount of water present and ignores the isopropyl alcohol. 

Analysis for Poly(Ethylene Oxide). Another special analytical method takes advantage of the fact that poly(ethylene oxide) forms a water-insoluble association compound with poly(acryhc acid). This reaction can be used in the analysis of the concentration of poly(ethylene oxide) in a dilute aqueous solution. Ereshly prepared poly(acryhc acid) is added to a solution of unknown poly(ethylene oxide) concentration. A precipitate forms, and its concentration can be measured turbidimetricaHy. Using appropriate caUbration standards, the precipitate concentration can then be converted to concentration of poly(ethylene oxide). The optimum resin concentration in the unknown sample is 0.2—0.4 ppm. Therefore, it is necessary to dilute more concentrated solutions to this range before analysis (97). Low concentrations of poly(ethylene oxide) in water may also be determined by viscometry (98) or by complexation with KI and then titration with Na2S202 (99). 

CPA. Copolymer alloy membranes (CPAs) are made by alloying high molecular weight polymeries, plasticizers, special stabilizers, biocides, and antioxidants with poly(vinyl chloride) (PVC). The membrane is typically reinforced with polyester and comes in finished thicknesses of 0.75—1.5 mm and widths of 1.5—1.8 m. The primary installation method is mechanically fastened, but some fully adhered systems are also possible. The CPA membranes can exhibit long-term flexibiHty by alleviating migration of the polymeric plasticizers, and are chemically resistant and compatible with many oils and greases, animal fats, asphalt, and coal-tar pitch. The physical characteristics of a CPA membrane have been described (15). 

Introduced in 1972, the whoUy aromatic polyamide, poly i ra-phenylene teraphthalamide), termed aramid, was the subject of extensive evaluation as a tire cord in all types of tires (8,14). As of the late 1990s, however, only specialized appHcations have emerged for aramid tire cord that draw on their high strength-to-weight ratio to produce tires with lower weight (16). 

Vinylidene Chloride Copolymer Latex. Vinyhdene chloride polymers are often made in emulsion, but usuaUy are isolated, dried, and used as conventional resins. Stable latices have been prepared and can be used direcdy for coatings (171—176). The principal apphcations for these materials are as barrier coatings on paper products and, more recently, on plastic films. The heat-seal characteristics of VDC copolymer coatings are equaUy valuable in many apphcations. They are also used as binders for paints and nonwoven fabrics (177). The use of special VDC copolymer latices for barrier laminating adhesives is growing, and the use of vinyhdene chloride copolymers in flame-resistant carpet backing is weU known (178—181). VDC latices can also be used to coat poly(ethylene terephthalate) (PET) bottles to retain carbon dioxide (182). 

The wash primer is a special type of vinyl coating. This material contains a poly(vinyl butyral) resin, zinc chromate, and phosphoric acid in an alcohol-water solvent. The coating is so thin it is HteraUy washed onto a freshly blasted steel surface, where it passivates the metal surface by converting it to a thin iron phosphate-chromate coating. The alcohol solvent makes it possible to apply the coating over damp surfaces. The coating forms the first coat of... 

The anthraquinones are useful in acrylics and are compatible with polystyrene and ceUulosics. Solvent Red 111 has a special affinity for poly(methyl methacrylate) as the red in automobile taillights exposure for a year in Florida or Arizona produces only a very slight darkening. Acid types are usehil for phenohcs (see Dyes, anthraquinone). 

---