Vinyl acetate-based resin

A typical ethylene-vinyl acetate based hot melt is composed mainly of three components (1) a polymer, 30-40% (2) a modifying or tackifying resin, 30-40%, and (3) a petroleum wax, 20-30%. The quantity and relative amount of each material is governed by the performance requirements of the adhesive. The polymer forms the backbone of the adhesive, providing strength and toughness. The modi-... 

PVC/Vinyl Acrylate Copolymers These resins can be used in many of the plastisol applications where PVC/vinyl acetate copolymer resins are presently used. Although PVC/vinyl acrylate copolymer resins are more expensive than their PVC/vinyl acetate copolymer counterparts, they do offer two advantages. One benefit is that the viscosity stability of PVC plastisols containing PVC/vinyl acrylate copolymers is better over time than those based on PVC/vinyl acetate copolymers. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

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). 

A series of compounded flame retardants, based on finely divided insoluble ammonium polyphosphate together with char-forming nitrogenous resins, has been developed for thermoplastics (52—58). These compounds are particularly useful as iatumescent flame-retardant additives for polyolefins, ethylene—vinyl acetate, and urethane elastomers (qv). The char-forming resin can be, for example, an ethyleneurea—formaldehyde condensation polymer, a hydroxyethylisocyanurate, or a piperazine—triazine resin. 

Types of internal enamel for food containers include oleoresins, vinyl, acryflc, phenoHc, and epoxy—phenoHc. Historically can lacquers were based on oleoresinous products. PhenoHc resins have limited flexibiHty and high bake requirements, but are used on three-piece cans where flexibiHty is not required. Vinyl coatings are based on copolymers of vinyl chloride and vinyl acetate dissolved in ketonic solvents. These can be blended with alkyd, epoxy, and phenoHc resins to enhance performance. FlexibiHty allows them to be used for caps and closures as weU as drawn cans. Their principal disadvantage is high sensitivity to heat and retorting processes this restricts their appHcation to cans which are hot filled, and to beer and beverage products. 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

Rosin, modified rosins, and derivatives are used in hot-melt adhesives. They are based primarily on ethylene—vinyl acetate copolymers. The rosin derivative is used in approximately a 1 1 1 concentration with the polymer and a wax. The resin provides specific adhesion to the substrates and reduces the viscosity at elevated temperatures, allowing the adhesive to be appHed as a molten material. 

Extension of the chlorosulfonation technology to base resins other than polyethylene, where value can be added, seems a logical next step. Polypropylene and ethylene copolymers containing additional functionaUty, ie, maleic anhydride graft, vinyl acetate, acrylic acid, etc, have been chlorinated and chlorosulfonated to broaden the appHcation base, particularly in coatings and adhesives (9,10). 

Ethylene has also been copolymerised with a number of non-olefinic monomers and of the copolymers produced those with vinyl acetate have so far proved the most significant commercially . The presence of vinyl acetate residues in the chain reduces the polymer regularity and hence by the vinyl acetate content the amount of crystallinity may be controlled. Copolymers based on 45% vinyl acetate are rubbery and may be vulcanised with peroxides. They are commercially available (Levapren). Copolymers with about 30% vinyl acetate residues (Elvax-Du Pont) are flexible resins soluble in toluene and benezene at room temperature and with a tensile strength of about lOOOlbf/in (6.9 MPa) and a density of about 0.95 g/cm. Their main uses are as wax additives and as adhesive ingredients. 

The PVF is made by acidic reaction between poly(vinyl alcohol) (PVA) and formaldehyde. The poly(vinyl alcohol) is, in turn, made by hydrolysis of poly(vinyl acetate) or transesterification of poly(vinyl acetate). Thus, residual alcohol and ester functionality is usually present. Cure reportedly occurs through reaction of phenolic polymer hydroxyls with the residual hydroxyls of the PVA [199]. The ester residues are observed to reduce bond strength in PVF-based systems [199]. This does not necessarily extend to PVF-P adhesives. PVF is stable in strong alkali, so participation of the acetals in curing is probably unimportant in most situations involving resoles. PVF is physically compatible with many phenolic resins. 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

Emulsion paints are based on aqueous synthetic resin dispersions, which afford a lacquer-like paint film. The resin dispersions which are commonly used by the paint industry contain water as the carrier phase. A large number of such dispersions are available, based on different resins such as poly(vinyl acetate), which may be employed as a copolymer with vinyl chloride, maleic dibutyl ester, ethylene, acrylic acid esters, polyacrylic resin, and copolymers of the latter with various monomers, as well as styrene-butadiene or poly(vinyl propionate). These disper-... 

Latexes are usually copolymer systems of two or more monomers, and their total solids content, including polymers, emulsifiers, stabilizers etc. is 40-50% by mass. Most commercially available polymer latexes are based on elastomeric and thermoplastic polymers which form continuous polymer films when dried [88]. The major types of latexes include styrene-butadiene rubber (SBR), ethylene vinyl acetate (EVA), polyacrylic ester (PAE) and epoxy resin (EP) which are available both as emulsions and redispersible powders. They are widely used for bridge deck overlays and patching, as adhesives, and integral waterproofers. A brief description of the main types in current use is as follows [87]. 

Isophorone is a solvent for a large number of natural and synthetic polymers, resins, waxes, fats, and oils. Specifically, it is used as a solvent for concentrated vinyl chloride/acetate-based coating systems for metal cans, other metal paints, nitrocellulose finishes, printing inks for plastics, some herbicide and pesticide formulations, and adhesives for plastics, poly(vinyl) chloride and polystyrene materials (Papa and Sherman 1981). Isophorone also is an intermediate in the synthesis of 3, 5-xylenol, 3, 3, 5-trimethylcyclohexanol (Papa and Sherman 1981), and plant growth retardants (Haruta et al. 1974). Of the total production, 45-65% is used in vinyl coatings and inks, 15-25% in agricultural formulations, 15-30% in miscellaneous uses and exports, and 10% as a chemical intermediate (CMA 1981). 

There have been attempts in the past to formulate removable chewing gum bases and chewing gum compositions. For example, a non-stick chewing gum may contain a blend of different molecular weight poly(vinyl acetate), filler, non-elastomer solvent resin, and is essentially free of fats and waxes (82). In Table 6.8 a chewing gum cud formulation is given, which can be easily removed from surfaces. 

Tile is based mainly on vinyl chloride and vinyl acetate copolymers. Some polypropylene tile systems have recently been introduced. A petroleum resin is usually employed as an extender and processing aid conventional vinyl plasticizers and stabilizers also are incorporated. Reinforcing fibers and limestone constitute the remainder of the tile composition the fibers contribute hot strength for processing and dimensional stability in the finished tile, limestone supplies bulk at an economical cost. Stable pigments are also incorporated. Since tile is installed on and below grade level, it is important that the finished product be resistant to the effects of moisture and alkali. 

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