Patent GB-957391-A (GB)
Title: Improvements in or relating to polymerization of epoxides
IPC: C08G65/12
Filed: 1962-06-27
Abstract: Epoxides are polymerised in presence of a catalyst formed by reacting an aluminium compound having the formula AlR3, wherein each R may be the same or different and represents a hydrogen atom or a hydrocarbon radical, at least one R being hydrocarbon, with a nitrogen containing compound consisting of NH3 or an organic basic nitro-containing compound wherein any active hydrogen is attached to the nitrogen, the molar ratio of nitrogen to aluminium being in the range 0.01:1 to 0.95:1. In addition, water may be added to the aluminium compound at the time of, or subsequent to the addition of nitrogen containing compound. The process, which may be batchwise or continuous, is preferably carried out at -80 DEG C. to +150 DEG C. and the amount of catalyst compound used is 0.2 to 100 mole per cent based on the monomer used. Specified monomers which may be homopolymerised or copolymerised include ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-hexene oxide, cyclohexene oxide, styrene oxide, glycidyl ethers of phenol and of bis-phenol vinyl cyclohexene mono and dioxides, butadiene monoxide, allyl glycidyl ether, epichlorohydrin, epibromohydrin; epifluorohydrin, trifluoromethylethylene oxide, perfluoropropylene oxide and perfluoroethylene oxide. Hydrocarbon aluminium compounds used include triethyl aluminium, tripropylaluminium, tri-n-butylaluminium, tri isobutylaluminium, trihexyl aluminium, trioctylaluminium, diethylaluminium hydride; diisobutyl aluminium hydride, or any mixture of these aluminium compounds and the corresponding alkenyl, cycloalkyl, cycloalkenyl, aryl and aralkyl aluminium compounds, e.g. triisoprenylaluminium, tricyclohexylaluminium, tricyclohexenylaluminium, triphenylaluminium and tribenzylaluminium. Specified nitrogen containing compounds are acetamide, succinimide, NH3, saturated and unsaturated aliphatic, alicyclic, heterocyclic or aromatic primary, secondary and tertiary amines, monoamines or diamines.  Other amides specified include aliphatic, cycloaliphatic and aromatic amides which may be N-mono or disubstituted amides, amidines, imides, imines, cyclic imines, hydrazine, alkyl hydrazine or ureas. Examples given are ethyl amine, butylamine, diethylamine, triethylamine, tributylamine, diethylene triamine, triethylene diamine, cyclohexylamine, pyridine, piperidine, morpholine, 2-6 dimethylmorpholine, N-methyl pyrrolidine, N-methylmorpholine, quinoline, o-phenanthroline; formamide, dimethylformamide, acetamide; benzamidine, succinimide, maleimide, phthalimide, ethylenimine, hexamethylenimine, urea, methylurea, dimethyl urea, diethylurea, and dibutylurea. The catalyst may be formed by adding the amine to a hydrocarbon solution of the aluminium compound or may be prepared in situ by addition of the catalyst components separately or simultaneously to the monomer solution.  Inert diluents are ether and hydrocarbons.  Additives such as antioxidants, C black, zinc stearate, sulphur, accelerators and curing agents may be present during polymerization.  Examples describe the polymerization of ethylene oxide, propylene oxide, epichlorohydrin and the copolymerization of (a) propylene oxide and allylglycidyl ether and (b) propylene-oxide and epichlorohydrin.ALSO:A catalyst, formed by reacting an aluminium compound having the formula AlR3, wherein each R may be the same or different and represents a hydrogen atom or a hydrocarbon radical, at least one R being hydrocarbon, with a nitrogen-containing compound consisting of NH3 or an organic basic nitrogen-containing compound wherein any active hydrogen is attached to the nitrogen, the molar ratio of nitrogen to aluminium being in the range 0,01 : 1 to 0,95 : 1, is used in the polymerization of epoxides (see Division C3).  In addition, water may be added to the aluminium compound, at the time of, or subsequent to, the addition of the nitrogen-containing compound.  Specified nitrogen-containing compounds are acetamide, succinimide, NH3, saturated and unsaturated aliphatic, alicyclic, heterocyclic or aromatic primary, secondary and tertiary amines, monoamines and diamines. In addition aliphatic, cycloaliphatic and aromatic amides, amidines, imides, imines, cyclic imines, hydrazine, alkyl hydrazine and ureas are used.  The catalyst may be formed by adding the amine to a hydrocarbon solution of the aluminium compound or may be prepared in situ by addition of the catalyst components separately or simultaneously to the monomer solution. Inert diluents are ether and hydrocarbons.  In examples, the catalyst mixtures used in varying mole ratios are mixtures of (a) triisobutyl aluminium with triethylamine, N-methyl morpholine, triethylene diamine, N-methylpyrrolidine, pyridine, piperidene, diethylamine, 2,6-di-methylmorpholine, dimethylformamide, phthalimide, 1-1-dibutyl urea, n-butylamine or o-phenanthroline; (b) triethyl aluminium with morpholine and 2-6-dimethyl morpholine; and (c) diisobutyl aluminium hydride and ammonia.