Poly emulsions, adhesion

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

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). 

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(vmyl acetate). This is also known as white glue. ... 

Poly(vinyl acetate) latex is used in the production of water-based emulsion paints, adhesives, and textile and paper treatments. Emulsion paints are stable, dry quickly, and are relatively low cost. PVAC emulsion adhesives are used in labeling and packaging, and as the popular consumer white glue. Copolymers with dibutyl fumarate, vinyl stearate, 2-ethylhexyl acrylate, or ethyl acrylate are used to obtain compositions that are softer for emulsion use. As indicated above, a major use of poly(vinyl acetate) is in the production of poly(vinyl alcohol), which is itself the starting material for poly(viityl butyral) and poly(vinyl formal). 

Poly (vinyl acetate) was used as a solvent-based adhesive in the 1930s, and later as a hot melt, but was not of commercial importance until its introduction in the 1940s, as an emulsion adhesive used mainly to bond paper and wood. Today, in emulsion form as a white glue, it is the most widely used thermoplastic adhesive worldwide. Vinyl acetate-ethylene (VAE) emulsion adhesives, with over 55% vinyl acetate content, were developed in the early 1950s but did not become of commercial importance in the United States until the mid-1960s. 

Casing In. Depending on the case material and the machine speed, normally emulsion adhesives [poly(vinyl acetate) or copolymer-based] with good flowing properties are used for casing in. 

Lamination of Paper and Board. Adhesives based on starch, dextrin, glutin and poly(vinyl alcohol), and also emulsion adhesives, mainly polyfvinyl acetate), are used for the lamination of paper and board. Only when high initial tack and a lay-flat effect are required are hot glues based on glutin still in use. Starch-based adhesives modified with silicate, casein-stabilized copolymer dispersions, and rubber latices are used in the lamination of paper to aluminum foils. Modified polyacrylate solutions and reactive polyurethane adhesives are used mainly for paper-to-plastic lamination. 

Acrylic ester homopolymers or statistical copolymers, whose annual world production is higher than 1 million tons, are used in the fields of paints in emulsion, adhesives, textile fiber processing, and paper industry. These applications are in close relationship with their glass transition temperature, which is relatively low. Poly(methyl acrylate) is much more stable against hydrolytic attack by acids and bases than its isomer poly(vinyl acetate). The poly(butyl acrylate) exhibits an elastomeric character which induces multiple applications. 

Four other groups of synthetic adhesives find uses in secondary processing, ie, overlaying, assembly gluing, etc, and in furniture and cabinet manufacture. Poly(vinyl acetate) (PVA) adhesives are widely used in appHcation of veneers and other overlays to panel substrates and in some unit-assembly operations. PVA adhesives are an emulsion of polyvinyl acetate in water and cure by loss of water. The PVA adhesives are somewhat... 

Poly(viayl acetate) emulsions or hot-melt adhesives are typically used to form the manufacturer s or glue lap joiat of the box. The main criteria for the adhesive is that it provide a strong and tough final bond and that it set up quickly enough to allow fast box production speeds. Production rates ia excess of 240 boxes per minute are not uncommon ia the iadustry. 

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). 

Poly(vinyl acetate) emulsions can be made with a surfactant alone or with a protective coUoid alone, but the usual practice is to use a combination of the two. Normally, up to 3 wt % stabilizers may be included in the recipe, but when water sensitivity or tack of the wet film is desired, as in some adhesives, more may be included. The most commonly used surfactants are the anionic sulfates and sulfonates, but cationic emulsifiers and nonionics are also suitable. Indeed, some emulsion compounding formulas require the use of cationic or nonionic surfactants for stable formulations. The most commonly used protective coUoids are poly(vinyl alcohol) and hydroxyethyl cellulose, but there are many others, natural and synthetic, which are usable if not preferable for a given appHcation. 

Growth in PVAc consumption is illustrated in Eigure 3. The emulsions continue to dominate the adhesives and paint markets. It also shows the distribution of PVAc and copolymer usage by market. The companies Hsted in Table 10 are among the principal suppHers of poly(vinyl acetate)s and vinyl acetate copolymers, but there are numerous other suppHers. Many other companies produce these polymers and consume them internally in the formulation of products. 

