Poly , combination

Combination and disproportionation are competitive processes and do not occur to the same extent for all polymers. For example, at 60°C termination is virtually 100% by combination for polyacrylonitrile and 100% by disproportionation for poly (vinyl acetate). For polystyrene and poly (methyl methacrylate), both reactions contribute to termination, although each in different proportions. Each of the rate constants for termination individually follows the Arrhenius equation, so the relative amounts of termination by the two modes is given by... 

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

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...

The cured polymers are hard, clear, and glassy thermoplastic resins with high tensile strengths. The polymers, because of their highly polar stmcture, exhibit excellent adhesion to a wide variety of substrate combinations. They tend to be somewhat britde and have only low to moderate impact and peel strengths. The addition of fillers such as poly (methyl methacrylate) (PMMA) reduces the brittleness somewhat. Newer formulations are now available that contain dissolved elastomeric materials of various types. These mbber-modifted products have been found to offer adhesive bonds of considerably improved toughness (3,4). 

Nitrile mbber finds broad application in industry because of its excellent resistance to oil and chemicals, its good flexibility at low temperatures, high abrasion and heat resistance (up to 120°C), and good mechanical properties. Nitrile mbber consists of butadiene—acrylonitrile copolymers with an acrylonitrile content ranging from 15 to 45% (see Elastomers, SYNTHETIC, NITRILE RUBBER). In addition to the traditional applications of nitrile mbber for hoses, gaskets, seals, and oil well equipment, new applications have emerged with the development of nitrile mbber blends with poly(vinyl chloride) (PVC). These blends combine the chemical resistance and low temperature flexibility characteristics of nitrile mbber with the stability and ozone resistance of PVC. This has greatly expanded the use of nitrile mbber in outdoor applications for hoses, belts, and cable jackets, where ozone resistance is necessary. 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Two-Phase Aqueous Extraction. Liquid—Hquid extraction usually involves an aqueous phase and an organic phase, but systems having two or more aqueous phases can also be formed from solutions of mutually incompatible polymers such as poly(ethylene glycol) (PEG) or dextran. A system having as many as 18 aqueous phases in equiHbrium has been demonstrated (93). Two-phase aqueous extraction, particularly useful in purifying biological species such as proteins (qv) and enzymes, can also be carried out in combination with fermentation (qv) so that the fermentation product is extracted as it is formed (94). 

Antagonism between antimony oxide and phosphoms flame retardants has been reported in several polymer systems, and has been explained on the basis of phosphoms interfering with the formation or volatilization of antimony haUdes, perhaps by forming antimony phosphate (12,13). This phenomenon is also not universal, and depends on the relative amounts of antimony and phosphoms. Some useful commercial poly(vinyl chloride) (PVC) formulations have been described for antimony oxide and triaryl phosphates (42). Combinations of antimony oxide, halogen compounds, and phosphates have also been found useful in commercial flexible urethane foams (43). 

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). 

The presence of carbon—fluorine bonds in organic polymers is known to characteristically impart polymer stabiUty and solvent resistance. The poly(fluorosibcones) are siloxane polymers with fluorinated organic substituents bonded to siUcon. Poly(fluorosibcones) have unique appHcations resulting from the combination provided by fluorine substitution into a siloxane polymer stmcture (see Silicon compounds, silicones). 

The combination of stmctural strength and flotation has stimulated the design of pleasure boats using a foamed-in-place polyurethane between thin skins of high tensUe strength (231). Other ceUular polymers that have been used in considerable quantities for buoyancy appHcations are those produced from polyethylene, poly(vinyl chloride), and certain types of mbber. The susceptibUity of polystyrene foams to attack by certain petroleum products that are likely to come in contact with boats led to the development of foams from copolymers of styrene and acrylonitrUe which are resistant to these materials... 

Miscellaneous Applications. CeUular plastics have been used for display and novelty pieces from their eady development. Polystyrene foam combines ease of fabrication with lightweight, attractive appearance, and low cost to make it a favorite in these uses. PhenoHc foam has its principal use in doral displays. Its abiHty to hold large amounts of water for extended periods is used to preserve cut dowers. CeUular poly(vinyl chloride) is used in toys and athletic goods, where its toughness and ease of fabrication into intricate shapes have been valuable. 

A variety of cellular plastics exists for use as thermal iasulation as basic materials and products, or as thermal iasulation systems ia combination with other materials (see Foamed plastics). Polystyrenes, polyisocyanurates (which include polyurethanes), and phenoHcs are most commonly available for general use, however, there is increasing use of other types including polyethylenes, polyimides, melamines, and poly(vinyl chlorides) for specific appHcations. 

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). 

Figure 5 illustrates the type of encapsulation process shown in Figure 4a when the core material is a water-immiscible Hquid. Reactant X, a multihmctional acid chloride, isocyanate, or combination of these reactants, is dissolved in the core material. The resulting mixture is emulsified in an aqueous phase that contains an emulsifier such as partially hydroly2ed poly(vinyl alcohol) or a lignosulfonate. Reactant Y, a multihmctional amine or combination of amines such as ethylenediamine, hexamethylenediamine, or triethylenetetramine, is added to the aqueous phase thereby initiating interfacial polymerisation and formation of a capsule shell. If reactant X is an acid chloride, base is added to the aqueous phase in order to act as an acid scavenger. 

Ghdants are needed to faciUtate the flow of granulation from the hopper. Lubricants ensure the release of the compressed mass from the punch surfaces and the release/ejection of the tablet from the die. Combinations of siUcas, com starch, talc (qv), magnesium stearate, and high molecular weight poly(ethylene glycols) are used. Most lubricants are hydrophobic and may slow down disintegration and dmg dissolution. 

Purified terephthalic acid and dimethyl terephthalate are used as raw materials for the production of saturated polyesters. During 1993, the combined worldwide production of purified terephthafic acid plus dimethyl terephthalate exceeded 14 x 10 t (42), which is 80% of the total benzenepolycarboxyfic acid production. Terephthafic acid is also produced ia technical or cmde grades which are not pure enough for manufacture of poly(ethylene terephthalate). In almost all cases, the technical-grade material is immediately converted to purified terephthafic acid or dimethyl terephthalate, which together are the articles of commerce. 

Automotive appHcations account for about 116,000 t of woddwide consumption aimuaHy, with appHcations for various components including headlamp assembHes, interior instmment panels, bumpers, etc. Many automotive appHcations use blends of polycarbonate with acrylonitrile—butadiene—styrene (ABS) or with poly(butylene terephthalate) (PBT) (see Acrylonitrile polymers). Both large and smaH appHances also account for large markets for polycarbonate. Consumption is about 54,000 t aimuaHy. Polycarbonate is attractive to use in light appHances, including houseware items and power tools, because of its heat resistance and good electrical properties, combined with superior impact resistance. 

PEN film for audio- and videotape and various electronic appHcations and blow molded PEN containers for hot-fill appHcations are already being marketed in Japan. NDA is unlikely to ever become as inexpensive as terephthaUc acid but novel NDA-based polyesters will become available if a market need exists. One example could be the experimental polyester PBN (Celanese Corp.) this is the NDA analogue of PBT, poly(l,4-butylene naphthalene-2,6-dicarboxylate) [28779-82-0]. It has a high rate of crystallization, faster even than that of PBT, and its combination of physical properties is weU-suited for injection molding. 

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