Reaction of ethylene oxidations

What IS the principal organic product formed in the reaction of ethylene oxide with each of the following ... 

Nonreactive additive flame retardants dominate the flexible urethane foam field. However, auto seating appHcations exist, particularly in Europe, for a reactive polyol for flexible foams, Hoechst-Celanese ExoHt 413, a polyol mixture containing 13% P and 19.5% Cl. The patent beHeved to describe it (114) shows a reaction of ethylene oxide and a prereacted product of tris(2-chloroethyl) phosphate and polyphosphoric acid. An advantage of the reactive flame retardant is avoidance of windshield fogging, which can be caused by vapors from the more volatile additive flame retardants. 

Ethylene glycol can be manufactured by the reaction of ethylene oxide with carbon dioxide to form ethylene carbonate (eq. 17) which can be hydroly2ed to ethylene glycol (eq. 18). 

A variety of substituted alkanolamines (Table 2) can also be made by reaction of oxide with the appropriate amine. Aminoethylethanolamine is made from the reaction of ethylenediamine [107-15-3J and ethylene oxide. Methyldiethanolamine is made from the reaction of ethylene oxide and methylamine [74-89-5J. Diethylethanolamine is made by the reaction of diethylamine [109-87-7] and ethylene oxide. 

Polyall lene Oxide Block Copolymers. The higher alkylene oxides derived from propjiene, butylene, styrene (qv), and cyclohexene react with active oxygens in a manner analogous to the reaction of ethylene oxide. Because the hydrophilic oxygen constitutes a smaller proportion of these molecules, the net effect is that the oxides, unlike ethylene oxide, are hydrophobic. The higher oxides are not used commercially as surfactant raw materials except for minor quantities that are employed as chain terminators in polyoxyethylene surfactants to lower the foaming tendency. The hydrophobic nature of propylene oxide units, —CH(CH2)CH20—, has been utilized in several ways in the manufacture of surfactants. Manufacture, properties, and uses of poly(oxyethylene- (9-oxypropylene) have been reviewed (98). 

Ethylene Cyanohydrin. This cyanohydrin, also known as hydracrylonitnle or glycocyanohydrin [109-78-4] is a straw-colored Hquid miscible with water, acetone, methyl ethyl ketone, and ethanol, and is insoluble in benzene, carbon disulfide, and carbon tetrachloride. Ethylene cyanohydrin differs from the other cyanohydrins discussed here in that it is a P-cyanohydrin. It is formed by the reaction of ethylene oxide with hydrogen cyanide. 

About 60% of the ethylene oxide produced is converted to ethylene glycol by reaction of ethylene oxide ia the presence of excess water and an acidic catalyst at 50—70°C. This is followed by hydrolysis at relatively high temperatures (140—230°C) and 2—4 MPa (20—40 bar) (see Glycols, ethylene glycol). When the water concentration is lowered, poly(ethylene glycol) is obtained. 

Polymerization. The reaction of ethylene oxide with a nucleophile introduces the hydroxyethyl group ... 

With Phenols. The 2-hydroxylethyl aryl ethers are prepared from the reaction of ethylene oxide with phenols at elevated temperatures and pressures (78,79). 2-Phenoxyethyl alcohol is a perfume fixative. The water-soluble alkylphenol ethers of the higher poly(ethylene glycol)s are important surface-active agents. They are made by adding ethylene oxide to the alkylphenol at ca 200°C and 200—250 kPa (>2 atm), using sodium acetate or... 

Many other reactions of ethylene oxide are only of laboratory significance. These iaclude nucleophilic additions of amides, alkaU metal organic compounds, and pyridinyl alcohols (93), and electrophilic reactions with orthoformates, acetals, titanium tetrachloride, sulfenyl chlorides, halo-silanes, and dinitrogen tetroxide (94). 

Ethanolamines. These are produced by the reaction of ethylene oxide and ammonia (see Alkanolamines). Approximately one-third of the production is used in detergents. Other appHcations include natural gas purification, cosmetics, metalworking, textiles, and chemical intermediates (282). 

Glycol Ethers. These are made by reaction of ethylene oxide with various alcohols. They are used for solvents, detergents, brake fluids, and jet fuel deicing. 

