Vinyhdene chloride

Polyimides for use ia molded products and high temperature films can be produced by the reaction of pyromelHtic dianhydride [89-32-7] and 4,4 -diaminodiphenyl ether [13174-32-8] ia DMAC to form a polyamide that can be converted iato a polyimide (13). DMAC can also be used as a spinning solvent for polyimides. AdditionaUy, polymers containing over 50% vinyHdene chloride are soluble up to 20% at elevated temperatures ia DMAC. Such solutions are useful ia preparing fibers (14). 

This principle is illustrated in Figure 10 (45). Water adsorption at low pressures is markedly reduced on a poly(vinyhdene chloride)-based activated carbon after removal of surface oxygenated groups by degassing at 1000°C. Following this treatment, water adsorption is dominated by capillary condensation in mesopores, and the si2e of the adsorption-desorption hysteresis loop increases, because the pore volume previously occupied by water at the lower pressures now remains empty until the water pressure reaches pressures 0.3 to 0.4 times the vapor pressure) at which capillary condensation can occur. 

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

The commercially preferred monomer precursor HCFC-142b has been prepared by hydrofluorination of acetylene (29), vinyHdene chloride (30—32), or 1,1,1-trichloroethane (33—39). 

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. 

Heat stabilizers protect polymers from the chemical degrading effects of heat or uv irradiation. These additives include a wide variety of chemical substances, ranging from purely organic chemicals to metallic soaps to complex organometaUic compounds. By far the most common polymer requiring the use of heat stabilizers is poly(vinyl chloride) (PVC). However, copolymers of PVC, chlorinated poly(vinyl chloride) (CPVC), poly(vinyhdene chloride) (PVDC), and chlorinated polyethylene (CPE), also benefit from this technology. Without the use of heat stabilizers, PVC could not be the widely used polymer that it is, with worldwide production of nearly 16 million metric tons in 1991 alone (see Vinyl polymers). 

Among nonmetallic materials, glass, chemical stoneware, enameled steel, acid-proof brick, carbon, graphite, and wood are resistant to iodine and its solutions under suitable conditions, but carbon and graphite may be subject to attack. Polytetrafluoroethylene withstands Hquid iodine and its vapor up to 200°C although it discolors. Cloth fabrics made of Saran, a vinyHdene chloride polymer, have lasted for several years when used in the filtration of iodine recovered from oil-weU brines (64). 

Because of the intractabiHty of poly(vinyHdene chloride), these studies have used copolymers containing various comonomers however, the results are beheved to be indicative of the interactions with vinyHdene chloride units and not primarily those of the comonomer. 

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane chloral [75-87-6] (trichloroacetaldehyde) trichloroethylene [7901-6]-, 1,1-dichloroethane cis- and /n j -l,2-dichloroethylenes [156-59-2 and 156-60-5]-, 1,1-dichloroethylene [75-35-4] (vinyhdene chloride) 2-chloroethanol [107-07-3]-, ethyl chloride vinyl chloride mono-, di-, tri-, and tetrachloromethanes (methyl chloride [74-87-3], methylene chloride [75-09-2], chloroform, and carbon tetrachloride [56-23-5])-, and higher boiling compounds. The production of these compounds should be minimized to lower raw material costs, lessen the task of EDC purification, prevent fouling in the pyrolysis reactor, and minimize by-product handling and disposal. Of particular concern is chloral, because it polymerizes in the presence of strong acids. Chloral must be removed to prevent the formation of soflds which can foul and clog operating lines and controls (78). 

Vinyl chloride has gained worldwide importance because of its industrial use as the precursor to PVC. It is also used in a wide variety of copolymers. The inherent flame-retardant properties, wide range of plastici2ed compounds, and low cost of polymers from vinyl chloride have made it a major industrial chemical. About 95% of current vinyl chloride production worldwide ends up in polymer or copolymer appHcations (83). Vinyl chloride also serves as a starting material for the synthesis of a variety of industrial compounds, as suggested by the number of reactions in which it can participate, although none of these appHcations will likely ever come anywhere near PVC in terms of volume. The primary nonpolymeric uses of vinyl chloride are in the manufacture of vinyHdene chloride and tri- and tetrachloroethylene [127-18-4] (83). 

The principal solution to fabrication difficulties is copolymerization. Three types of comonomers are commercially important vinyl chloride acrylates, including alkyl acrylates and alkyimethacrylates and acrylonitrile. When extmsion is the method of fabrication, other solutions include formulation with plasticizers, stabilizers, and extmsion aids plus applying improved extmsion techniques. The Hterature on vinyHdene chloride copolymers through 1972 has been reviewed (1). 

