Ethylene-Vinyl Acetates

3 Vinyl Acetate Copolymers 7.3.1 Ethylene-vinyl Acetate 

Carbon Moiety Structure segment C Chemical shift (ppm) 

A summary of the chemical shift assignments together with the structural block segment to which the carbon moiety belongs is summarised in Table 7.11. 

Acetic acid, ethylene ester polymer with ethane CoTran-ethylene/vinyl acetate copolymer EVA EVA copolymer EVM poly (ethylene-co-vinyl acetate) VA/ethylene copolymer vinyl acetate/ethylene copolymer. 

Ethylene vinyl acetate copolymer is a random copolymer of ethylene and vinyl acetate. 

Ethylene vinyl acetate copolymers are used as membranes and backings in laminated transdermal drug delivery systems. They can also be incorporated as components in backings in transdermal systems. Ethylene vinyl acetate copolymers have been shown to be an effective matrix and membrane for the controlled delivery of atenolol triprolidine, and furose-mide. The system for the controlled release of atenolol can be further developed using ethylene vinyl acetate copolymers and plasticizers.  

Ethylene vinyl acetate is available as white waxy solids in pellet or powder form. Films are translucent. 

Grade Vinyl acetate (%) Thickness (gm) Moisture vapor transmission rate (g/m /24h) 

There are two methods for this determination, depending on the concentration of vinyl acetate. At levels 10%, a band at 2.89 pm is used. This band is not suitable for higher concentrations because the necessary film thickness is 0.1 mm. For higher concentrations, the carbonyl overtone band at 16.39 pm can be used because much thicker films are needed to give suitable absorbance levels. Here the carbonyl overtone band was used for a series of standards with vinyl acetate concentrations up to 35%, the nominal thickness being about 0.5 mm. 

A combination of CDS and QUANT software on a Perkin Elmer model 683 infrared spectrometer was used to establish the calibration for this analysis. Once the calibration has been carried out, the simplest way to measure an unknown sample would be with an OBEY routine in the CDS II software. This would incorporate calibration data so that the single routine would measure the spectrum and calculate the vinyl acetate concentration with an error of approximately 5%. 

Pallacini and co-workers [ 17] and Jones and McClelland [18] also used IR spectroscopy to analyse ethylene-vinyl acetate copolymers. 

This is another important and widely used polymer. Nanocomposites have been prepared based on this rubber mostly for flame-retardancy behavior. Blends with acrylic functional polymer and maleic anhydride-grafted ethylene vinyl acetate (EVA) have also been used both with nanoclays and carbon nanotubes to prepare nanocomposites [65-69]. 

Suggested Uses Mattress Ticking Coating High Pile Coating Textile Finishing 

Suggested Uses Upholstery/Carpet Coatings High Pile Coating 

Resists staining by acrylic dyes. Excellent for acrylic upholstery fabric coatings. 

Ardhyananta and co-workers [101] demonstrated the Young s Modulus of EVA/ organoclay nanocomposites increased as the clay loading was increased up to a value of 92%. 

Peak number Molecular ion found Elemental composition Deviation (mmu) Probable structure 

Peak numbers 1 and 2 from Trap 1, others Deviation = (theoretical mass - observed mj Reproduced with permission from T.R. Crom Smithers Rapra Technology Ltd, Shrewsbury, Rapra Technology Ltd rom Trap 2 iss) X 1000 pton. Polymer Reference Book, UK, 2006 p.355. 2006, Smithers  

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Low-density Medium-density High-density Ultra high-molecular-weight Glass-fiber- reinforced, high-density Ethylene-vinyl acetate copolymer... 

INFRARED TECHNOLOGY AND RAMAN SPECTKOSCOPY - INFRARED TECHNOLOGY] (Vol 14) EVA. See Ethylene-vinyl acetate. 

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. 

Pentaerythritol in rosin ester form is used in hot-melt adhesive formulations, especially ethylene—vinyl acetate (EVA) copolymers, as a tackifier. Polyethers of pentaerythritol or trim ethyl ol eth an e are also used in EVA and polyurethane adhesives, which exhibit excellent bond strength and water resistance. The adhesives maybe available as EVA melts or dispersions (90,91) or as thixotropic, one-package, curable polyurethanes (92). Pentaerythritol spko ortho esters have been used in epoxy resin adhesives (93). The EVA adhesives are especially suitable for cellulose (paper, etc) bonding. 

