VINYLIDENE CHLORIDE COPOLYMER

Vinylidene chloride copolymers were among the first synthetic polymers to be commercialized. Their most valuable property is low permeabiUty to a wide range of gases and vapors. From the beginning in 1939, the word Saran has been used for polymers with high vinylidene chloride content, and it is still a trademark of The Dow Chemical Company in some countries. Sometimes Saran and poly (vinylidene chloride) are used interchangeably in the Hterature. This can lead to confusion because, although Saran includes the homopolymer, only copolymers have commercial importance. The homopolymer, ie, poly (vinylidene chloride), is not commonly used because it is difficult to fabricate. 

Table 5. Common Solvents for Vinylidene Chloride Copolymers...

Fig. 4. Oxygen permeability in a vinylidene chloride copolymer film at selected levels of plasticizer (Citroflex A-4). Plasticizer level in parts pet hundred resin...

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). 

Table 19. Film Properties of Vinylidene Chloride Copolymer Latex ...

Vinylidene Chloride Copolymer Foams. Low density, fine-celled VDC copolymer foams can be made by extmsion of a mixture of vinylidene chloride copolymer and a blowing agent at 120—150°C (190). The formulation must contain heat stabilizers, and the extmsion equipment must be made of noncatalytic metals to prevent accelerated decomposition of the polymer. The low melt viscosity of the VDC copolymer formulation limits the size of the foam sheet that can be extmded. 

Expandable VDC copolymer microspheres are prepared by a microsuspension process (191). The expanded microspheres are used in reinforced polyesters, blocking multipair cable, and in composites for furniture, marble, and marine appHcations (192—195). Vinylidene chloride copolymer microspheres are also used in printing inks and paper manufacture (196). 

Ninety-six percent of the EDC produced in the United States is converted to vinyl chloride for the production of poly(vinyl chloride) (PVC) (1) (see Vinyl polymers). Chloroform and carbon tetrachloride are used as chemical intermediates in the manufacture of chlorofluorocarbons (CECs). Methjiene chloride, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene have wide and varied use as solvents. Methyl chloride is used almost exclusively for the manufacture of silicone. Vinylidene chloride is chiefly used to produce poly (vinylidene chloride) copolymers used in household food wraps (see Vinylidene chloride and poly(vinylidene chloride). Chloroben2enes are important chemical intermediates with end use appHcations including disinfectants, thermoplastics, and room deodorants. 

Table 7. Absorption Maxima of the Colored Form of Spiroindolinobenzothiopyran 44 in Vinyl Chloride-Vinylidene Chloride Copolymer...

First, the recording layer which contains photochromic spirobenzothiopyran in liquid-crystal polymer or polymer such as vinyl chloride-vinylidene chloride copolymer, is made colored by UV irradiation. In the recording (writing) process, a colorless recording dot in the recording layer is formed by semiconductor laser beams (789 nm, 15-20 mW).100 This process is essentially thermal decoloration of the photomerocyanine form by laser beam. 

Conversely, cling film (plasticised PVC/PVDC, (poly(vinyl chloride)/poly (vinylidene chloride), copolymer, which has very high gas-barrier properties) on peeling from a roll generates static electricity thus promoting adhesion to a surface, e.g., ceramics, but not metallic surfaces which conduct the static electricity away... 

The stability of vinylidene chloride copolymers generated using different polymerization initiators has also been examined. The two common types of initiators for radical polymerization are azo compounds and peroxides. A common azo initiator is azoisobutronitrile or AIBN. The initiation of vinylidene chloride polymerization using AIBN is illustrated in scheme 3. 

Scheme 5. Proposed Mode of Stabilization of Vinylidene Chloride Copolymers Containing Pendant Butyl Ester Groups.

Scheme 8. Possible Mode of Stabilization of a Vinylidene Chloride Copolymer Containing Pendant sec-Butyl Ester Groups.

From the data presented here it is clear that little stabilization is provided by the presence of pendant buytl groups of any structure despite the fact that abstractable hydrogen atoms, particularly in the case of the sec-butyl acrylate copolymer, are available. This stands in contrast to an earlier observation that the presence of aliphatic pendant groups afforded stability for vinylidene chloride copolymers. [43] It may be that the size of the pendant groups in this case is too small, i.e., that the availability of abstractable hydrogen atoms is not great. Further work will be required to resolve this issue. 

Both methyl acrylate and butyl acrylate have been used to prepare vinylidene chloride copolymers with sufficient stability to permit thermal processing. The presence of alkyl acrylate units in the polymer mainchain limits the size of vinylidene chloride sequences and thus the propagation of degradative dehydrochlorination. More importantly it lowers the melt... 

Limited studies suggest that the nature of the initiator, azo versus peroxide, used for the preparation of vinylidene chloride copolymers has little influence on the stability of the resulting polymers. The nature of the comonomer incorporated, methyl versus butyl acrylate, also seems to have little impact on the stability of the copolymers generated. The incorporation of isomeric butyl acrylate esters into vinylidene chloride copolymers also displays little impact on the stability of the resulting polymer, beyond that obtained by incorporation of any comonomer, independent of butyl structure. 

Plasticizers are used in the polymer industry to improve flexibility, workability, and general handling properties. Dibutyl sebacate and phthalates, such as dibutyl phthalate, diethyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, and diphenyl-2-ethylhexyl phosphate, serve widely as plasticizers in vinylidene chloride copolymers, nitrocellulose-coated regenerated cellulose film, and cellulose acetate (Castle et ah, 1988a). In PVC, di(2-ethylhexyl)... 

To illustrate the compaction process that occurs in an extruder, a Maddock solidification [1] experiment (described in detail in Section 10.3.1) was performed using a 63.5 mm diameter machine [2]. The extruder was operated at a screw speed of 60 rpm with a poly(vinylidene chloride) copolymer (PVDC) powder. After the extruder reached a steady-state operation, screw rotation was stopped and full cooling was applied to the extruder. After several hours of cooling, the screw and PVDC resin were removed from the extruder and the density of the bed was measured using Archimedes s principle. The compaction phenomenon in the extruder is shown by the density measurements of the solid bed in Fig. 4.1. As shown in this figure, the density of the solid bed increased from the feedstock bulk density of 0.73 g/cm to nearly the solid density of 1.7 g/cmT... 

Henschler D, Broser F, Hopf HC Polyneuritis cranialis following poisoning with chlorinated acetylenes while handling vinylidene chloride copolymers. (Ger.) Arch Toxicol 26 62-75, 1970... 

Saran PVC and poly(vinylidene chloride) copolymer Dow Plastics... 

Vinylidene chloride copolymers are available as resins for extrusion, lalices for coating, and resins for solvent coating. Comonomer levels range from 5 to 20 wt %. Common comonomers are vinyl chloride, acrylonitrile, and alkyl acrylates. The permeability of the polymer is a function of type and amount of comonomer, As the comonomer fraction of these semicrystalhne copolymers is increased, the melting temperature decreases and the permeability increases The permeability of vinylidene chloride homopolymer has not been measured. 

Vinylidene chloride copolymers are marketed under a variety of trade names fiaran is a trademark of The Dow Chemical Company for vinylidene chloride copolymers. Other trade names include Daran W.R. Grace), Amsco Res l Union Oil), and Sertene (Morton Chemical) in the United States and Haloflex (Imperial Chemical Industries, Ltd.), Diofan (BASF), lxan (Solvay and Cie SA), and Polyidene (Scott-Bader) in Europe. 

Values for vinylidene chloride copolymer and ethylene-vinyl alcohol are extrapolated fromhighertemperatures. ... 

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