Glycol, tertiary ethers

Polyglycol ethers. See Glycol, Monophenyl-ether of and Glycol, Tertiary ethers of in Vol 6, G116... 

In the absence of basic catalyst and in the presence of anhydrous excess alcohol the mono adducts are obtained in good yields [37,38]. For example, ethanol is reacted with ethylene oxide to give ethylene glycol monoethyl ether [37,38]. The mono adducts are also obtained by the use of acid catalysts such as BF3 etherate in the addition of ethylene oxide to primary, secondary, and tertiary alcohols [39]. Some typical examples are described in Table II. 

Table 11.57 DIpropylene Glycol Tertiary Butyl Ether (70)...

Anionic polymerizations are initiated in polar systems by bases and Lewis bases. For example, alkali metals, alcoholates, metal ketyls, metal alkyls, amines, phosphines, and Grignard compounds act as initiators. However, the polymerization mechanism does not depend on the nature of the initiator alone. For example, tertiary amines and phosphines do not only initiate anionic polymerizations under certain conditions, they can also initiate zwitterion polymerizations. In addition, polyinsertions can proceed in less polar systems. Thus, anionic polymerizations are often carried out in polar solvents. Ethers and nitrogen compounds, such as tetrahydrofuran, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), pyridine, and ammonia are most commonly used. 

DPtB Dipropylene glycol tertiary butyl ether... 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

A change from an aliphatic or aromatic hydrocarbon solvent (cyclohexane, benzene) to a polar solvent (THF) leads to a large increase in trans-1,4 and 3,4 microstructure (58). Organolithium compounds are highly associated sec-butyllithium in benzene or cyclohexane exists as a tetramer, and -butyllithium as a hexamer (64,65). This association in hydrocarbon solvents results pardy in the slow initiation observed between some organolitbiirms and isoprene (66). At low initiator concentrations, the polymerization rate of isoprene in alkyUithium polymerization is proportional to monomer and alkyUithium concentrations (67). 3,4-Polyisoprenes are obtained by modification of the lithium polymerization with ethers, such as the dialky] ethers of ethylene glycol or tertiary amines (68,69). 

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