Ethylene dichloride

Ethylene dichloride (1,2-dichloroethane, CH2C1CH2C1), a colorless toxic liquid (boiling point 84°C, density 1.2560, flashpoint 13°C) is manufactured by two methods. 

The classical method for the manufacture of ethylene dichloride is the addition of chlorine to the double bond of ethylene (Fig. 1). 

Ferric chloride is often used as the catalyst. The yield is high (96 to 98%, based on ethylene) and the reaction can be carried out in the vapor phase or in the liquid phase at varying temperatures and the product is easily purified by fractional distillation. 

However, when chlorine is added to olefins such as ethylene, many and mixed derivatives are formed. In addition to ethylene dichloride, dichloroeth-ylene, trichloroethylene, tetrachloroethane, and chloromethanes form. Other halogens produce similar mixtures. With good reaction control, high yields of the desired product are possible. 

FIGURE 1 Manufacture of ethylene dichloride by direct chlorination. 

2-Dichloroet hone sym-Dichloroethane Ethylene Chloride Dutch Oil Elayl Chloride 

Color (500-mm tube) fLovibond) Dielectric constant 20 C Electrical conductivity Explosive limits in air Fire point 

Specific gravity 20/20 C Specific heat Specific resistivity Surface tension 25 C Thermal conductivity 20 C Vapor density (B. P., 760 mm) Vapor pressure 20 C 30 C 

Ter Haar G. An investigation of possible sterility and health effects from exposure to ethylene dibromide. In Banbury Report 5— Ethylene Dichloride A Potential Health Risk pp 167-188. Cold Spring Harbor, NY, Cold Spring Harbor Laboratory, 1980 

Agency for Toxic Substances and Disease Registry (ATSDR) Toxicoloffcal Profile for 1,2-Dibromoethane. TP-91/13, 148pp, US Department of Health and Human Services, Public Health Service, 1992 

lARC Monographs on the Evaluation of Carcinogenic Risks to Humans, Vol 71, Re-evaluation of some organic chemicals, hydrazine and hydrogen peroxide, pp 641-69. Lyon, International Agency for Research on Cancer, 1999 

Synonyms 1,2-Dichloroethane dichloro-ethane ethylene chloride 

Manufacture of vinyl chloride antiknock agent fumigant, insecticide degreaser compounds rubber cements 

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Most of the ethylene dichloride produced is utilized for the manufacture of vinyl chloride, which may be obtained from it by pyrolysis or the action of caustic soda. Large quantities are also used in anti-knock additives for gasoline. As a solvent It has been displaced by trichloroethylene and tetrachloroelhyJene. U.S. production 1978 4-75 megatonnes. 

CH3CHCICH2CI. Colourless liquid with a pleasant odour b.p. 96 C, Manufactured by treating liquid chlorine with an excess of liquid propene. It is very similar in properties to ethylene dichloride, and is used for similar purposes. 

Polyhydric alcohols are compounds containing two or more hydroxyl groups in the molecule. The two most important are ethylene glycol HOCHjCHjOH (a dihydric alcohol) and glycerol HOCHjCH(OH)CH. OH (a trihydric alcohol). Ethylene glycol may be obtained by the hydrolysis of ethylene dibromide or ethylene dichloride with dilute aqueous sodium hydroxide or sodium carbonate solution ... 

Place a mixture of 1 0 g. of the hydrocarbon, 10 ml. of dry methylene chloride or ethylene dichloride or syw.-tetrachloroethane, 2 5 g. of powdered anhydrous aluminium chloride and 1-2 g. of pure phthalic anhydride in a 50 ml. round-bottomed flask fitted with a short reflux condenser. Heat on a water bath for 30 minutes (or until no more hydrogen chloride fumes are evolved), and then cool in ice. Add 10 ml. of concentrated hydrochloric acid cautiously and shake the flask gently for 5 min utes. Filter oflf the solid at the pump and wash it with 10-15 ml. of cold water. Boil the resulting crude aroylbenzoic acid with 10 ml. of 2 -5N sodium carbonate solution and 0 2 g. of decolourising carbon for 5 minutes, and filter the hot solution. Cool, add about 10 g. of crushed ice and acidify... 

To prevent the solid complex from caking (which occurs if the stirring is not sufficiently rapid) about 75 ml. of dry ethylene dichloride may be added. 

The solid appears to be a mixture of the complexes CH,COOH.BF, and 2CH COOH.BF,. The latter appears to be a liquid and is alone soluble in ethylene dichloride the former is a solid. The solid moiioocetic acid complex is obtained by saturating an ethylene dichloride solution of acetic acid with boron trifluoride, filtering and washing the precipitate with the solvent it is hygroscopic and should be protected from moisture. It may be used as required 0-75 mol is employed with 0-26 mol of ketone and 0 6 mol of anhydride. 

Cool the filtrate (A) to 5-10° and add concentrated hydrochloric acid dropwise and with vigorous stirring (FUME CUPBOARD hydrogen cyanide is evolved) to a pH of 1-2 (about 50 ml.) a crude, slightly pink 3-indoleacetic acid is precipitated. The yield of crude acid, m.p. 159-161°, is 20 g. Recrystallise from ethylene dichloride containing a small amount of ethanol 17 -5 g. of pure 3 indoleacetic acid, m.p. 167-168°, are obtained. 

Polysulphide rubbers. Ethylene dichloride and excess of sodium tetrasulphide when heated together give a polymeric polysulphide, Thiokol A, with properties resembling those of rubber ... 

