106-89-8 Epichlorohydrin

Epichlorohydrin is used to a large extent os a row material in the manufacture of epoxy resins. When condensed with di-hydric phenols or phenolic resins, epoxy resins are obtained which ronge from liquids to solids. It is also used in the monufacture of ion exchange resins, odhesion resins ond o large number of other chemicals. 

Virtually all epoxy resins are made with starting materials based on epichlorohydrin, principally by reaction with bisphenol A. It is also used for the preparation of resins to increase the wet strength of paper. Both epichlorohydrin and glycidol are used in the manufacture of pharmaceuticals. 

Epoxy resins are widely used in high-strength adhesives, corrosion-resistant coatings, and corrosion-resistant pipes and tanks. The simplest starting material for these thermoset polymers is made from phenol, acetone (to bisphenol A), and epichlorohydrin. 

The final resin product is obtained by reacting (curing or crosslinking) the above di-epoxide with acid anhydrides or polyamines. The curing agents (sometimes incorrectly called catalysts) react with the three-membered epoxide rings to produce a highly crosslinked polymer. 

Properties Colorless, odorless, flammable gas, boiling point. 7°C (23.5°F). Dimerizes thermally and forms explosive peroxides on contact with oxygen. 

Commercial grades Inhibited butadiene is shipped as a liquid in tank trucks, tank cars, and steel cylinders. It is stored cold to prevent dimerization.  

Solubility 6.6 wt% in water sol alcohol, acetone, THF, toluene, -heptane. 

Form Supplied in neat liquid both enantiomers available. 

Handling, Storage, and Precautions should only be handled in a well ventilated fume hood because of its low permissible exposure limit of 2 ppm and reports of allergic skin reactions and lung, liver, and kidney damage. MSDSs are available from the two principal manufacturers (Dow and Shell). The material is not moisture or air sensitive. 

Introduction. Epichlorohydrin (1) is most widely used in polymer synthesis. Other common uses include an in situ trapping agent for HCl, HBr, or the alcohol generated during formation of Meerwein s reagent (eq 1).  

Reactions with Nucleophiles. The epoxide is, by far, the more reactive site and a wide variety of nucleophiles have been used (eq 2) to open the ring at C-3 such as HCl (96%), HOAc ( 50%), H2S (65% as cyclized product 3-thietanol), HCN (66%), ethanol (90%), t-butanol (86%), phenyl or benzyl thiol (99% or 93%, respectively), and phenyl selenide (generated in situ from the diselenide and sodium hydroxymethyl sulfite) ( 55%). If desired, the epoxide is easily formed from the chlorohydrin by treatment with excess KOH or Et3N. 

Synonyms l-Chloro-2,3-epoxypropane 3-chloro-1,2 -epoxypropane (chloromethyl)-ethyleneoxide chloromethyloxirane  

Toxicology. Epichlorohydrin is a severe irritant of skin, eye, and respiratory tract. Repeated or prolonged exposure can cause lung liver and kidney damage. It is a direct-acting mutagen and is carcinogenic in experimental animals. 

Exposed workers had a marked increase in percentage of lymphocytes with chromatid breaks, chromosome breaks, severely damaged cells, and abnormal cells.  

Skin contact causes itching, erythema, and severe burns that appear after a latent period ranging from several minutes to days, depending on the intensity of exposure. One worker who failed to remove contaminated shoes for 6 hours developed severe skin damage, with 

Male rats administered five oral doses of 20mg/kg had a temporary fertility loss, whereas a single lOOmg/1 dose caused spermatocele formation and probable permanent sterility. Eifty inhalation exposures at 50ppm for 6 hours each caused transient infertility in male rats no changes were observed in reproductive parameters of female rats rabbits remained fertile. There was no evidence of teratogenicity in rat fetuses at doses that caused death in some of the treated dams.  

Prepared by H. T. Clarke and W. W. Hartman. Checked by Roger Adams and H. O. Cal very. 

