Ethylenes, Halogenated

A large number of ethylene halogen derivatives peroxidise easily at ambient temperature, by forming peroxides and polyperoxides that are particularly dangerous. 

The risks related to the polymerisation of ethylene halogen derivative are... 

Ethylene halogen derivatives presenting a poiymerisation risk Compound... 

Keywords 1,2-bis(4-pyridyl)ethylene, halogen-bonding, [2+2]photodimerization... 

The beneficial effects of solid surfaces on the rates of bromination reactions were observed as eai ly as 1923 [4-6], The polarity of the glass surface was found to enhance the rates of bromination of ethylene. Halogenation reactions over zeolite catalysts have been reviewed [1]. A summary of halogenations over non-zeolite (until mid-1999) and zeolite (1995-mid 1999) catalysts is given in Table 1. 

Acids, chromium, ethylene, halogens, hydrogen, mercury, nitrogen, oxidizers, plastics, sodium chloride, sulfur Halogenated hydrocarbons, water Acids, aldehydes, amides, halogens, heavy metals, oxidizers, plastics, sulfur... 

NFPA Health 1, Flammability 4, Reactivity 0 Uses Component of natural gas propellant in cosmetics petrochemicals (source of ethylene, halogenated ethanes) fuel refrigerant prod, of carbon tetrachloride, ethyl chloride, ethylene, perchloroethylene in food-contact textiles... 

Halogenethers s. a. Alkoxy-halides, Dihalogenethers, Monochloromethyl ether Halogenethylen... s. a. Ethylene-halogen... 

Many of the features of the generally accepted mechanism for the addition of halogens to alkenes can be introduced by referring to the reaction of ethylene with bromine... 

Alkali metals Moisture, acetylene, metal halides, ammonium salts, oxygen and oxidizing agents, halogens, carbon tetrachloride, carbon, carbon dioxide, carbon disul-flde, chloroform, chlorinated hydrocarbons, ethylene oxide, boric acid, sulfur, tellurium... 

Ammonia, anhydrous Mercury, halogens, hypochlorites, chlorites, chlorine(I) oxide, hydrofluoric acid (anhydrous), hydrogen peroxide, chromium(VI) oxide, nitrogen dioxide, chromyl(VI) chloride, sulflnyl chloride, magnesium perchlorate, peroxodisul-fates, phosphorus pentoxide, acetaldehyde, ethylene oxide, acrolein, gold(III) chloride... 

Magnesium Air, beryllium fluoride, ethylene oxide, halogens, halocarbons, HI, metal cyanides, metal oxides, metal oxosalts, methanol, oxidants, peroxides, sulfur, tellurium... 

Methane has also been used in aerobic bioreactors that are part of a pump-and-treat operation, and toluene and phenol have also been used as co-substrates at the pilot scale (29). Anaerobic reactors have also been developed for treating trichloroethylene. Eor example, Wu and co-workers (30) have developed a successful upflow anaerobic methanogenic bioreactor that converts trichloroethylene and several other halogenated compounds to ethylene. 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

Another use of hydrogen fluoride, although not in halogen exchange, is the reaction with ethylenes or acetylenes to form the addition products, 1,1-difluoroethane [75-37-6] and vinyl fluoride [75-02-5]-. 

Vlayl fluoride [75-02-5] (VF) (fluoroethene) is a colorless gas at ambient conditions. It was first prepared by reaction of l,l-difluoro-2-bromoethane [359-07-9] with ziac (1). Most approaches to vinyl fluoride synthesis have employed reactions of acetylene [74-86-2] with hydrogen fluoride (HF) either directly (2—5) or utilizing catalysts (3,6—10). Other routes have iavolved ethylene [74-85-1] and HF (11), pyrolysis of 1,1-difluoroethane [624-72-6] (12,13) and fluorochloroethanes (14—18), reaction of 1,1-difluoroethane with acetylene (19,20), and halogen exchange of vinyl chloride [75-01-4] with HF (21—23). Physical properties of vinyl fluoride are given ia Table 1. 

Polymerization. The first successful polymerizations of VDE in aqueous medium using peroxide initiators at 20—150°C and pressures above 30 MPa were described in a patent issued in 1948 (73). About a year later, the first copolymerizations of VDE with ethylene and halogenated ethylenes were also patented (74). After a hiatus of over 12 years a commercially feasible process was developed and PVDE was ready for market introduction (2). 

