Poly , made

In polymers made of dis-symmetric monomers, such as, for example, poly(propylene), the stmcture may be irregular and constitutional isomerism can occur as shown in figure C2.1.1(a ). The succession of the relative configurations of the asymmetric centres can also vary between stretches of the chain. Configuration isomerism is characterized by the succession of dyads which are named either meso, if the two asymmetric centres have the same relative configurations, or racemo if the configurations differ (figure C2.1.1(b )). A polymer is called isotactic if it contains only one type of dyad and syndiotactic if the dyad sequence strictly alternates between the meso and racemo fonns. 

Mention may here be made of the fact that natural unvulcanised rubber is poly-isoprene (2-methylbutadiene) ... 

Poly (methyl Acrylate). The monomer used for preparing poly(methyl acrylate) is produced by the oxidation of propylene. The resin is made by free-radical polymerization initiated by peroxide or azo catalysts and has the following formula ... 

Commonly used isocyanates are toluene dhsocyanate, methylene diphenyl isocyanate, and polymeric isocyanates. Polyols used are macroglycols based on either polyester or polyether. The former [poly(ethylene phthalate) or poly(ethylene 1,6-hexanedioate)] have hydroxyl groups that are free to react with the isocyanate. Most flexible foam is made from 80/20 toluene dhsocyanate (which refers to the ratio of 2,4-toluene dhsocyanate to 2,6-toluene dhsocyanate). High-resilience foam contains about 80% 80/20 toluene dhsocyanate and 20% poly(methylene diphenyl isocyanate), while semi-flexible foam is almost always 100% poly(methylene diphenyl isocyanate). Much of the latter reacts by trimerization to form isocyanurate rings. 

Capillary Tubes Figure 12.42 shows a cross section of a typical capillary tube. Most capillary tubes are made from fused silica coated with a 20-35-)J,m layer of poly-imide to give it mechanical strength. The inner diameter is typically 25-75 )J,m, which is smaller than that for a capillary GC column, with an outer diameter of 200-375 )J,m. 

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. 

The windows of the absorption cell are made from polymer material such as polyethylene, poly(ethylene terephthalate Terylene ) or polystyrene. 

Under conditions of extreme acidity or alkalinity, acryhc ester polymers can be made to hydroly2e to poly(acryhc acid) or an acid salt and the corresponding alcohol. However, acryhc polymers and copolymers have a greater resistance to both acidic and alkaline hydrolysis than competitive poly(vinyl acetate) and vinyl acetate copolymers. Even poly(methyl acrylate), the most readily hydroly2ed polymer of the series, is more resistant to alkah than poly(vinyl acetate) (57). Butyl acrylate copolymers are more hydrolytically stable than ethyl acrylate copolymers (58). 

However, because of the low melting poiats and poor hydrolytic stabiUty of polyesters from available iatermediates, Carothers shifted his attention to linear ahphatic polyamides and created nylon as the first commercial synthetic fiber. It was nearly 10 years before. R. Whinfield and J. T. Dickson were to discover the merits of poly(ethylene terephthalate) [25038-59-9] (PET) made from aromatic terephthaUc acid [100-21-0] (TA) and ethylene glycol [107-21-1] (2G). 

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). 

Fully modified yams had smooth, all-skin cross sections, a stmcture made up of numerous small crystaUites of cellulose, and filament strengths around 0.4 N/tex (4.5 gf/den). They were generally known as the Super tire yams. Improved Super yams (0.44—0.53 N/tex (5—6 gf/den)) were made by mixing modifiers, and one of the best combiaations was found to be dimethylamine with poly-(oxyethylene) glycol of about 1500 mol wt (25). Ethoxjlated fatty acid amines have now largely replaced dimethylamine because they are easier to handle and cost less. 

AUoys of ceUulose with up to 50% of synthetic polymers (polyethylene, poly(vinyl chloride), polystyrene, polytetrafluoroethylene) have also been made, but have never found commercial appUcations. In fact, any material that can survive the chemistry of the viscose process and can be obtained in particle sizes of less than 5 p.m can be aUoyed with viscose. 

Quenched sheet is pulled horizontally from the stack and is then either wound on roUs or sheared into sheets of the required dimension. Among the polymers made into sheet this way are the polyolefins, poly(vinyl chloride), amorphous polyester, polycarbonate, and polyarjiate. 

Poly(ethylene oxide)s [25372-68-3] are made by condensation of ethylene oxide with a basic catalyst. In order to achieve a very high molecular weight, water and other compounds that can act as chain terminators must be rigorously excluded. Polymers up to a molecular weight of 8 million are available commercially in the form of dry powders (27). These must be dissolved carefliUy using similar techniques to those used for dry polyacrylamides. Poly(ethylene oxide)s precipitate from water solutions just below the boiling point (see Polyethers, ethylene oxide polymers). 

Allyl polymers are made by free-radical polymerization of diaHyl compounds, most frequently diallyl dimethyl ammonium chloride (DADMAC) [7398-69-8] forming a chain containing a five-membered ring (28) poly(DADMAC) [26062-79-3]. 