In a s-1. flask (Note 1) provided with a mechanical stirrer, a reflux condenser, and a hopper which can be opened or closed at the bottom by means of a rubber bung attached to a glass rod 

The mixture is finally cooled and the ethereal solution carefully decanted from the solid, which is carefully rinsed twice with 250 cc. portions of dry ether. The united liquids are then distilled from a water bath held at 40-60°, the residue is fractionated with a column, and the fractions boiling at the following points are collected up to 110° at 110-115° at 115-117° and at 117-140°. The portion boiling at 115-117° is pure epichlorohydrin the lower and higher fractions are systematically redistilled, yielding a further quantity of pure material. The yield is 705-747 g. (76-81 per cent of the theoretical amount). The residue, varying from 16 to 150 g., consists of nearly pure glycerol dichlorohydrin, and may be employed in subsequent runs (Note 4). 

A flask fitted with three necks (Vol. I, p. 12) is very satisfactory for this reaction if it be not available, the tubes leading from the reflux condenser and the hopper must be bent at slight angles to prevent congestion of apparatus. 

The principal difficulties in the preparation are connected with the use of finely powdered alkali. Care must be taken to expose the powder as little as possible to a moist atmosphere, for if it becomes at all damp it tends to clump together and difficulty is experienced in adding it to the mixture. For this reason, and also on account of the irritating action of alkali on the mucous membranes, the sieve should be provided with wellfitting cover and receiver the sifted material should be weighed out into a stoppered bottle and placed in the apparatus directly from this container. The hopper from which the alkali is added to the mixture should be covered with a card with a hole through 

Data were last reviewed in lARC (1976) and the compound was classified in lARC Monographs Supplement 7 (1987). 

106-89-8 Chem. Abstr. Name. (Chloromethyl)oxirane lUPAC Systematic Name-. l-Chloro-2,3-epoxypropane Synonym-. Chloropropylene oxide 

2 Structural and molecular formulae and relative molecular mass 

Total world production figures for epichlorohydrin are not available. In the United States, production increased from 156 thousand tonnes in 1973 to 250 thousand tonnes in 1975 and 213 thousand tonnes in 1978. Epichlorohydrin was also produced in Czechoslovakia, France, Germany, the Netherlands and the USSR (WHO, 1984). 

Epichlorohydrin is a major raw material for epoxy and phenoxy resins, and is used in the manufacture of glycerine, in curing propylene-based rubbers, as a solvent for cellulose esters and ethers, and in resins with high wet-strength for the paper industry (Lewis, 1993). 

EPA Classified Toxic Waste, RCRA Waste Number U041 DOT Label Flammable Liquid and Poison, UN 2023 Formula C3H5CIO MW 92.53 CAS [106- 

Epichlorohydrin is used to make glycerol, epoxy resins, adhesive, and castings as derivatives for producing dyes, pharmaceuticals, surfactants, and plasticizers and as a solvent for resins, gums, paints, and varnishes. 

Colorless, mobile liquid with chloroform-like smeU exists as a racemic mixture of its optical isomers in equal amounts bp 116°C (240°F) freezes at —57°C (—70°F) density 1.1807 at 20°C (68°F) soluble in most organic solvents, moderately soluble in water (6.6% by weight). 

LDso valne, oral (gninea pigs) 280 mg/kg LCso valne, (rats) 250 ppm (8 h) 

A 25 ppm concentration may be detectable by odor. Exposure at this level may cause burning of the eyes and nose in hnmans. Above 100 ppm even a short exposnre may be hazardous to humans, cansing nansea, dyspnea, Inng edema, and kidney injnry. 

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Glycerol ct-dichlorohydrin, sym-dichloroiso-propyl alcohol, 1,3-dichloro-2-hydroxypropane, CH2CI-CHOH-CH2C1. Colourless liquid with an ethereal odour b.p. 174-175" C. Prepared by passing dry HCl into glycerin containing 2% elhanoic acid at 100-1 lO C. Converted to x-epichlorohydrin by K.OH, Used as a solvent for cellulose nitrate and resins. 

