Vinyl fluoride monomer

VINYL FLUORIDE or VINYL FLUORIDE MONOMER (75-02-S) Flammable gas. Able to polymerize unless inhibited (0.2% terpenes are recommended). Violent reaction with oxidizers. Heat of combustion forms toxic hydrogen fluoride gas. May accumulate static electrical charges, and may cause ignition of its vapors. 

Synonyms/Trade Names Fluoroethene, Fluoroethylene, Monofluoroethylene, Vinyl fluoride monomer... 

Vinyl fluoride monomer from a commercial supplier of specialty gases has been purified by passing the gas through silica gel. Then the compound was fi ed of air by conventional degassing procedures using liquid air to freeze the monomer [15]. 

Vinyl fluoride monomer exhibits solubility in a variety of organic solvents, e.g., the lower alcohols, ethers, mono- and dinitriles, butyrolactone, liquid amides such as diethylformamide [6], and heptane [38]. As mentioned before, the polymer is generally quite insoluble at ordinary temperatures. At temperatures in the range of 100 C, some of these compoimds dissolve the polymer. During the polymerization of vinyl fluoride, one would, therefore, expect to find that the polymer precipitates as it forms. Solvents also tend to act as chain-transfer agents which yield products of lower molecular weights than those formed in the absence of solvents. Procedure 2-2 shows the effect of a solvent on the intrinsic viscosity and on the overall conversion. Since the procedure is patented it is given here only to illustrate the procedure. 

Vinyl fluoride monomer can be prepared by addition of HF to acetylene. The monomer is a gas at room temperature and boils at —72.2°C. Conunercially, vinyl fluoride is polymerized in aqueous medium using either redox initiation or one from thermal decomposition of peroxides. Pressures of up... 

The addition of hydrogen fluoride to acetylene is the most common commercial approach to the preparation of vinyl fluoride monomer. As catalysts, mercury oxide, carbon pellets, or charcoal-containing mercuric chloride or fluoride were mentioned [464],... 

Vinyl Fluoride. Vinyl fluoride [75-02-5] C2H2F, the monomer for poly(vinyl fluoride), is manufactured by addition of hydrogen fluoride to acetylene (see Fluorine COMPOUNDS, ORGANIC, POLY(viNYL FLUORIDE)). 

Copolymers of VF and a wide variety of other monomers have been prepared (6,41—48). The high energy of the propagating vinyl fluoride radical strongly influences the course of these polymerizations. VF incorporates well with other monomers that do not produce stable free radicals, such as ethylene and vinyl acetate, but is sparingly incorporated with more stable radicals such as acrylonitrile [107-13-1] and vinyl chloride. An Alfrey-Price value of 0.010 0.005 and an e value of 0.8 0.2 have been determined (49). The low value of is consistent with titde resonance stability and the e value is suggestive of an electron-rich monomer. 

Poly(vinyl fluoride) [24981-14-4] (PVF) is a semicrystaltiae polymer with a planar, zig-zag configuration (50). The degree of crystallinity can vary significantly from 20—60% (51) and is thought to be primarily a function of defect stmctures. Wide-line nmr and x-ray diffraction studies show the unit cell to contain two monomer units and have the dimensions of a = 0.857 nm, b = 0.495 nm, and c = 0.252 nm (52). Similarity to the phase I crystal form of poly (vinytidene fluoride) suggests an orthorhombic crystal (53). 

Vinyl fluoride (fluoroethene), is manufactured from the cataly2ed addition of hydrogen fluoride to acetylene. It is used to prepare poly(vinyl fluoride) which has found use in highly weather-resistant films (Tedlar film, Du Pont). Poly(vinyhdene fluoride) also is used in weather-resistant coatings (see Eluorine compounds, organic). The monomer can be prepared from acetylene, hydrogen fluoride, and chlorine but other nonacetylenic routes are available. 

Poly(vinyl fluoride) was first introduced in the early 1960s, in film form, by Du Pont under the trade name Tedlar. Details of the commercial method of preparing the monomer have not been disclosed but it may be prepared by addition of hydrogen fluoride to acetylene at about 40°C. 

The addition of hydrogen fluoride to acetylene has been widely investigated because the initial product, vinyl fluoride, is a commercially important monomer Acetylene reacts with hydrogen fluoride in the liquid phase in the absence of catalyst to give vinyl fluoride and 1,1 -ditluoroethane in modest yields [7 ], but better results are achieved by conducting the addition with various additives or catalysts... 

Monomer addition under radical propagation conditions leads to mainly an atactic configuration. As a consequence, radical polymerisations of asymmetric vinyl polymers usually lead to amorphous materials. However, if the substituent is small enough to enter into the crystal cell, atactic vinyl polymers can crystallise (an example is poly(vinyl fluoride)). 

The resulting complexes can be effectively employed as single component catalysts to homopolymerize ethylene or copolymerize ethylene with acrylates [50, 51] and a variety of other polar monomers including vinyl ethers, [51,52] vinyl fluoride [53], iV-vinyl-2-pyrrolidinone, and AMsopropylacrylamide [54], In fact, the resulting catalysts are so robust that they can be used as single component catalysts in aqueous emulsion homo-polymerization of ethylene and copolymerization of ethylene with norbomenes and acylates [55]. 