Other Derivatives. Ethylene carbonate, made from the reaction of ethylene oxide and carbon dioxide, is used as a solvent. Acrylonitrile (qv) can be made from ethylene oxide via ethylene cyanohydrin however, this route has been entirely supplanted by more economic processes. Urethane intermediates can be produced using both ethylene oxide and propylene oxide in their stmctures (281) (see Urethane polymers). 

Explosion prevention can be practiced by mixing decomposable gases with inert diluents. For example, acetylene can oe made nonexplosive at a pressure of 100 atm (10.1 MPa) by including 14.5 percent water vapor and 8 percent butane (Bodurtha, 1980). One way to prevent the decomposition reaction of ethylene oxide vapor is to use methane gas to blanket the ethylene oxide hquid. 

An entirely different approach was taken by Dale and Daasvatn (see also Sect. 1.4), who isolated 18-crown-6 from a cyclooligomerization reaction of ethylene oxide" . 

Ethylene oxide is a highly active intermediate. It reacts with all compounds that have a labile hydrogen such as water, alcohols, organic acids, and amines. The epoxide ring opens, and a new compound with a hydroxyethyl group is produced. The addition of a hydroxyethyl group increases the water solubility of the resulting compound. Eurther reaction of ethylene oxide produces polyethylene oxide derivatives with increased water solubility. 

We may also be transferred from a point A to a point B in Fig. 21 (or vice versa) by a change in temperature [at Z = const., as appears from (30)]. Thus, a given impurity (at a given concentration) may act as a promoter at one temperature and as a poison at another. This has also been observed experimentally. As an example, we cite the reaction of ethylene oxidation on MgO. CrsOs doped with NasS04, according to the data of Krylov and Margolis (73). 

Graft copolymers of nylon, protein, cellulose, starch, copolymers, or vinyl alcohol have been prepared by the reaction of ethylene oxide with these polymers. Graft copolymers are also produced when styrene is polymerized by Lewis acids in the presence of poly-p-methoxystyrene. The Merrifield synthesis of polypeptides is also based on graft copolymers formed from chloromethaylated PS. Thus, the variety of graft copolymers is great. 

Automobile Antifreeze. Ethylene glycol and diethylene glycol are used as automobile antifreeze, and are produced by the reactions of ethylene oxide with water, as follows ... 

Ethanolamines became available commercially in the early 1930s they assumed steadily growing commercial importance as intermediates after 1945, because of the large-scale production of ethylene oxide. Since the mid-1970s, economical production of very pure, colourless ethanolamines has been possible. Ethanolamines are produced on an industrial scale exclusively by reaction of ethylene oxide (see lARC, 1994) with excess ammonia. This reaction takes place slowly but is accelerated by water. An... 

The propagation reaction of ethylene oxide anionic polymerization has been studied in THF at 20 C with " , " + [222], Cs+ and Cs + [TC] as counterions (10,11). [TC] is a spheroidal macrotricyclic tetramine hexaether (25) which forms a very stable complex with Cs+. 

Eastham and co-workers473 have determined the velocity of the-, reaction of ethylene oxide itself with diothylamine, aniline, and pyridine in aqueous solutions of pH 4-14. The reaction rate oould be expressed by a second-order equation, amine and epoxide terms cadi appearing to the first powor. Kate constants for the various aminos examined were, however, remarkably similar, showing little relation to their structure or basicity. Qualitatively similar trends had been reported previously by Smith and oo-workors.1587 1588... 

Eastham and Derwent474 have also studied the kinetics of the perchloric acid-catalyzed reaction of ethylene oxide with pyridine. In excess of pyridine the rate was found to be dependent on the Conor Titrations of ethylene oxide and perchloric add. Addition of stronger bases,. g. ammonia, triethylamine, or benzylamiae, depressed the vum of cleavage, presumably by competing with ethylene oxide for thr-available proton source, believed to be pyridinium perchlorate in this case. Other acids examined included nitric acid and hydroiodie irireaction rate depended to a certain extent... 

Reactions of ethylene oxide, propylene oxide, and epihromo-hydrin with phosgene Excess of... 

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