Glycerol -dichlorohydrin, 2.3-dichloro-propanol, CH2CI CHC1 CH2 0H. Colourless liquid, b.p. 182 C. Prepared by the chlorination of propenyl alcohol. Oxidized by nitric acid to 1,2-dichloropropionic acid. Reacts with NaOH to give epichlorohydrin. 

Epichlorohydrin (1 mol) was added dropwise over a period of 1.5 h to a solution of 2.2 mol of sodium acetylide in 1.5 1 of liquid ammonia. During, as well as for a period of 1.5 h after, the addition the temperature of the mixture was kept at about -45°C. The cooling bath was removed after this period and the mixture was agitated vigorously for another 3 h. The thermometer and vent were removed, and 75 g of powdered ammonium chloride v/ere added in 2-g portions with vigorous stirring. The atimonia was allowed to evaporate. 

Epichlorohydrin is a product of covulcanization of epichlorohydrin (epoxy) polymers with rubbers, especially di-polybutadiene. 

Poly(epichlorohydrin-co-ethylene oxide-co-allyl glycidyl ether) [26587-37-1... 

Polypropylene oxide-co-epichlorohydrin-co-allyl glycidyl ether)[25213-15-4... 

Cationic monomers are used to enhance adsorption on waste soHds and faciHtate flocculation (31). One of the first used in water treatment processes (10) is obtained by the cyclization of dimethyldiallylammonium chloride in 60—70 wt % aqueous solution (43) (see Water). Another cationic water-soluble polymer, poly(dimethylarnine-fi9-epichlorohydrin) (11), prepared by the step-growth... 

Epoxy Resins. The chemistry of epoxy resin adhesives is quite varied. However, the most widely used is that formed from the reaction of 4,4 -isopropyhdene diphenol (bisphenol A) [80-05-7] and epichlorohydrin [106-89-8] C H CIO. This epoxy resin is more commonly known as... 

Category includes only direct chlorine consumption the majority of consumption is included in Epichlorohydrin, propylene oxide. 

PoIya.mines are condensation polymers containing nitrogen they are made by a variety of synthetic routes. Most of the commercial polyamines are made by reaction of epichlorohydrin with amines such as methylamine [25988-97-0] or dimethylamine [39660-17-8] (18,19). Branching can be increased by a dding small amounts of diamines such as ethylenediamine [42751-79-1]. A typical stmcture of this type of polyamine is stmcture (9). 

The boric and sulfuric acids are recycled to a HBF solution by reaction with CaF2. As a strong acid, fluoroboric acid is frequently used as an acid catalyst, eg, in synthesizing mixed polyol esters (29). This process provides an inexpensive route to confectioner s hard-butter compositions which are substitutes for cocoa butter in chocolate candies (see Chocolate and cocoa). Epichlorohydrin is polymerized in the presence of HBF for eventual conversion to polyglycidyl ethers (30) (see Chlorohydrins). A more concentrated solution, 61—71% HBF, catalyzes the addition of CO and water to olefins under pressure to form neo acids (31) (see Carboxylic acids). 

One of the first attempts to produce polyurethane was from the reaction of an intermediate polyol of 1,3- and l,4-bis(hydroxyhexa uoroisopropyl)benzene m- and -12F-diols) by reaction with epichlorohydrin. This polyol was subsequentiy allowed to react with a commercial triisocyanate, resulting in a tough, cross-linked polyurethane (129,135,139). ASTM and military specification tests on these polyurethanes for weather resistance, corrosion prevention, bUster resistance, and ease of cleaning showed them to compare quite favorably with standard resin formulations. 

Polyoxymethylene Ionomers. Ionic copolymers have been prepared from trioxane and epichlorohydrin, followed by reaction with disodium thioglycolate (76). The ionic forces in these materials dismpt crystalline order and increase melt viscosity (see Acetalresins). 

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