PVAc

Poly(vinyl acetate). The dielectric and mechanical spectra of hybrids produced by mixing a poly(vinyl acetate)—THE solution with TEOS, followed by the addition of HCl have been investigated (45). Mixtures were made which were beheved to be 0, 5, 10, 15, and 20 wt % Si02, respectively. These composites were transparent and Eourier transform infrared spectroscopy (ftir) revealed hydrogen bonding between the siUcate network and carbonyl units of the poly(vinyl acetate) (PVAc). No shift in the T of the composites from that of the pure PVAc was observed. Similarly, the activation... 

Transparent, homogeneous hybrids using a 50 50 PVAc-to-TEOS mixture and an acid-catalyzed reaction have been produced and characterized by dsc and dms (46). Dsc indicated only a slight increase in the T of the hybrid with incorporation of sihca. Dynamic mechanical tan 8 responses indicate a strong interaction between the organic and inorganic phases and, hence, weU-dispersed phases that lead to high modulus mbbery plateaus. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Vinyl acetate [108-05-4] (VAc), CH2=CHOOCCH2, the ethenyl ester of acetic acid, is primarily use for the manufacture of poly(vinyl acetate) [9003-20-7] (PVAc) and vinyl acetate copolymers. Poly(vinyl acetate) homo- and copolymers are found as components in coatings, paints and sealants, binders (adhesives, nonwovens, constmction products, and carpet-backing), and miscellaneous uses such as chewing gum and tablet coatings. AppHcations have grown over the years in a number of areas (1 4). 

Fig. 2. U.S. consumption of vinyl acetate, where represents PVAc I, poly(vinyl alcohol) (PVA) A, ethylene—vinyl acetate (EVA) O, PVB , EVOFl ...

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

In poly(vinyl acetate) copolymer emulsions, the properties are significantly affected by the composition of the aqueous phase and by the stabilizers and buffers used iu the preparation of these materials, along with the process conditions (eg, monomer concentrations, pH, agitation, and temperature). The emulsions are milk-white Hquids containing ca 55 wt % PVAc, the balance being water and small quantities of wetting agents or protective coUoids. 

An important property of a PVAc film is its permeabiUty to water vapor. The permeabiUty to saturated water vapor at 40°C is 2.1 g/(h-m ) for a film 0.025-mm thick. This allows the film to be laid down on a damp surface with trapped moisture gradually passiug through the film without lifting or blistering it. 

Often a chain-transfer agent is added to vinyl acetate polymerizations, whether emulsion, suspension, solution, or bulk, to control the polymer molecular weight. Aldehydes, thiols, carbon tetrachloride, etc, have been added. Some emulsion procedures call for the recipe to include a quantity of preformed PVAc emulsion and sometimes antifoamers must be added (see Foams). 

Suspension Polymerization. At very low levels of stabilizer, eg, 0.1 wt %, the polymer does not form a creamy dispersion that stays indefinitely suspended in the aqueous phase but forms small beads that setde and may be easily separated by filtration (qv) (69). This suspension or pearl polymerization process has been used to prepare polymers for adhesive and coating appHcations and for conversion to poly(vinyl alcohol). Products in bead form are available from several commercial suppHers of PVAc resins. Suspension polymerizations are carried out with monomer-soluble initiators predominantly, with low levels of stabilizers. Suspension copolymerization processes for the production of vinyl acetate—ethylene bead products have been described and the properties of the copolymers determined (70). Continuous tubular polymerization of vinyl acetate in suspension (71,72) yields stable dispersions of beads with narrow particle size distributions at high yields. 

Porous membranes with selective permeabiUty to organic solvents have been prepared by the extraction of latex films prepared with moderate ratios of PVA—PVAc graft copolymer fractions. The extracted films are made up of a composite of spherical cells of PVA, PVAc microgel, and PVA—PVAc graft copolymers (113). 

Economic Aspects. Prices for PVAc polymers depend on the form of the polymer, ie, whether it is resin or emulsion, homopolymer or copolymer, as well as on the specific product. As of 1994, emulsion prices were 0.57— 0.86/wet kg of resin. Prices of VAE copolymer emulsions tend to be higher than those of the homopolymer priced at 0.97— 1.43/wet kg. Vinyl acryUc copolymers Hsted for 0.66— 0.88/wet kg of 55% soHds emulsion (138). Specialty copolymers generally have a premium price. These price ranges are for large shipments. 

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. 

Speciali2ed copolymer latices, which are inherently and permanently tacky, are available as pressure-sensitive emulsions. They are mechanically stable and have excellent machinabiUty. They are compatible with many other PVAc latices and, therefore, can be easily blended with other resins for modification of surface tack, peel strength, and creep. 

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. 

PVAc is another important type of adhesive, especially in furniture manufacturing and for carpentry. They form the bond line in a physical process by losing their water content to the two wooden adherends. PVAc adhesives are ready to use, have short setting time and give flexible and invisible joints. They are easy to clean and show long storage life. Limitations are their thermoplasticity and the creep behavior. 

PVAc is a thermoplastic polymer due to the manifold variations (homo- or copolymerizate, unmodified or modified, with or without plasticizers) it shows a great variety of processing and bonding propeities. The various formulations differ in viscosity, drying speed, color of the bond line, flexibility or brittleness, hardness or smoothness and other criteria. 

Depending on the formulations various grades of water resistance can be achieved according to EN 204 (D1-D4) [172], For the two-component PVAc adhesives crosslinking and hence a duroplastic behavior is effectuated by addition of hardening resins (e.g. on basis of formaldehyde), complex forming salts (based... 

The addition of comonomers during the polymerization enables a higher flexibility compared to PVAc-homopolymerizates. This results in a lower glass transition temperature and a lower minimum temperature of the film formation. Possible comonomers are acrylic acid esters (butylacrylate, 2-ethylhexylacrylate), dialkylfumarates, ethylene and others. 

Plasticizers soften the film and increase the adhesion and the setting speed. The most common are phthalates, adipates and benzoates. The amount added can be in a broad range of 10-50%. They affect the swelling and softening of the PVAc emulsion particles, ensure film formation at room temperature, and the tack of the still wet adhesive. They also provide improved moisture resistance of the bond. Disadvantages are the lower resistance of the bond line against heat, possible migration of the plasticizers and enhanced cold flow. 

Fillers (calcium carbonate, calcium sulfate, aluminum oxide, bentonites, wood flour) increase the solid content of the dispersion. They are added up to 50%, based on PVAc. The purpose of the addition is the reduction of the penetration depth, provision of thixotropic behavior of the adhesive, gap filling properties and the reduction of the costs. Disadvantage can be the increase of the white point and a possible higher tool wear. 

Other components in PVAc-formulations are defoamers, stabilizers, filler dispersants, preservatives, thickeners (hydroxyethylcellulose, carboxymethylcellu-lose), polyvinyl alcohols, starch, wetting agents, tackifiers, solvents (alcoholes, ketone, esters), flame retardants and others. 

European Noim EN 204, Water resistance of PVAc adhesives, 1992. 

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