Barrier copolymer

Cava et al. [72] applied the IGC technique to examine the effect of moisture on the transport properties of several low-molecular-weight alcohols through high-barrier copolymers. The apphcation of Romdhane-Danner methods allowed an estimation of the diffusion coefficient Dp at different humidity conditions, that is, at various values of relative humidity (%RH). The sorption of water by the... 

In the late 1960s a new class of AN copolymers and multipolymers was introduced that contain >60% acrylonitrile. These are commonly known as barrier resins and have found thek greatest acceptance where excellent barrier properties toward gases (5), chemicals, and solvents are needed. They may be processed into bottles, sheets, films, and various laminates, and have found wide usage in the packaging industry (see Barrier polymers). 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

Acrylonitrile copolymeri2es readily with many electron-donor monomers other than styrene. Hundreds of acrylonitrile copolymers have been reported, and a comprehensive listing of reactivity ratios for acrylonitrile copolymeri2ations is readily available (34,102). Copolymeri2ation mitigates the undesirable properties of acrylonitrile homopolymer, such as poor thermal stabiUty and poor processabiUty. At the same time, desirable attributes such as rigidity, chemical resistance, and excellent barrier properties are iacorporated iato melt-processable resias. 

Acrylonitrile—methyl acrylate—iadene terpolymers, by themselves, or ia blends with acrylonitrile—methyl acrylate copolymers, exhibit even lower oxygen and water permeation rates than the iadene-free copolymers (110,111). Terpolymers of acrylonitrile with iadene and isobutjlenealso exhibit excellent barrier properties (112), and permeation of gas and water vapor through acrylonitrile—styrene—isobutjleneterpolymers is also low (113,114). 

Useflil properties of acrylonitrile copolymers, such as rigidity, gas barrier, chemical and solvent resistance, and toughness, are dependent upon the acrylonitrile content in the copolymers. The choice of the composition of SAN copolymers is dictated by their particular appHcations and performance requirements. The weU-balanced and unique properties possessed by these copolymers have led to broad usage in a wide variety of appHcations. 

Some cast (unoriented) polypropylene film is produced. Its clarity and heat sealabiUty make it ideal for textile packaging and overwrap. The use of copolymers with ethylene improves low temperature impact, which is the primary problem with unoriented PP film. Orientation improves the clarity and stiffness of polypropylene film, and dramatically increases low temperature impact strength. BOPP film, however, is not readily heat-sealed and so is coextmded or coated with resins with lower melting points than the polypropylene shrinkage temperature. These layers may also provide improved barrier properties. 

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. 

Thermoform able sheet may be mono- or multilayer with the latter produced by lamination or coextmsion. Multilayers are employed to incorporate high oxygen-barrier materials between stmctural or high water-vapor barrier plastics. Both ethylene vinyl alcohol copolymers and poly(vinyhdene chloride) (less often) are used as high oxygen-barrier interior layers with polystyrene or polypropylene as the stmctural layers, and polyolefin on the exterior for sealing. 

Alkenylsuccinic anhydrides made from several linear alpha olefins are used in paper sizing, detergents, and other uses. Sulfosuccinic acid esters serve as surface active agents. Alkyd resins (qv) are used as surface coatings. Chlorendric anhydride [115-27-5] is used as a flame resistant component (see Flame retardants). Tetrahydrophthalic acid [88-98-2] and hexahydrophthalic anhydride [85-42-7] have specialty resin appHcations. Gas barrier films made by grafting maleic anhydride to polypropylene [25085-53-4] film are used in food packaging (qv). Poly(maleic anhydride) [24937-72-2] is used as a scale preventer and corrosion inhibitor (see Corrosion and corrosion control). Maleic anhydride forms copolymers with ethylene glycol methyl vinyl ethers which are partially esterified for biomedical and pharmaceutical uses (189) (see Pharmaceuticals). 

Because of the capacity to tailor select polymer properties by varying the ratio of two or more components, copolymers have found significant commercial appHcation in several product areas. In fiber-spinning, ie, with copolymers such as nylon-6 in nylon-6,6 or the reverse, where the second component is present in low (<10%) concentration, as well as in other comonomers with nylon-6,6 or nylon-6, the copolymers are often used to control the effect of sphemUtes by decreasing their number and probably their size and the rate of crystallization (190). At higher ratios, the semicrystalline polyamides become optically clear, amorphous polymers which find appHcations in packaging and barrier resins markets (191). 