Cables are available in a variety of constmctions and materials, in order to meet the requirements of industry specifications and the physical environment. For indoor usage, such as for Local Area Networks (LAN), the codes require that the cables should pass very strict fire and smoke release specifications. In these cases, highly dame retardant and low smoke materials are used, based on halogenated polymers such as duorinated ethylene—propylene polymers (like PTFE or FEP) or poly(vinyl chloride) (PVC). Eor outdoor usage, where fire retardancy is not an issue, polyethylene can be used at a lower cost. 

Ethylene vinyl acetate (EVA) polymers are used in thermoplastic and thermosetting jacketing compounds for apphcations that require flame retardancy combined with low smoke emission during the fire as well as the absence of halogen in the composition. 

Flame-Retardant Resins. Flame-retardant resins are formulated to conform to fire safety specifications developed for constmction as well as marine and electrical appHcations. Resins produced from halogenated intermediates (Table 5) are usually processed at lower temperatures (180°C) to prevent excessive discoloration. Dibromoneopentyl glycol [3296-90-0] (DBNPG) also requires glass-lined equipment due to its corrosive nature. Tetrabromophthahc anhydride (TBPA) and chlorendic anhydride (8) are formulated with ethylene glycols to maximize fiame-retardant properties reaction cycle times are about 12 h. Resins are also produced commercially by the in situ bromination of polyester resins derived from tetrahydrophthahc anhydride... 

Ethylene oxide is produced in large, multitubular reactors cooled by pressurized boiling Hquids, eg, kerosene and water. Up to 100 metric tons of catalyst may be used in a plant. Typical feed stream contains about 30% ethylene, 7—9% oxygen, 5—7% carbon dioxide the balance is diluent plus 2—5 ppmw of a halogenated moderator. Typical reactor temperatures are in the range 230—300°C. Most producers use newer versions of the Shell cesium-promoted silver on alumina catalyst developed in the mid-1970s. 

The fact that the polymer contains no halogens along with certain unique compounding techniques for flame resistance prompts the selection of ethylene—acryflc as jacketing material on certain transportation/mifltary electrical cables and in floor tiles. 

Other thermoplastic elastomer combiaations, ia which the elastomer phase may or may not be cross-linked, include blends of polypropylene with nitrile (30,31), butyl (33), and natural (34) mbbers, blends of PVC with nitrile mbber (35,36), and blends of halogenated polyolefins with ethylene interpolymers (29). Collectively, thermoplastic elastomers of this type ate referred to herein as hard polymer/elastomer combinations. Some of the more important examples of the various types are shown in Table 3. 

Addition. Addition reactions of ethylene have considerable importance and lead to the production of ethylene dichloride, ethylene dibromide, and ethyl chloride by halogenation—hydrohalogenation ethylbenzene, ethyltoluene, and aluminum alkyls by alkylation a-olefms by oligomerization ethanol by hydration and propionaldehyde by hydroformylation. 

Halogenation—Hydrohalogenation. The most important iatermediate is ethylene dichloride [107-06-2] (EDC) which is produced from ethylene either by direct chlorination or by oxychloriaation. Direct chlorination is carried out ia the Hquid or vapor phase over catalysts of iron, alumiaum, copper, or antimony chlorides, and at conditions of 60°C. Oxychloriaation is carried out ia a fixed or fluidized bed at 220°C with a suitable soHd chloride catalyst. 

Acyl halides may also be added to ethylene ia the presence of aluminum chloride to form halogenated ketones. At low temperatures, ethylene reacts with halogens to yield dihaloethanes. At high temperatures, trichloroethylene and perchloroethylene are formed. The most profitable route for chloroethylene is via ethylene dichloride (see Chlorocarbonsandchlorohydrocarbons). 

The per pass ethylene conversion in the primary reactors is maintained at 20—30% in order to ensure catalyst selectivities of 70—80%. Vapor-phase oxidation inhibitors such as ethylene dichloride or vinyl chloride or other halogenated compounds are added to the inlet of the reactors in ppm concentrations to retard carbon dioxide formation (107,120,121). The process stream exiting the reactor may contain 1—3 mol % ethylene oxide. This hot effluent gas is then cooled ia a shell-and-tube heat exchanger to around 35—40°C by usiag the cold recycle reactor feed stream gas from the primary absorber. The cooled cmde product gas is then compressed ia a centrifugal blower before entering the primary absorber. 

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