Prepare a saturated solution of sodium sulphide, preferably from the fused technical sodium polysulphide, and saturate it with sulphur the sulphur content should approximate to that of sodium tetrasulphide. To 50 ml. of the saturated sodium tetrasulphide solution contained in a 500 ml. round-bottomed flask provided with a reflux condenser, add 12 -5 ml. of ethylene dichloride, followed by 1 g. of magnesium oxide to act as catalyst. Heat the mixture until the ethylene dichloride commences to reflux and remove the flame. An exothermic reaction sets in and small particles of Thiokol are formed at the interface between the tetrasulphide solution and the ethylene chloride these float to the surface, agglomerate, and then sink to the bottom of the flask. Decant the hquid, and wash the sohd several times with water. Remove the Thiokol with forceps or tongs and test its rubber-like properties (stretching, etc.). 

Once the principal route to vinyl chloride, in all but a few percent of current U.S. capacity this has been replaced by dehydrochlorination of ethylene dichloride. A combined process in which hydrogen chloride cracked from ethylene dichloride was added to acetylene was advantageous but it is rarely used because processes to oxidize hydrogen chloride to chlorine with air or oxygen are cheaper (7) (see Vinyl polymers). 

Chlorine cannot be stored economically or moved long distances. International movements of bulk chlorine are more or less limited to movements between Canada and the United States. In 1987, chlorine moved in the form of derivatives was 3.3 million metric tons or approximately 10% of total consumption (3). Exports of ethylene dichloride, vinyl chloride monomer, poly(vinyl chloride), propylene oxide, and chlorinated solvents comprise the majority of world chlorine movement. Countries or areas with a chlorine surplus exported in the form of derivatives include Western Europe, Bra2il, USA, Saudi Arabia, and Canada. Countries with a chlorine deficit are Taiwan, Korea, Indonesia, Vene2uela, South Africa, Thailand and Japan (3). 

Chlorine reacts with saturated hydrocarbons either by substitution or by addition to form chlorinated hydrocarbons and HCl. Thus methanol or methane is chlorinated to produce CH Cl, which can be further chlorinated to form methylene chloride, chloroform, and carbon tetrachloride. Reaction of CI2 with unsaturated hydrocarbons results in the destmction of the double or triple bond. This is a very important reaction during the production of ethylene dichloride, which is an intermediate in the manufacture of vinyl chloride ... 

Ethylene dichloride, vinyl chloride monomer, trichloroethylene, perchloroethylene. 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

Ethylene Dichlonde and Vinyl Chloride. In the United States, all ethylene dichloride [107-60-2] (EDC) is produced from ethylene, either by chlorination or oxychlorination (oxyhydrochlorination). The oxychlorination process is particularly attractive to manufacturers having a supply of by-product HCl, such as from pyrolysis of EDC to vinyl chloride [75-01-4] monomer (VCM), because this by-product HCl can be fed back to the oxychlorination reactor. EDC consumption follows demand for VCM which consumed about 87% of EDC production in 1989. VCM is, in turn, used in the manufacture of PVC resins. Essentially all HCl generated during VCM production is recycled to produce precursor EDC (see Chlorocarbons and Cm OROHYDROCARBONS ViNYLPOLYAffiRS). 

Chlorinated C2> Perchloroethylene (PCE) and trichloroethylene (TCE) can be produced either separately or as a mixture in varying proportions by reaction of C2-chlorinated hydrocarbons, eg, C2-chlorinated waste streams or ethylene dichloride, with a mixture of oxygen and chlorine or HCl. 

Ethylene Dichloride," Chemical Economics Handbook, SRI International, Menlo Park, Calif., June 1992. 

The various fumigants often exhibit considerable specificity toward insect pests, as shown in Table 8. The proper choice for any control operation is determined not only by the effectiveness of the gas but by cost safety to humans, animals, and plants flammabdity penetratabdity effect on seed germination and reactivity with furnishings. The fumigants may be used individually or in combination. Carbon tetrachloride has been incorporated with carbon disulfide, ethylene dichloride, or ethylene dibromide to decrease flammability, and carbon dioxide is used with ethylene oxide for the same purpose. 

PMMA is not affected by most inorganic solutions, mineral oils, animal oils, low concentrations of alcohols paraffins, olefins, amines, alkyl monohahdes and ahphatic hydrocarbons and higher esters, ie, >10 carbon atoms. However, PMMA is attacked by lower esters, eg, ethyl acetate, isopropyl acetate aromatic hydrocarbons, eg, benzene, toluene, xylene phenols, eg, cresol, carboHc acid aryl hahdes, eg, chlorobenzene, bromobenzene ahphatic acids, eg, butyric acid, acetic acid alkyl polyhaHdes, eg, ethylene dichloride, methylene chloride high concentrations of alcohols, eg, methanol, ethanol 2-propanol and high concentrations of alkahes and oxidizing agents. 

Solvent Treatment. Solvent processes can be divided into two main categories, solvent extraction and solvent dewaxing. The solvent used in the extraction processes include propane and cresyHc acid, 2,2 -dichlorodiethyl ether, phenol (qv), furfural, sulfur dioxide, benzene, and nitrobenzene. In the dewaxing process (28), the principal solvents are benzene, methyl ethyl ketone, methyl isobutyl ketone, propane, petroleum naphtha, ethylene dichloride, methylene chloride, sulfur dioxide, and iV-methylpyrroHdinone. 

Chemical Processing Intermediates and Other Applications. Monoethanolamine can be used as a raw material to produce ethylenedianiine. This technology has some advantages over the ethylene dichloride process in that salts are not a by-product. Additional reactions are requked to produce the higher ethyleneamines that are normally produced in the ethylene dichloride process. 

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