Diblock copolymers consist of one sequence of anchor segments and a second sequence of backbone segments. The relative lengths of the two sequences can be controlled to provide a wide variety of adsorption and barrier characteristics. Typical commercial dispersants may use alkane... 

Copolymers are typically manufactured using weU-mixed continuous-stirred tank reactor (cstr) processes, where the lack of composition drift does not cause loss of transparency. SAN copolymers prepared in batch or continuous plug-flow processes, on the other hand, are typically hazy on account of composition drift. SAN copolymers with as Httle as 4% by wt difference in acrylonitrile composition are immiscible (44). SAN is extremely incompatible with PS as Httle as 50 ppm of PS contamination in SAN causes haze. Copolymers with over 30 wt % acrylonitrile are available and have good barrier properties. If the acrylonitrile content of the copolymer is increased to >40 wt %, the copolymer becomes ductile. These copolymers also constitute the rigid matrix phase of the ABS engineering plastics. 

Barrier Properties. VinyUdene chloride polymers are more impermeable to a wider variety of gases and Hquids than other polymers. This is a consequence of the combination of high density and high crystallinity in the polymer. An increase in either tends to reduce permeabiUty. A more subtle factor may be the symmetry of the polymer stmcture. It has been shown that both polyisobutylene and PVDC have unusually low permeabiUties to water compared to their monosubstituted counterparts, polypropylene and PVC (88). The values Hsted in Table 8 include estimates for the completely amorphous polymers. The estimated value for highly crystalline PVDC was obtained by extrapolating data for copolymers. 

The effect of copolymer composition on gas permeability is shown in Table 9. The inherent barrier in VDC copolymers can best be exploited by using films containing Htde or no plasticizers and as much VDC as possible. However, the permeabiUty of even completely amorphous copolymers, for example, 60% VDC—40% AN or 50% VDC—50% VC, is low compared to that of other polymers. The primary reason is that diffusion coefficients of molecules in VDC copolymers are very low. This factor, together with the low solubiUty of many gases in VDC copolymers and the high crystallinity, results in very low permeabiUty. PermeabiUty is affected by the kind and amounts of comonomer as well as crystallinity. A change from PVDC to 50 wt °/ VC or 40 wt % AN increases permeabiUty 10-fold, but has Httle effect on the solubiUty coefficient. 

Humidity does not affect the permeabihty, diffusion coefficient, or solubihty coefficient of flavor/aroma compounds in vinyhdene chloride copolymer films. Studies based on /n j -2-hexenal and D-limonene from 0 to 100% rh showed no difference in these transport properties (97,98). The permeabihties and diffusion coefficients of /n j -2-hexenal in two barrier polymers are compared in Table 12. Humidity does not affect the vinyhdene chloride copolymer. In contrast, transport in an EVOH film is strongly plasticized by humidity. 

Although Saran is a generic name for VDC copolymers in the United States, it is a Dow trademark in most foreign countries. Other trade names include Daran (Hampshire Chemical Corporation) and Serfene (Morton Chemical) in the United States, and Haloflex (Zeneca Resins), Diofan (BASE), Ixan (Solvay SA), and Polyidene (Scott-Bader) in Europe. The monomer is of particular economic interest because it is only 27 wt % hydrocarbon. In addition, B. E. Goodrich Chemicals (GEON) supply non-barrier VDC copolymers. 

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). 

Oil Repellent. Fluorochemicals are the only class of material that can provide oil repeUency without altering the porosity of the paper or paperboard. Physical barriers to oil penetration are used primarily for their moisture- or gas-barrier properties, with retarded oil penetration as a secondary benefit. The most common od-repeUent additives are long-chain perfluoroalkyl phosphate salts of ammonia or diethanol amine. Commercial sources include Scotchban (3M), Zonyl (DuPont), and Lodyne (Ciba Specialties). There are also a fluorochemical carboxylate salt, Lodyne (Ciba Specialties), and fluorochemical copolymers, eg, Scotchban (3M). The widest range of oily fluid holdout is provided by the fluorochemical copolymers. 

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