Poly(vinyl acetate) emulsions are excellent bases for water-resistant paper adhesives destined for use in manufacturing bags, tubes, and cartons. Glue-lap adhesives, which require moderate-to-high resistance to water, exemplify this type. When routine water resistance is required, a homopolymer vinyl acetate emulsion containing a ceUulosic protective coUoid is effective for most purposes. Next effective are emulsions containing fuUy hydrolyzed poly(vinyl alcohol) as a protective coUoid, foUowed by those containing partiaUy hydrolyzed poly(vinyl acetate). 

The viscosity of an adhesive directly influences its penetration into a substrate as the viscosity increases, the penetrating power decreases. It also determines the amount of mileage or spread that can be obtained. An optimum viscosity exists for each substrate and each set of machine conditions and must be achieved in order to manufacture an efficient adhesive. Poly(vinyl acetate) emulsions are frequently too low in viscosity to be metered efficiently or to perform well as adhesives by themselves. They must be bodied to working viscosities, eg, by adding thickeners. 

Pa.ints, Paints (qv) prepared from poly(vinyl acetate) and its copolymers form flexible, durable films with good adhesion to clean surfaces, including wood, plaster, concrete, stone, brick, cinder blocks, asbestos board, asphalt, tar paper, wahboards, aluminum, and galvani2ed iron (147). Adherence is also good on painted surfaces if the surfaces are free from dirt, grease, and mst. Developments in emulsion polymeri2ation for paint latices have been reviewed (148). 

Poly(vinyl acetate) emulsions are used to prime-coat fabrics to improve the adhesion of subsequent coatings or to make them adhere better to plastic film. Plasticized emulsions are appHed, generally by roUer-coating, to the backs of finished mgs and carpets to bind the tufts in place and to impart stiffness and hand. For upholstery fabrics woven from colored yams, PVAc emulsions may be used to bind the tufts of pile fabrics or to prevent sHppage of synthetic yams. 

In contrast to other polymers the resistance to water permeation is low due to the hydrolysis of the poly(vinyl acetate) (163,164). Ethylene copolymers have been developed which have improved water resistance and waterproofness. The polymer can be used in the latex form or in a spray-dried form which can be preblended in with the cement (qv) in the proper proportion. The compressive and tensile strength of concrete is improved by addition of PVAc emulsions to the water before mixing. A polymer-soHds-to-total-soHds ratio of ca 10 90 is best. The emulsions also aid adhesion between new and old concrete when patching or resurfacing. 

Adhesives. Poly(vinyl alcohol) is used as a component in a wide variety of general-purpose adhesives to bond ceUulosic materials, such as paper and paperboard, wood textiles, some metal foils, and porous ceramic surfaces, to each other. It is also an effective binder for pigments and other finely divided powders. Both fully and partially hydrolyzed grades are used. Sensitivity to water increases with decreasing degree of hydrolysis and the addition of plasticizer. Poly(vinyl alcohol) in many appHcations is employed as an additive to other polymer systems to improve the cohesive strength, film flexibiUty, moisture resistance, and other properties. It is incorporated into a wide variety of adhesives through its use as a protective coUoid in emulsion p olymerization. 

Emulsion Polymerization. Poly(vinyl acetate) and poly(vinyl acetate) copolymer latexes prepared in the presence of PVA find wide appHcations in adhesives, paints, textile finishes, and coatings. The emulsions show exceUent stabiHty to mechanical shear as weU as to the addition of electrolytes, and possess exceUent machining characteristics. 

Because of its high cold flow, poly(vinyl acetate) is of little value in the form of mouldings and extrusions. However, because of its good adhesion to a number of substrates, and to some extent because of its cold flow, a large quantity is produced for use in emulsion paints, adhesives and various textile finishing operations. A minor proportion of the material is also converted into poly(vinyl alcohol) and the poly(vinyl acetal)s which, are of some interest to the plastics industry. 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

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