VINYL ALCOHOL COPOLYMER

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). 

Thermoform able sheet may be mono- or multilayer with the latter produced by lamination or coextmsion. Multilayers are employed to incorporate high oxygen-barrier materials between stmctural or high water-vapor barrier plastics. Both ethylene vinyl alcohol copolymers and poly(vinyhdene chloride) (less often) are used as high oxygen-barrier interior layers with polystyrene or polypropylene as the stmctural layers, and polyolefin on the exterior for sealing. 

Small amounts of TAIC together with DAP have been used to cure unsaturated polyesters in glass-reinforced thermo sets (131). It has been used with polyfunctional methacrylate esters in anaerobic adhesives (132). TAIC and vinyl acetate are copolymerized in aqueous suspension, and vinyl alcohol copolymer gels are made from the products (133). Electron cure of poly(ethylene terephthalate) moldings containing TAIC improves heat resistance and transparency (134). 

Fig. 2. Oxygen permeabilities of ethylene—vinyl alcohol copolymers at 20°C (10). See Table 1 for unit conversions.

Permeation in the vinyUdene chloride copolymer and the polyolefins is not affected by humidity the permeability and diffusion coefficient in the ethylene—vinyl alcohol copolymer can be as much as 1000 times greater with high humidity (14—17). 

Several cleaning formulations for specific uses contain unreacted polyamines. Examples include mixtures of ammonium alkylbenzenesulfonate, solvents, and PIP which give good cleaning and shine performance on mirrors and other hard surfaces without rinsing (305), and a hard-surface cleaner composed of a water-soluble vinyl acetate—vinyl alcohol copolymer, EDA, cyclohexanone [108-94-1] dimethyl sulfoxide [67-68-5] a surfactant, and water (306). TEPA, to which an average of 17 moles of ethylene oxide are added, improves the clay sod removal and sod antiredeposition properties of certain hquid laundry detergents (307). 

In addition to the above materials a number of copolymers containing vinyl acetate have been marketed. Ethylene-vinyl acetate (EVA) copolymers are discussed in Chapter 11 and vinyl chloride-vinyl acetate copolymers in Chapter 12. On the other hand, the commercial ethylene-vinyl alcohol copolymers, although derived from EVA, are considered briefly in this chapter since in weight terms the ethylene component is usually the minor one. 

EVAL Ethylene-vinyl alcohol copolymer, PA6/6.6 Polyamide 6/6.6... 

HB Hopfenberg, A Apicella, DE Saleeby. Factors affecting water sorption in and solute release from glassy ethylene-vinyl alcohol copolymers. J Membrane Sci 8 273-281, 1981. 

MA Samus, G Rossi. Methanol absorption in ethylene-vinyl alcohol copolymers Relation between solvent diffusion and changes in glass transition temperature in glassy polymeric materials. Macromolecules 29 2275-2288, 1996. 

Recently, a new class of excipients based on ethylene oxide-vinyl alcohol copolymers (see Figure 17.12) has been developed (PEO-g-PVA). The combination of PVA and PEO should result in an excellent instant-release tablet coating. One way to... 

Oyane, A., Kawashita, M., Nakanishi, K, Kokubo,T., Minoda, M., Miyamoto, T. and Nakamura, T. (2003) Bonelike apatite formation on ethylene-vinyl alcohol copolymer modified with silane coupling agent and calcium silicate solutions. Biomaterials, 24, 1729-1735. 

Oyane, A., Uchida, M. and Ito, A. (2005) Laminin-apatite composite coating to enhance cell adhesion to ethylene-vinyl alcohol copolymer. Journal of Biomedical Materials Research, 72A, 168-174. 

Figure 7 Surface pressure(mN/m) dependence on time(hr. ) of vinyl acetate/vinyl alcohol copolymers(M =10 ),...

Ethylene-vinyl alcohol (EVOH), 18 49, 50 Ethylene-vinyl alcohol copolymers composition of commercial barrier, 3 385t... 

One of the PVA derivatives extensively used in this field is ethylene-vinyl alcohol copolymer (EVOH). Their blends with different polyolefins are also effective as oxigen barrier materials. 

PVA Formation Reaction. Poly(vinyl alcohol) is itself a modified polymer being made by the alcoholysis of poly(vinyl acetate) under acid or base catalysis as shown in Equation 1 (6.7). This polymer cannot be made by a direct polymerization because the vinyl alcohol monomer only exists in the tautomeric form of acetaldehyde. This saponification reaction can also be run on vinyl acetate copolymers and this affords a means of making vinyl alcohol copolymers. The homopolymer is water soluble and softens with decomposition at about 200°C while the properties of the copolymers would vary widely. Poly(vinyl alcohol) has been widely utilized in polymer modification because ... 

Vinyl alcohol copolymer gel is hydrophilic and has been developed for aqueous-phase size-exclusion liquid chromatography however, it is less polar than the polysaccharides. Its specificity permits the direct injection of a biological sample without deproteinization. For example, blood serum from a patient suffering from chronic nephritis has been injected directly as a measure of the degree of dialysis (Figure 3.17). Adenosine triphosphate, adenosine diphosphate, and adenosine monophosphate in red blood cells have also been separated directly (Figure 3.18). Theophylline in blood serum has been... 

Conditions columns, Asahipak GS320 (vinyl alcohol copolymer gel), 50 cm x 7.6 mm i.d. eluent, 0.1 M sodium phosphate containing 0.3 M sodium chloride pH 7.0 flow rate, 1 ml min-1 detection, UV 250 nm direct injection of sample. Peaks l, protein, 2, orotidine 3, creatinine, and 4, uric acid. 

The separation of basic and metal-sensitive compounds is difficult on silica-based stationary phase materials, but these separations can be performed on vinyl alcohol copolymer gels. Examples are the separation of methallothionein from dolphin kidney, a-, j8-, and y-endorphin, and nucleotide and nucleoside mixtures.8 However, an analytical-scale separation may also be performed on surface-modified wide-pore silica gels (pore size 300 A or more), using columns which showed a negative response in the heavy metal test described above. 

Column, octadecyl-bonded vinyl alcohol copolymer gel, 10 cm x 6 mm i.d. eluent, 0.05 M sodium phosphate solution in 20% acetonitrile flow rate 1 ml min-1 temperature, 30 °C. Compounds 3C1, 3-chlorobenzoic acid and 4Et, 4-ethylbenzoic acid. 

Enthalpy can be measured by liquid chromatography where enthalpy is a slope of the relationship between In k and the inverse value of the absolute temperature. A schematic diagram is shown in Figure 6.7. The slope depends upon the solutes being retained by the same liquid chromatographic mechanism. An example is given in Table 6.4. The results, measured on an octadecyl-bonded vinyl alcohol copolymer gel, did not show a simple linear relationship. This is due to a conformation change of the octadecyl-bonded vinyl alcohol copolymer gel stationary phase material, which has a phase transition point at about 33 °C. 

Several improved stationary phase materials have been synthesized for reversed-phase liquid chromatography. One material is vinyl alcohol copolymer gel. This stationary phase is quite polar and chemically very stable however, it demonstrated a strong retention capacity for polycyclic aromatic hydrocarbons.45 9 Although stable octadecyl- and octyl-bonded silica gels have been synthesized from pure silica gel50,51 and are now commercially available, such an optimization system has not yet been built. Further experiments are required to elucidate the retention mechanism, and to systematize it within the context of instrumentation. 

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