Properties. Pure vinyHdene chloride [75-35-4] (1,1-dichloroethylene) is a colorless, mobile Hquid with a characteristic sweet odor. Its properties are summarized in Table 1. VinyHdene chloride is soluble in most polar and nonpolar organic solvents. Its solubiHty in water (0.25 wt %) is nearly independent of temperature at 16—90°C (4). 

Eor many polymeri2ations, MEHQ need not be removed instead, polymeri2ation initiators are added. Vinyhdene chloride from which the inhibitor has been removed should be refrigerated in the dark at —10° C, under a nitrogen atmosphere, and in a nickel-lined or baked phenolic-lined storage tank. If not used within one day, it should be reinhibited. 

Vinyhdene chloride is hepatotoxic, but does not appear to be a carcinogen (13—18). Pharmacokinetic studies indicate that the behavior of vinyl chloride and vinyhdene chloride in rats and mice is substantially different (19). No unusual health problems have been observed in workers exposed to vinyhdene chloride monomer over varying periods (20). Because vinyhdene chloride degrades rapidly in the atmosphere, air pollution is not likely to be a problem (21). Worker exposure is the main concern. Sampling techniques for monitoring worker exposure to vinyhdene chloride vapor are being developed (22). 

The hquid is irritating to the skin after only a few minutes of contact. The inhibitor MEHQ may be partiy responsible for this irritation. Inhibited vinyhdene chloride is moderately irritating to the eyes. Contact causes pain and conjunctival irritation, and possibly some transient corneal injury and iritis. Permanent damage, however, is not likely. 

Copper, aluminum, and their alloys should not be used in handling vinyhdene chloride. Copper can react with acetylenic impurities to form copper acetyhdes, whereas aluminum can react with the vinyhdene chloride to form aluminum chloralkyls. Both compounds are extremely reactive and potentially ha2ardous. 

Vinyhdene chloride polymeri2es by both ionic and free-radical reactions. Processes based on the latter are far more common (23). Vinyhdene chloride is of average reactivity when compared with other unsaturated monomers. The chlorine substituents stabih2e radicals in the intermediate state of an addition reaction. Because they are also strongly electron-withdrawing, they polari2e the double bond, making it susceptible to anionic attack. For the same reason, a carbonium ion intermediate is not favored. 

The 1,1-disubstitution of chlorine atoms causes steric interactions in the polymer, as is evident from the heat of polymeri2ation (see Table 1) (24). When corrected for the heat of fusion, it is significantly less than the theoretical value of —83.7 kJ/mol (—20 kcal/mol) for the process of converting a double bond to two single bonds. The steric strain apparentiy is not important in the addition step, because VDC polymeri2es easily. Nor is it sufficient to favor depolymeri2ation the estimated ceiling temperature for poly (vinyhdene chloride) (PVDC) is about 400°C. 

Fig. 1. Bulk polymerization of vinyHdene chloride at 45°C, with 0.5 wt % benzoyl peroxide as initiator (29).

Redox initiator systems are normally used in the emulsion polymerization of VDC to develop high rates at low temperatures. Reactions must be carried out below - 80° C to prevent degradation of the polymer. Poly(vinyHdene chloride) in emulsion is also attacked by aqueous base. Therefore, reactions should be carried out at low pH. 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

Chain Structure. The chemical composition of poly (vinyhdene chloride) has been confirmed by various techniques, including elemental analysis, x-ray diffraction analysis, degradation studies, and in, Raman, and nmr spectroscopy. The polymer chain is made up of vinyhdene chloride units added head-to-tail ... 

The maximum rates of crystallisation of the more common crystalline copolymers occur at 80—120°C. In many cases, these copolymers have broad composition distributions containing both fractions of high VDC content that crystallise rapidly and other fractions that do not crystallise at all. Poly(vinyhdene chloride) probably crystallises at a maximum rate at 140—150°C, but the process is difficult to foUow because of severe polymer degradation. The copolymers may remain amorphous for a considerable period of time if quenched to room temperature. The induction time before the onset of crystallisation depends on both the type and amount of comonomer PVDC crystallises within minutes at 25°C. 

Solubility and Solution Properties. Poly(vinyhdene chloride), like many high melting polymers, does not dissolve in most common solvents at ambient temperatures. Copolymers, particularly those of low crystallinity, are much more soluble. However, one of the outstanding characteristics of vinyUdene chloride polymers is resistance to a wide range of solvents and chemical reagents. The insolubiUty of PVDC results less from its... 

Poly(vinyhdene chloride) also dissolves readily in certain solvent mixtures (82). One component must be a sulfoxide or A/,Al-diaIk5lamide. Effective cosolvents are less polar and have cycHc stmctures. They include aUphatic and aromatic hydrocarbons, ethers, sulfides, and ketones. Acidic or hydrogen-bonding solvents have an opposite effect, rendering the polar aprotic component less effective. Both hydrocarbons and strong hydrogen-bonding solvents are nonsolvents for PVDC. 

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. 

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