Sodium reaction with ethylene

The polymerization iavolves the reaction of sodium polysulftde with ethylene dichloride ia aqueous media at 70°C for 2—6 h, yielding an aqueous dispersion (latex) of the polysulftde mbber. 

Glycol/water mixture leaks from jacket into blender, reacts with aluminum powder and sodium hydrosulfite, and initiates exothermic decomposition No—N2 atmosphere, confinement in blender R NOAA Worksheet indicates combining sodium hydrosulfite with ethylene glycol is "explosive due to vigorous reaction or reaction products may produce detonation," "may cause fire," and indicates "flammable gas generation" and "heat generation by chemical reaction, may cause pressurization"... 

These catalysts require temperatures above 100° and usually 150-200° for reasonable rates. Alkylsodium compounds at their decomposition temperatures (50-90°) have also been used by Pines and Haag (9). Lithium reacted with ethylene diamine has also been reported by Reggel et al. (4) as a catalyst for this reaction. The homogeneous system thus formed seems to lower the temperature requirement to 100° (4), whereas the use of potassium amide in liquid ammonia requires 120° (S). Sodium reacted with ethylene diamine has been reported to be an ineffective catalyst (4)- The most active catalyst systems reported so far are high-surface alkali metals and activated-alumina supports. They are very effective at or near room temperature (10-12). 

And 4-alkylpyridines undergo reaction with ethylene under pressure at 140-1500 in the presence of sodium to form the corresponding 2-n-propyl- and (3-pentyl)-2- and 4-pyridines. Yields of 6-94 of monoethylated products are obtained from higher 2- and 4-alkylpyridines (28). The relative ethylation of 4-alkylpyridines is 3. 5 to 7.0 times greater than that of 2-alkylpyridines, and is associated with greater acidity of the 4 over the 2 isomers. 

Electron-transfer to monomer is not the only mode of initiation by radical-anions, although it is unique for non-polar monomers. With some polar monomers, especially cyclic ones, the initiation resembles protonation. For example, the reaction of sodium naphthalenide with ethylene oxide follows the route (9)... 

The ether content and the viscosity of the product are controlled by controlling the reaction conditions. In some cases, cellulose ethers are made by reacting sodium cellulose with ethylene or propylene oxide to yield the corresponding hydroxyalkyl ether. Such hydroxy-terminated cellulose ethers are of considerable interest. 

Despite the very early claims for its preparation, 9S3 eluded synthesis until 1977, when Ochrymowycz and coworkers prepared it in heartbreakingly low yield (0.04%) from the reaction of ethylene chloride with sodium 3-thiapentane-l,5-dithiolate in EtOH (Table 4) [11]. Subsequently, Glass and coworkers [62] improved the yield to 4.4% through use of BzMe3N OMe to deprotonate 3-thiapentane-1,5-dithiol for reaction with ethylene chloride (Table 4). Application of the cesium carbonate procedure (for the same reactants in DMF) affords 9S3 in 50% yield [59]. Sublimation of ligand from the crude reaction mixture greatly facilitates the isolation of what historically has been the most elusive of all the crown... 

Reaction of sodium hydrazide with ethylene derivatives Addition and hydrazinolysis Hydrazines, hydrazones, and hydrocarbons ... 

Another way of making this type of organic silicate is to add (HOC,H ),N OH to a solution of 3.75 1.0 ratio sodium silicate and then remove the sodium by ion exchange with (HOC2H4)4N ions on a cation-exchange resin. The mixture at first gels, but then forms a viscous solution. An alternative is to prepare a dilute solution of ethanolamine and silica in this way and then form the quaternary ammonium salt by reaction with ethylene oxide (130). Diethanol ammonium and morpholinium silicate and related salts have also been prepared (131). 

Partial esters of sorbitans with fatty acids can be modified by reaction with ethylene oxide (under pressure, at elevated temperatures and in the presence of sodium ethoxide or other catalysts), which yields a mixture of products substituted to varying degrees... 

Soon after the invention of the Wacicer process, the formation of vinyl acetate by the reaction of ethylene with PdCh in AcOH in the presence of sodium acetate was reported[106,107]. No reaction takes place in the absence of base. The reaction of Pd(OAc)T with ethylene forms vinyl acetate. 

Raw Material. PVA is synthesized from acetjiene [74-86-2] or ethylene [74-85-1] by reaction with acetic acid (and oxygen in the case of ethylene), in the presence of a catalyst such as zinc acetate, to form vinyl acetate [108-05-4] which is then polymerized in methanol. The polymer obtained is subjected to methanolysis with sodium hydroxide, whereby PVA precipitates from the methanol solution. 

The chain-growth catalyst is prepared by dissolving two moles of nickel chloride per mole of bidentate ligand (BDL) (diphenylphosphinobenzoic acid in 1,4-butanediol). The mixture is pressurized with ethylene to 8.8 MPa (87 atm) at 40°C. Boron hydride, probably in the form of sodium borohydride, is added at a molar ratio of two borohydrides per one atom of nickel. The nickel concentration is 0.001—0.005%. The 1,4-butanediol is used to solvent-extract the nickel catalyst after the reaction. 

V-Alkylation can also be carried out with the appropriate alkyl haUde or alkyl sulfate. Reaction of aniline with ethylene, in the presence of metallic sodium supported on an inert carrier such as carbon or alumina, at high temperature and pressure yields V/-ethyl- or /V,/V-diethylaniline (11). At pressures below 10 MPa (100 atm), the monosubstituted product predominates. 

Diphenylamine can be alkylated exclusively in the ortho positions by reacting with an olefin in the presence of aluminum diphenylamide (7), which can be readily obtained by heating DPA with powdered aluminum, or more easily by treating sodium diphenylamide with AIQ. - Ethylene is more reactive than propylene, which in turn is more reactive than isobutylene. Eor a typical reaction, a small amount of the amide is generated in a DPA melt and ethylene is introduced under pressure (5 —30 MPa) at 200—400°C. The absorption of ethylene stops after about 30 min and 2,2 -diethyldiphenylamine is obtained in 95% yield. With propylene only a 25% yield of the 2,2 -diisopropyldiphenylamine is obtained. 

A provocative reaction of ethylene glycol direcdy with siUcon dioxide that leads to a complex mixture of oligomeric and cycHc ester species has been reported (32). This reaction proceeds in the presence of sodium hydroxide or in the presence of high boiling tertiary amines (33). 

Passing a stream of nitrogen at 95—100°C through a reaction mixture of ethyl ether and 30 wt % oleum prepared at 15°C results in the entrainment of diethyl sulfate. Continuous operation provides a >50% yield (96). The most economical process for the manufacture of diethyl sulfate starts with ethylene and 96 wt % sulfuric acid heated at 60°C. The resulting mixture of 43 wt % diethyl sulfate, 45 wt % ethyl hydrogen sulfate, and 12 wt % sulfuric acid is heated with anhydrous sodium sulfate under vacuum, and diethyl sulfate is obtained in 86% yield the commercial product is >99% pure (97). 

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... 

Dinitroiodobenzene has been prepared by the nitration of 0- or /)-nitroiodobenzene, by treatment of 2,4-dinitrobenzenedi-azonium sulfate with potassium iodide, and by the reaction of sodium iodide with 2,4-dinitrochlorobenzene in refluxing ethylene glycol. The present procedure is a modification of the last-mentioned one. 

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