Poly , conventional

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

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. 

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). 

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). 

Thermoplasticity. High molecular weight poly(ethylene oxide) can be molded, extmded, or calendered by means of conventional thermoplastic processing equipment (13). Films of poly(ethylene oxide) can be produced by the blown-film extmsion process and, in addition to complete water solubiUty, have the typical physical properties shown in Table 3. Films of poly(ethylene oxide) tend to orient under stress, resulting in high strength in the draw direction. The physical properties, melting behavior, and crystallinity of drawn films have been studied by several researchers (14—17). 

Thermoplastic Processing. Poly(ethylene oxide) resins can be thermoplasticaHy formed into soHd products, eg, films, tapes, plugs, retainers, and fillers (qv). Through the use of plasticizers (qv), poly(ethylene oxide) can be extmded, molded, and calendered on conventional thermoplastic... 

Fig. 1. U.S. reinforcement consumption for tires, where A shows cotton B, rayon C, total all-fibers D, nylon E, conventional poly(ethylene terephthalate)...

Dynamic membranes are concentration—polarization layers formed in situ from the ultrafiltration of coUoidal material analogous to a precoat in conventional filter operations. Hydrous zirconia has been thoroughly investigated other materials include bentonite, poly(acryhc acid), and films deposited from the materials to be separated (18). 

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). 

Polyesters. Polyesters (qv) are widely used as the matrix for conventional composites. Two resins of particular importance because of the large amounts used are (poly(ethylene terephthalate) [25038-59-9] (PET) and poly(butylene terephthalate) [24968-12-5] (PBT). Although polyesters can be made from diacids and diols by direct condensation. 

A large volume usage of S—B—S-based compounds is ia footwear. Canvas footwear, such as sneakers and unit soles, can be made by injection mol ding. Frictional properties resemble those of conventionally vulcanised mbbers and are superior to those of the flexible thermoplastics, such as plasticized poly(vinyl chloride). The products remain flexible under cold conditions because of the good low temperature properties of the polybutadiene segment. 

The most chemical-resistant plastic commercially available today is tetrafluoroethylene or TFE (Teflon). This thermoplastic is practically unaffected by all alkahes and acids except fluorine and chlorine gas at elevated temperatures and molten metals. It retains its properties up to 260°C (500°F). Chlorotrifluoroethylene or CTFE (Kel-F, Plaskon) also possesses excellent corrosion resistance to almost all acids and alkalies up to 180°C (350°F). A Teflon derivative has been developed from the copolymerization of tetrafluoroethylene and hexafluoropropylene. This resin, FEP, has similar properties to TFE except that it is not recommended for continuous exposures at temperatures above 200°C (400°F). Also, FEP can be extruded on conventional extrusion equipment, while TFE parts must be made by comphcated powder-metallurgy techniques. Another version is poly-vinylidene fluoride, or PVF2 (Kynar), which has excellent resistance to alkahes and acids to 150°C (300°F). It can be extruded. A more recent development is a copolymer of CTFE and ethylene (Halar). This material has excellent resistance to strong inorganic acids, bases, and salts up to 150°C. It also can be extruded. 

The inability to process PTFE by conventional thermoplastics techniques has nevertheless led to an extensive search for a melt-processable polymer but with similar chemical, electrical, non-stick and low-friction properties. This has resulted in several useful materials being marketed, including tetrafluoro-ethylene-hexafluoropropylene copolymer, poly(vinylidene fluoride) (Figure 13.1(d)), and, most promisingly, the copolymer of tetrafluoroethylene and perfluoropropyl vinyl ether. Other fluorine-containing plastics include poly(vinyl fluoride) and polymers and copolymers based on CTFE. 

Mention may also be made here of a number of polyfunctional compounds such as allyl methacrylate and glycol dimethacrylates which have been used to produce a cross-linked sheet of enhanced heat resistance compared with conventional poly(methyl methacrylate). Some manufacturers supply the sheet in an incompletely cross-linked state which allows a limited amount of forming after which the sheet may be further heated to complete the cure. 

The simplest aromatic polysulphone, poly-(p-phenylene sulphone) (formula I of Table 21.3) does not show thermoplastic behaviour, melting with decomposition above 500°C. Hence in order to obtain a material capable of being processed on conventional equipment the polymer chain is made more flexible by incorporating ether links into the backbone. 

Polymers with very good heat resistance (both in terms of deformation and of heat aging resistance) but which may be processed by conventional techniques, e.g. polysulphones and poly(phenylene oxides). 

The resulting poly(cw-syndiotactic-phenylsilsesquioxanes) are claimed to have equal thermal stability to conventional silicones but with markedly improved hydrolytic stability. 

A number of examples have been studied in recent years, including liquid sulfur [1-3,8] and selenium [4], poly(o -methylstyrene) [5-7], polymer-like micelles [9,11], and protein filaments [12]. Besides their importance for applications, EP pose a number of basic questions concerning phase transformations, conformational and relaxational properties, dynamics, etc. which distinguish them from conventional dead polymers in which the reaction of polymerization has been terminated. EP motivate intensive research activity in this field at present. 

Monodispersed poly (methyl methacrylate-ethyleneglycol dimethacrylate) is prepared by a multistep swelling and polymerization method. When a good solvent such as toluene is applied as a porogen, the seed polymer severely affects the pore structure, whereas no effects are observed with poor solvents, such as cyclohexanol, as a porogen, in comparison with the conventional suspension polymerization (68,69). 

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