Vinylidene chloride polymers processing

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). 

Copolymers of acrylonitrile and vinylidene chloride have been used for many years to produce films of low gas permeability, often as a coating on another material. Styrene-acrylonitrile with styrene as the predominant free monomer (SAN polymers) has also been available for a long time. In the 1970s materials were produced which aimed to provide a compromise between the very low gas permeability of poly(vinylidene chloride) and poly(acrylonitrile) with the processability of polystyrene or SAN polymers (discussed more fully in Chapter 16). These became known as nitrile resins. 

Vinylidene chloride polymerises spontaneously into polyfvinylidene chloride), a polymer sufficiently thermally unstable to be unable to withstand melt processing... 

By copolymerising the vinylidene chloride with about 10-15% of vinyl chloride, processable polymers may be obtained which are used in the manufacture of filaments and films. These copolymers have been marketed by the Dow Company since 1940 under the trade name Saran. Vinylidene chloride-acrylonitrile copolymers for use as coatings of low moisture permeability are also marketed (Saran, Viclan). Vinylidene chloride-vinyl chloride copolymers in which the vinylidene chloride is the minor component (2-20%) were mentioned in Chapter 12. 

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. 

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... 

The 1,1-disubstitution of chlorine atoms causes steric interactions in the polymer, as is evident from the heat of polymerization (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 apparendy is not important in the addition step, because VDC polymerizes easily. Nor is it sufficient to favor depolymerization the estimated ceiling temperature for poly(vinylidene chloride) (PVDC) is about 400°C. 

The maximum rates of crystallization 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 crystallize rapidly and other fractions that do not crystallize at all. Poly(vinylidene chloride) probably crystallizes at a maximum rate at 140—150°C, but the process is difficult to follow 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 crystallization depends on both the type and amount of comonomer PVDC crystallizes within minutes at 25°C. 

Poly(vinylidene chloride) may be obtained from The Dow Chemical Co. as a white powder, designated saran A. To prepare saran charcoal from this powder it is first pressed into a convenient shape by use of a hydraulic press and steel die at a pressure of 15,000 p.s.i. The compressed polymer is then heated slowly in vacuo, starting at 125° C. and gradually increasing the temperature up to 750° C. The heating process takes about 3 weeks and the resulting piece of carbon retains the shape of the original polymer but is reduced in size in all directions by about 20%. 

In addition to homopolymers of varying molecular and particle structure, copolymers are also available commercially in which vinyl chloride is the principal monomer. Comonomers used commercially include vinyl acetate, vinylidene chloride, propylene, acrylonitrile, vinyl isobutyl ether, and maleic, fumaric and acrylic esters. Of these the first three only are of importance to the plastics industry. The main function of introducing comonomer is to reduce the regularity of the polymer structure and thus lower the interchain forces. The polymers may therefore be processed at much lower temperatures and are useful in the manufacture of gramophone records and flooring compositions. 

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