Patent GB-975368-A (GB)
IPC: C08G63/46
Filed: 1962-05-23
Abstract: Acid derivatives are produced by reacting approximately equivalent amounts of acid mono-or di-halides with hydroxy, carboxy or peroxy compounds in the presence of water, an amount of an alkali metal or alkaline earth metal hydroxide or carbonate which is at least chemically equivalent to the amount of hydrogen halide formed during the reaction and a catalytic amount of a tertiary amine or quaternary ammonium compound thereof, the amine being characterized in that it has a pK6 value below 8, it reduces the interfacial tension between methylene chloride and water at 20 DEG C. by at least 20% with a content of 0.0025 mol of amine in 1000 ml. of methylene chloride and its tertiary nitrogen atom is not sterically hindered. Preferred tertiary amines have the formula R4-N(R5)-R6 wherein at least one of the substituents R4, R5 and R6 signifies an o -hydroxyalkyl, o -hydroxyalkyl ether or o -hydroxyalkyl polyether group, the alkyl radical of which can be substituted, and the other substituents are unsubstituted or substituted alkyl, cycloalkyl, aralkyl or arylcycloalkyl radicals, or their quaternary ammonium compounds. For example, the reaction products of N,N-dimethyl ethanolamine, di-isopropylamine, di-isobutylamine, N-methyl stearylamine, N-methyl cyclohexylamine or piperidine with ethylene oxide and/or propylene oxide; the reaction products of triethanolamine with ethylene oxide; and the reaction products of di-isobutylamine with styrene oxide and ethylene oxide.  Other suitable tertiary amines specified are N,N-dimethyl -ndodecylamine, N,N-dimethyl -n-stearylamine, N,N-dimethylaminocaproic acid stearylamide, N,N-dimethylaminocaproic acid dodecylamide, N,N-dimethyl amino undecanic acid stearylamide, N-methyl-di-n-octylamine and N-methyl-di-n-stearylamine.  Quaternary ammonium compounds specified are trimethyldodecyl-, trimethyl octadecyl-, didodecyl-dimethyl- and N,N-dimethyl-N-octyl-ethanol ammonium chlorides. Acid derivatives which can be produced by the process include carboxylic acid esters, carboxylic acid anhydrides and mixed carboxylic acid-carbonic acid mono-ester anhydrides by the reaction of carboxylic acid halides with alcohols or phenols, carboxylic acids and carbonic acid monoesters, respectively; carbonic acid diesters, mixed carboxylic acid-carbonic acid monoester anhydrides and pyroacrbonic acid esters by the reaction of carbonic acid monoester halides with alcohols or phenols, carboxylic acids and carbonic acid monoesters, respectively; carbonic acid diesters from carbonic acid dihalides and alcohols or phenols; and carboxylic acid peresters from carboxylic acid halides and alkyl or aralkyl hydroperoxides. Specifications 808,490 and 975,367 are referred to.ALSO:Polycarbonates are prepared by reacting phosgene with dihydroxy compounds in the presence of water, an amount of an alkali metal or alkaline earth metal hydroxide or carbonate which is at least chemically equivalent to the amount of hydrogen chloride formed during the reaction and a catalytic amount of a tertiary amine or quaternary ammonium compound thereof, the amine being characterized in that it has a pK6 value below 8, it reduces the interfacial tension between methylene chloride and water at 20 DEG C. by at least 20% with a content of 0.0025 mol of amine in 1000 ml of methylene chloride and its tertiary nitrogen atom is not sterically hindered. Preferred tertiary amines have the formula R4-N(R5)-R6 wherein at least one of the substituents R4, R5 and R6 signifies an o -hydroxyalkyl, o -hydroxyalkyl ether or o -hydroxyalkyl polyether group, the alkyl radical of which can be substituted, and the other substituents are unsubstituted or substituted alkyl, cycloalkyl, aralkyl or arylcycloalkyl radicals, or their quaternary ammonium compounds. For example, the reaction products of N,N-dimethyl ethanolamine, di-isopropylamine, diisobutylamine, N-methyl stearylamine, N-methyl cyclohexylamine or piperidine with ethylene oxide and/or propylene oxide; the reaction products of triethanolamine with ethylene oxide; and the reaction products of di-isobutylamine with styrene oxide and ethylene oxide. Other suitable tertiary amines specified are N,N-dimethyl -ndodecylamine, N,N-dimethyl -n-stearylamine, N,N-dimethylaminocaproic acid stearylamide, N,-N-dimethyl aminocaproic acid dodecylamide, N,N-dimethyl aminoundecanic acid stearylamide, N-methyl-di-n-octylamine and N-methyl-di-n-stearylamine.  Quaternary ammonium compounds specified are trimethyldodecyl-, trimethyl-octadecyl-, didodecyl-di-methyl- and N,N-dimethyl -N- octyl-ethanol ammonium chlorides. In Example 6 a polycarbonate is prepared by reacting phosgene with 2,2-(4,4 1-dihydroxy-diphenyl)-propane in the presence of water, methylene chloride, sodium hydroxide and ethoxylated N-methyl-stearylamine. Specifications 808,490 and 975,367 are referred to.