The Fe, Co, and Ni deposits are extremely fine grained at high current density and pH. Electroless nickel, cobalt, and nickel—cobalt alloy plating from fluoroborate-containing baths yields a deposit of superior corrosion resistance, low stress, and excellent hardenabiUty (114). Lead is plated alone or ia combination with tin, iadium, and antimony (115). Sound iasulators are made as lead—plastic laminates by electrolyticaHy coating Pb from a fluoroborate bath to 0.5 mm on a copper-coated nylon or polypropylene film (116) (see Insulation, acoustic). Steel plates can be simultaneously electrocoated with lead and poly(tetrafluoroethylene) (117). Solder is plated ia solutioas containing Pb(Bp4)2 and Sn(Bp4)2 thus the lustrous solder-plated object is coated with a Pb—Sn alloy (118). 

Poly etrafluoroethylene is manufactured and sold in three forms granular, fine powder, and aqueous dispersion each requires a different fabrication technique. Granular resins are manufactured in a wide variety of grades to obtain a different balance between powder flows and end use properties (Pig. 1). Pine powders that are made by coagulating aqueous dispersions also are available in various grades. Differences in fine powder grades correspond to their usefulness in specific appHcations and to the ease of fabrication. Aqueous dispersions are sold in latex form and are available in different grades. A variety of formulation techniques are used to tailor these dispersions for specific appHcations. 

Poly(vinylchloride). Cellular poly(vinyl chloride) can be produced from several expandable formulations as well as by decompression techniques. Rigid or flexible products can be made depending on the amount and type of plasticizer used (43). 

Butanediol. 1,4-Butanediol [110-63-4] made from formaldehyde and acetylene, is a significant market for formaldehyde representing 11% of its demand (115). It is used to produce tetrahydrofuran (THF), which is used for polyurethane elastomers y-butyrolactone, which is used to make various pyrroHdinone derivatives poly(butylene terephthalate) (PBT), which is an engineering plastic and polyurethanes. Formaldehyde growth in the acetylenic chemicals market is threatened by alternative processes to produce 1,4-butanediol not requiring formaldehyde as a raw material (140) (see Acetylene-derived chemicals). 

Poly(vinyl acetate). The dielectric and mechanical spectra of hybrids produced by mixing a poly(vinyl acetate)—THE solution with TEOS, followed by the addition of HCl have been investigated (45). Mixtures were made which were beheved to be 0, 5, 10, 15, and 20 wt % Si02, respectively. These composites were transparent and Eourier transform infrared spectroscopy (ftir) revealed hydrogen bonding between the siUcate network and carbonyl units of the poly(vinyl acetate) (PVAc). No shift in the T of the composites from that of the pure PVAc was observed. Similarly, the activation... 

It has also been found that polymers possessing functional groups such as amines and pyridines are soluble in pregeUed sol solutions, especially, poly(2-vin5ipyridine) and poly(N-vinylpyrroHdinone) (PVP) (49). There, materials were made as part of a study of the synthesis of nonshrinking sol—gel-derived networks (49). 

Jippliance wires require a higher temperature rating (105°C or higher). Therefore, the insulation is made of duorinated thermoplastics, such as poly-tetrafluoroethylene (PTEE) or duorinated ethylene—propjdene (EEP). 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

The viscosity of the latex can also be dependent on pH. In the case of some latices, lowering the pH with a weak acid such as glycine is an effective method for raising the viscosity without destabilising the system. Latices made with poly(vinyl alcohol) as the primary emulsifier can be thickened by increasing the pH with a strong alkaU. 

In the second quarter of the twentieth century, with the development of poly(vinyl chloride), nylon, polyurethane, and other polymers, many new and improved leather-like materials, so-called coated fabrics (qv), were placed on the market. Shortages of leather after World War 11 led to the expansion of these leather-like materials ("man-made" leathers) to replace leather in shoes, clothing, bags, upholstery, and other items. DurabiUty and waterproof quahties superior to leather made coated fabrics advantageous, in spite of imperfection in breathabihty and flexibiUty. Demands for shoes, clothing, and other items are stiU increasing due to growing world population and urbanization. 

Poly(alI lene glycol)s. While these can be made from polymeri2ation of any alkylene oxide, they are usually prepared either from propylene oxide as the water-insoluble type, or as water-soluble copolymers of propylene oxide and up to 50% ethylene oxide (35,36) (see Polyethers, propylene OXIDE polymers). Current worldwide production is estimated to be about 45,000 t. 

Alkenylsuccinic anhydrides made from several linear alpha olefins are used in paper sizing, detergents, and other uses. Sulfosuccinic acid esters serve as surface active agents. Alkyd resins (qv) are used as surface coatings. Chlorendric anhydride [115-27-5] is used as a flame resistant component (see Flame retardants). Tetrahydrophthalic acid [88-98-2] and hexahydrophthalic anhydride [85-42-7] have specialty resin appHcations. Gas barrier films made by grafting maleic anhydride to polypropylene [25085-53-4] film are used in food packaging (qv). Poly(maleic anhydride) [24937-72-2] is used as a scale preventer and corrosion inhibitor (see Corrosion and corrosion control). Maleic anhydride forms copolymers with ethylene glycol methyl vinyl ethers which are partially esterified for biomedical and pharmaceutical uses (189) (see Pharmaceuticals). 

---