Vinyl acetal polymers

Vinyl acetal polymers are made by the acid-cataly2ed acetalization of poly(viQyl alcohol) [9002-89-5] with aldehydes (1). 

Analogously, poly(vinyl ketals) can be prepared from ketones, but since poly(vinyl ketals) are not commercially important, they are not discussed here. The acetalization reaction strongly favors formation of the 1,3-dioxane ring, which is a characteristic feature of this class of resins. The first of this family, poly(vinyl ben2al), was prepared in 1924 by the reaction of poly(vinyl alcohol) with ben2aldehyde in concentrated hydrochloric acid (2). Although many members of this class of resins have been made since then, only poly(vinyl formal) [9003-33-2] (PVF) and poly(vinyl butyral) [63148-65-2] (PVB) continue to be made in significant commercial quantities. 

The poly(vinyl acetal) prepared from acetaldehyde was developed in the early 1940s by Shawinigan Chemicals, Ltd., of Canada and sold under the trade name Alvar. Early uses included injection-molded articles, coatings for paper and textiles, and replacement for shellac. Production peaked in the early 1950s and then decreased as a result of competition from less expensive resins such as poly(vinyl chloride) (see Vinyl polymers, poly(vinyl chloride)). 

Poly(vinyl alcohol) used to manufacture the poly(vinyl acetal)s is made from poly(vinyl acetate) homopolymer (see Vinyl polymers, vinyl alcohol polymers Vinyl POLYMERS, vinyl acetate polymers). Hydrolysis of poly(vinyl acetate) homopolymer produces a polyol with predominandy 1,3-glycol units. The polyol also contains up to 2 wt % 1,2-glycol units that come from head-to-head bonding during the polymeri2ation of vinyl acetate monomer. Poly(vinyl acetate) hydrolysis is seldom complete, and for some appHcations, not desired. For example, commercial PVF resins may contain up to 13 wt % unhydroly2ed poly(vinyl acetate). Residual vinyl acetate units on the polymer help improve resin solubiHty and processibiHty (15). On the other hand, the poly(vinyl alcohol) preferred for commercial PVB resins has less than 3 wt % residual poly(vinyl acetate) units on the polymer chain. 

Commercial poly(vinyl acetal)s are terpolymers with varying amounts of vinyl acetate and vinyl alcohol units remaining on the backbone after acetaH2ation. The class can be represented by the foUowing stmcture, showing acetal (1), vinyl alcohol (2), and vinyl acetate (3) units. 

Assuming that acetalization is irreversible and that both 1,3- and 1,2-glycol units are present in poly (vinyl alcohol), the highest degree of acetalization that can be expected on a statistical basis is 81.6% (18). However, acetalization is reversible (19), and even higher degrees of acetalization are possible (7,20,21). For most applications, complete acetalization is not needed, and would be difficult to achieve on a commercial scale without a significant amount of intermolecular acetalization. 

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PVF resins [VINYL POLYhffiRS - VINYL ACETAL POLYMERS] (Vol 24)... 

Poly(vinyl acetal). See Vinyl acetal polymers. 

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). 

OOCCH3 vinyl acetate A-CH2—CH Vinyl POLYMERS, vinyl acetate polymers... 

Tackifiers are used to increase the tackiness and the setting speed of adhesives. They increase tackiness by softening the poly(vinyl acetate) polymer in the wet and the dry adhesive film. Tackifiers are usually rosin or its derivatives or phenoHc resins. Other additives frequently needed for specific apphcation and service conditions are antifoams, biocides, wetting agents, and humectants. 

Vinyl acetate polymers have long been used as chewing gum bases. They have been studied as controUed release agents for programmed administration of dmgs and as a base for antifouling marine paints (166,167). 

MATTHEWS, G. A. R., Vinyl and Allied Polymers Vol. II, Vinyl Chloride and Vinyl Acetate Polymers, lliffe, London (1972). 

Approximately 2.5 million tons of acetic acid is produced each year in the United States for a variety of purposes, including preparation of the vinyl acetate polymer used in paints and adhesives. About 20% of the acetic acid synthesized industrially is obtained by oxidation of acetaldehyde. Much of the remaining 80% is prepared by the rhodium-catalyzed reaction of methanol with carbon monoxide. 

Figure 12.5 Pyrogram of Mowilith 30, a vinyl acetate polymer used in conservation. Peak assignments 1, acetic acid 2, benzene 3, styrene 4, indene 5, 1,2 dihydro naphthalene 6, naphthalene 7, 2 methyl naphthalene 8, 1 methyl naphthalene 9, biphenyl 10, fluorene 11, anthracene...

PVA in, 25 617 setting speed of, 25 579-580 smectites application, 6 697t solution, 1 532-534 structural, 1 534-545 styrenic block copolymers in, 24 714 use of latex in, 14 711-712 vinyl acetate polymers in, 25 578-583 viscosity of, 25 581 water-borne, 25 475 Adhesive systems, microencapsules in, 16 460... 

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