VINYL CHLORIDE POLYMER

It is an interesting paradox that one of the least stable of commercially available polymers should also be, in terms of tonnage consumption at least, one of the two most important plastics materials available today. Yet this is the unusual position held by poly(vinyl chloride) (PVC), a material whose commercial success has been to a large extent due to the discovery of suitable stabilisers and other additives which has enabled useful thermoplastic compounds to be produced. 

The polymerisation in sealed tubes of vinyl chloride and vinyl bromide, when exposed to sunlight, was reported in 1872 by Baumann. Further work on these polymerisations was carried out by Ostromislensky in Moscow and this was duly reported in 1912.  

Commercial interest in poly(vinyl chloride) was revealed in a number of patents independently filed in 1928 by the Carbide and Carbon Chemical Corporaration, Du Pont and IG Farben. In each case the patents dealt with vinyl chloride-vinyl acetate copolymers. This was because the homopolymer could only be processed in the melt state at temperatures where high decomposition rates occurred. In comparison the copolymers, which could be processed at much lower temperatures, were less affected by processing operations. 

An alternative approach, which in due course became of great commercial significance, was made by W. L. Semon. He found that if poIy(vinyl chloride) 

During the next few years PVC was steadily developed in the United States and in Germany. Both countries were producing the material commercially before World War II. In Great Britain, ICI in 1942 and the Distillers Company in 1943 also commenced pilot-plant production of PVC, a material then in demand as a rubber substitute for cable insulation. Paste-forming grades suitable for the production of leathercloth also became available soon afterwards. 

Polymer United States Canada Mexico North American Total 

Morphology as Polymerized. The principal type of polymerization of PVC is the suspension polymeriza tion route. The morphology formed during polymerization strongly influences the processibiUty and physical properties. Mass-polymerized PVC has a similar morphology to suspension PVC. 

In the suspension polymerization of PVC, droplets of monomer 30—150 p.m in diameter are dispersed in water by agitation. A thin membrane is formed at the water—monomer interface by dispersants such as poly(vinyl alcohol) or methyl cellulose. This membrane, isolated by dissolving the PVC in tetrahydrofuran and measured at 0.01—0.02-p.m thick, has been found to be a graft copolymer of polyvinyl chloride and poly(vinyl alcohol) (4,5). Early in the polymerization, particles of PVC deposit onto the membrane from both the monomer and the water sides, forming a skin 0.5—5-p.m thick that can be observed on grains sectioned after polymerization (4,6). Primary particles, 1 p.m in diameter, deposit onto the membrane from the monomer side (Pig. 1), whereas water-phase polymer, 0.1 p.m in diameter, deposits onto the skin from the water side of the membrane (Pig. 2) (4). These domain-sized water-phase particles may be one source of the observed domain stmcture (7). 

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

PVC has a unique ability to be compounded with a wide variety of additives, making it possible to produce materials that range from flexible elastomers to rigid compounds, that are virtually unbreakable with a notched Izod impact greater than 0.5 J/mm at —40 C, that are weatherable with good property retention for over 30 years, as well as compounds that have stiff melts and litde elastic recovery for outstanding dimensional control in profile extrusion, and also low viscosity melts for thin-walled injection molding. 

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Vinyl chloride is used almost exclusively for the manufacture of polymers and copolymers. U.S. production 1983 2-6 megatonnes. See vinyl chloride polymers. 

Raw Materials. PVC is inherently a hard and brittle material and very sensitive to heat it thus must be modified with a variety of plasticizers, stabilizers, and other processing aids to form heat-stable flexible or semiflexible products or with lesser amounts of these processing aids for the manufacture of rigid products (see Vinyl polymers, vinyl chloride polymers). Plasticizer levels used to produce the desired softness and flexibihty in a finished product vary between 25 parts per hundred (pph) parts of PVC for flooring products to about 80—100 pph for apparel products (245). Numerous plasticizers (qv) are commercially available for PVC, although dioctyl phthalate (DOP) is by far the most widely used in industrial appHcations due to its excellent properties and low cost. For example, phosphates provide improved flame resistance, adipate esters enhance low temperature flexibihty, polymeric plasticizers such as glycol adipates and azelates improve the migration resistance, and phthalate esters provide compatibiUty and flexibihty (245). 

Vinyl chloride polymers are produced in two main types, homopolymers and copolymers, usually with vinyl acetate. Both types can be plasticized by a wide variety of plasticizers (qv), usually esters. Rigid or unplasticized PVC is used extensively for pipe. The plasticized material is used largely in floor coverings. The homopolymer itself is inherently fire-resistant, but addition of plasticizers, unless they are especially fire-resistant, considerably reduces this characteristic (see Elame retardants). 

Liquid trichloroethylene has been polymerized by irradiation with Co y-rays or 20-keV x-rays (9). Trichloroethylene has a chain-transfer constant of <1 when copolymerized with vinyl chloride (10) and is used extensively to control the molecular weight of poly(vinyl chloride) polymer. 

X-ray studies indicate that the vinyl chloride polymer as normally prepared in commercial processes is substantially amorphous although some small amount of crystallinity (about 5% as measured by X-ray diffraction methods) is present. It has been reported by Fuller d in 1940 and Natta and Carradini in 1956 that examination of the crystalline zones indicates a repeat distance of 5.1 A which is consistent with a syndiotactic (i.e. alternating) structure. Later studies using NMR techniques indicate that conventional PVC is about 55% syndiotactic and the rest largely atactic in structure. 

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