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. 

Other Films. Although commercially less important than polyethylenes and polypropylenes, a number of other plastic films are in commercial use or development for special appHcations, including ethylene—vinyl acetate, ionomer, and polyacrylonitrile [25014-41-9]. 

Ethylene vinyl acetate copolymer (EVA) forms a soft, tacky film with good water-vapor barrier but very poor gas-barrier properties. It is widely used as a low temperature initiation and broad-range, heat-sealing medium. The film also serves for lamination to other substrates for heat-sealing purposes. 

Hydrocarbon resins (qv) are prepared by copolymerization of vinyltoluene, styrene, and a-methylstyrene in the presence of a Eriedel-Crafts catalyst (AlCl ). These resins are compatible with wax and ethylene—vinyl acetate copolymer (197). 

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). 

Plasticizers. Monomeric (mol wt 250—450) plasticizers (qv) are predominantiy phthalate, adipate, sebacate, phosphate, or trimeUitate esters. Organic phthalate esters like dioctyl phthalate (DOP) are by far the most common plasticizers in flexible PVC. Phthalates are good general-purpose plasticizers which impart good physical and low temperature properties but lack permanence in hot or extractive service conditions and are therefore sometimes called migratory plasticizers. Polymeric plasticizers (mol wt up to 5000 or more) offer an improvement in nonmigratory permanence at a sacrifice in cost, low temperature properties, and processibiHty examples are ethylene vinyl acetate or nitrile polymers. 

Ethylene vinyl acetate (EVA) polymers are used in thermoplastic and thermosetting jacketing compounds for apphcations that require flame retardancy combined with low smoke emission during the fire as well as the absence of halogen in the composition. 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

Fig. 10. Preparation and morphology of toughened PVC (a) secondary PVC grain (50—250 flm) (b) modified PVC with coherent primary grain (ca 1 -lm) (220). CPE = chlorinated polyethylene EVA = ethylene—vinyl acetate copolymers ABS = acrylonitrile—butadiene—styrene MBS = methyl...

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

Pubhcations on curing polymers with TAIC include TEE—propylene copolymer (135), TEE—propylene—perfluoroaHyl ether (136), ethylene—chlorotrifluoroethylene copolymers (137), polyethylene (138), ethylene—vinyl acetate copolymers (139), polybutadienes (140), PVC (141), polyamide (142), polyester (143), poly(ethylene terephthalate) (144), sdoxane elastomers (145), maleimide polymers (146), and polyimide esters (147). 

Substituted amides (not of the alkanolamide variety) are sold to diverse low volume markets. They have some utility ki polymers such as polyethylene, ethylene-vinyl acetate copolymers, acryUc polymers, PVC, polyamides, and polyesters. They have been found effective as pharmaceutical processkig aids, defoamers (qv), antimicrobials, pesticides, kisect repellents, dispersion stabilizers, and corrosion inhibitors. 

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. 

Natural mbber comes generally from southeast Asia. Synthetic mbbers are produced from monomers obtained from the cracking and refining of petroleum (qv). The most common monomers are styrene, butadiene, isobutylene, isoprene, ethylene, propylene, and acrylonitrile. There are numerous others for specialty elastomers which include acryUcs, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin, ethylene—acryUc, ethylene octene mbber, ethylene—propylene mbber, fluoroelastomers, polynorbomene, polysulftdes, siUcone, thermoplastic elastomers, urethanes, and ethylene—vinyl acetate. 

Materials are also blended with VDC copolymers to improve toughness (211—214). VinyHdene chloride copolymer blended with ethylene—vinyl acetate copolymers improves toughness and lowers heat-seal temperatures (215,216). Adhesion of a VDC copolymer coating to polyester can be achieved by blending the copolymer with a linear polyester resin (217). 

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. 

The low vinyl acetate ethylene—vinyl acetate copolymers, ie, those containing 10—40 wt % vinyl acetate, are made by processes similar to those used to make low density polyethylene for which pressures are usually > 103 MPa (15,000 psi). A medium, ie, 45 wt % vinyl acetate copolymer with mbber-like properties is made by solution polymerisation in /-butyl alcohol at 34.5 MPa (5000 psi). The 70—95 wt % vinyl acetate emulsion copolymers are made in emulsion processes under ethylene pressures of 2.07—10.4 MPa (300—1500 psi). 

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