Many vinyl monomers were reported to have been grafted onto fluoropolymers, such as (meth)acrylic acid and (meth)acrylates, acrylamide, acrylonitryl, styrene, 4-vinyl pyridine, N-vinyl pyrrolidone, and vinyl acetate. Many fluoropolymers have been used as supports, such as PTFE, copolymers of TFE with HFP, PFAVE, VDF and ethylene, PCTFE, PVDF, polyvinyl fluoride, copolymers ofVDF with HFP, vinyl fluoride and chlorotrifluoroethylene (CTFE). The source of irradiation has been primarily y-rays and electron beams. The grafting can be carried out under either direct irradiation or through the use of preliminary irradiated fluoropolymers. Ordinary radical inhibitors can be added to the reaction mixture to avoid homopolymerization of functional monomers. 

The effect of pressure on polymerization, although not extensively studied, is important from the practical viewpoint since several monomers are polymerized at pressures above atmospheric. Pressure affects polymerization through changes in concentrations, rate constants, and equilibrium constants [Ogo, 1984 Weale, 1974 Zutty and Burkhart, 1962], The commercial polymerizations of most gaseous monomers (e.g., vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinyl fluoride) are carried out at very moderate pressures of about 5-10 MPa (1 MPa = 145 psi), where the primary effect is one of increased... 

PDD as well as other dioxoles have been copolymerized with monomers such as vinyl fluoride, vinylidene fluoride, tiifluoroediylene, perfluoroalkylethylenes, chlorotrifluoroethylene, hexafluoropropylene, and perfluorovinyl ethers, some of which contain functional groups. 

The literature reports direct grafting by gamma-rays exposure of Nylon fibers or films to the following monomers carbon monoxide (/65), ethylene (157), propylene (157), acetylene (166), butadiene (157.162,163), styrene (158, 161,163,167,168), vinyl chloride (157,163), vinyl fluoride (169-172), vinyl acetate (161,163,173), vinyl propionate (161), vinyl butyrate (161), vinyl crotonate (161), vinyl 2-ethyl hexanoate (161), acrylic add (173,174), methyl acrylate (162, 163), ethyl acrylate (162,163), allyl acrylate (163), methyl methacrylate (28,161, 163,164), butyl methacrylate (161), acrylamide (158), methylol acrylamide (163), acrylonitrile (157,160-163, 167, 175-179), divinyl sulfone (161), vinyl pyridine (167,173), vinyl pyrrolidone (28) and triallyl cyanurate (158). 

Vinyl fluoride is an interesting monomer, precursor of PVF or Tedlar (produced by the Dupont Company), known for its good resistance to UV radiation. But in telomerisation, the most intensive work was achieved by Tedder and Walton who used several telogens exhibiting cleavable C-Br or C-I bonds, under UV at various temperatures (Table 17). Their surveys were mostly devoted to the obtaining of monoadduct and to their kinetics (e.g., determination of relative rate constants of formation of normal and reverse isomers and of Arrhenius parameters). 

Vinyl fluoride and 1,1,1-trifluoropropene have shown a great efficiency in telomerisation with various telogens,but concerning the other ones, less interest has been focused on. This may be due to the lack of availability of monomers, and consequently studies on monoadduct were mostly investigated. 

There are several methods to prepare vinyl fluoride (VF) monomer. One of the methods described in patent literature is a two-step method.60 The first step is the reaction of hydrogen fluoride with acetylene in the presence of a suitable catalyst to yield ethylidene fluoride, which is subsequently pyrolyzed ... 

PDD readily copolymerizes with tetrafluoroethylene and other monomers containing fluorine, such as VDF, CTFE, vinyl fluoride, and PVE via free radical copolymerization, which can be carried out in either aqueous or nonaqueous media. It also forms an amorphous homopolymer with a Tg of 335°C (635°F).2... 

Polymerization of Styrene Solutions of Volatile Hydrocarbons. Addition of Hydrocarbon before Polymerization. Bulk Polymerization. Expandable polystyrene was prepared inadvertently in 1945 in an attempt to bulk copolymerize 10% isobutylene with styrene. The product formed a low density foam when heated (96). An early method (1950) for rendering polystyrene expandable by petroleum ether was to dissolve 6 parts of petroleum ether in a 40% solution of polystyrene in benzoyl peroxide-catalyzed styrene and to hold the mass for 28 days at 32 °C. (124). In a recent version of this process, the monomer (chlorostyrene) and blowing agent (trichlorofluoromethane) in a poly (vinyl fluoride) bag were irradiated with y-rays (105). 

The major commercial fluoropolymers are made by homopolymerization of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE),vinyhdene fluoride (VF2), and vinyl fluoride (VF), or by co-polymerization of these monomers with hexafluoropropylene (HFP), perfluoro(propyl vinyl ether) (PPVE), per-fluoro(methyl vinyl ether) (PMVE), or ethylene. The polymers are formed by free-radical polymerization in water or fluorinated solvents. 

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