PVDC

Fig. 10. Adsorption ( , O)"desorption (A, A) isotherms of water vapor on poly(vinylidene chloride) (PVDC) carbon before (filled symbols) and after...

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). 

Polyester. Poly(ethylene terephthalate) [25038-59-9] (PET) polyester film has intermediate gas- and water- vapor barrier properties, very high tensile and impact strengths, and high temperature resistance (see Polyesters, thermoplastic). AppHcations include use as an outer web in laminations to protect aluminum foil. It is coated with PVDC to function as the flat or sealing web for vacuum/gas flush packaged processed meat, cheese, or fresh pasta. 

Poly(vinylidene chloride). Poly(viayHdene chloride) [9002-85-1] (PVDC), most of which is produced by Dow Chemical, is best known in its saran or PVC-copolymerized form (see Vinylidene chloride and poly(VINYLIDENE chloride)). As solvent or emulsion coating, PVDC imparts high oxygen, fat, aroma, and water-vapor resistance to substrates such as ceUophane, oriented polypropylene, polyester, and nylon. 

Of the common commercial resias and films, PVDC has the best water-vapor and oxygen-barrier properties. High crystallinity confers resistance to the permeation of odors and flavors, as weU as to fat and oil. Because of its high chloride content, PVDC tends to corrode processing equipment, which increases manufacturing costs. Unlike other high oxygen-barrier materials, PVDC is almost insensitive to water and water vapor. 

Copolymer film is produced by extmsion blowing foUowed by water quenching. In-line, the film is blown, crystallized, and oriented. PVDC copolymer film is difficult to produce. 

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). 

Glass offers good resistance to strong acid at high temperatures. However, it is subject to thermal shock and a gradual loss in integrity as materials such as iron and siUca are leached out into the acid. Nonmetallic materials such as PTFE, PVDC, PVDF, and furan can be used for nitric acid to a limited degree, but are mainly restricted to weak acid service at ambient to moderate temperatures. 

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. 

The infrared spectra of PVDC often show traces of unsaturation and carbonyl groups. The slighdy yeUow tinge of many of these polymers comes from the same source the pure polymer is colorless. Elemental analyses for chlorine are normally slightly lower than the theoretical value of 73.2%. 

Molecular weights of PVDC can be determined directly by dilute solution measurements in good solvents (62). Viscosity studies indicate that polymers having degrees of polymerization from 100 to more than 10,000 are easily obtained. Dimers and polymers having DP < 100 can be prepared by special procedures (40). Copolymers can be more easily studied because of thek solubiUty in common solvents. Gel-permeation chromatography studies indicate that molecular weight distributions are typical of vinyl copolymers. 

Crystal Structure. The crystal stmcture of PVDC is fairly well estabhshed. Several unit cells have been proposed (63). The unit cell contains four monomer units with two monomer units per repeat distance. The calculated density, 1.96 g/cm, is higher than the experimental values, which are 1.80—1.94 g/cm at 25°C, depending on the sample. This is usually the case with crystalline polymers because samples of 100% crystallinity usually cannot be obtained. A dkect calculation of the polymer density from volume changes during polymerization yields a value of 1.97 g/cm (64). If this value is correct, the unit cell densities may be low. 

The repeat distance along the chain axis (0.468 nm) is significantly less than that calculated for a planar zigzag stmcture. Therefore, the polymer must be in some other conformation (65—67). Based on k and Raman studies of PVDC single crystals and normal vibration analysis, the best conformation appears to be where the skeletal angle, is 120°, and the torsional of opposite sign) is 32.5°. This conformation is in... 

The melting temperature, T, of PVDC is independent of molecular weight above DP = 100. However, as shown in Eigure 2, it drops sharply at lower molecular weights. Below the hexamer, the products are noncrystalline Hquids. 

The properties of PVDC (Table 3) ate usually modified by copolymerization. Copolymers of high VDC content have lower melting temperatures than PVDC. Copolymers containing mote than mol % acrylate or methacrylate ate amorphous. Substantially mote acrylonitrile (25%) or vinyl chloride (45%) is required to destroy crystallinity completely. 

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. 

As-polymerized PVDC does not have a well-defined glass-transition temperature because of its high crystallinity. However, a sample can be melted at 210°C and quenched rapidly to an amorphous state at <—20°C. The amorphous polymer has a glass-transition temperature of — 17°C as shown by dilatometry (70). Glass-transition temperature values of —19 to — 11°C, depending on both method of measurement and sample preparation, have been determined. 

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... 

The polarity of the polymer is important only ia mixtures having specific polar aprotic solvents. Many solvents of this general class solvate PVDC strongly enough to depress the melting temperature by more than 100°C. SolubiUty is normally correlated with cohesive energy densities or solubiUty parameters. For PVDC, a value of 20 0.6 (J/cm (10 0.3 (cal/cm ) has been estimated from solubiUty studies ia nonpolar solvents. The value... 

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. 

As-polymerized PVDC is not in its most stable state annealing and recrystaUization can raise the temperature at which it dissolves (78). Low crystallinity polymers dissolve at a lower temperature, forming metastable solutions. However, on standing at the dissolving temperature, they gel or become turbid, indicating recrystaUization into a more stable form. 

In early hterature, the molecular weights of PVDC and VDC copolymers were characterized by the absolute viscosity of a 2 wt % solution in (9-dichlorobenzene at 140°C. The exact correlation between this viscosity value and molecular weight is not known. Gel-permeation chromatography is the... 

In cases where the copolymers have substantially lower glass-transition temperatures, the modulus decreases with increasing comonomer content. This results from a drop in crystallinity and in glass-transition temperature. The loss in modulus in these systems is therefore accompanied by an improvement in low temperature performance. However, at low acrylate levels (< 10 wt %), T increases with comonomer content. The brittle points in this range may therefore be higher than that of PVDC. 

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. 

The storage capacity of an ANG storage system is always greater than its delivered capacity, usually by about fifteen percent. For some carbons, however, it can be as high as thirty percent because of the large amount of methane which is held by the adsorbent at less than one bar, (0.1 MPa). Carbons which are very microporous, such as polyvinylidene chloride (PVDC) carbons, tend to have very steep initial slopes to their methane isotherm, and as much as thirty percent of their overall uptake occurs at less than 0.1 MPa. These carbons have a high storage capacity but a much lower deliverable VfV. 

Monolithic carbons may also be manufactured in finished form fi om PVDC as has been done by Quinn [18]. The porosity and density compare favourably with those of conventional granular carbons and the Sutcliffe Speakmann monoliths but the manufacturing process is not easy to scale up from the laboratory to commercial levels. The properties, (including K and n from the D-A equation) are compared in Table 3 below, taken from Critoph [4]. 

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