Improvements in or relating to a process for preparing polyethers

摘要

Monooxirane compounds are polymerized with a catalyst formed from (1) trialkylaluminium and/or a dialkylaluminium hydride and (2) 0.1 to 1.0 moles of water per mole of (1), and (3) 0.01 to 1.2 moles of a chelating agent per mole of (1), and (4) 0.5 to 1.5 moles of a modifying agent, which is an alcohol, phenol or hydrogen halide, per mole of (1). Suitable oxiranes include alkylene oxides, haloalkylene oxides, cycloaliphatic epoxides, epoxy ethers, glycidyl esters, and ethylonically unsaturated epoxides, both separately and in admixture. The polymerization is preferably carried out in the presence of an inert diluent. Suitable trialkylaluminium compounds are trimethylaluminium, triethylaluminium, triisobutyl aluminium, tri-n-butylaluminium, trioctylaluminium, and suitable dialkylaluminium hydrides are diethylaluminium hydride and diisobutylaluminium hydride. Chelating agents mentioned are the diketones, keto- and aldooximes, dioximes, and the dicarboxylic acids and their mono- and diesters. Alcohols which may be used as modifying agents include aliphatic, cycloaliphatic, aralkyl and polyhydric alcohols. In the examples, the polymers are also stabilized by addition of phenyl-b -naphthylamine or 4,41 - thiobis - (6 - tert - butyl - m -cresol). In Examples 1-42, the catalyst system used was trithyl aluminium, water and acetylacetone, with the following modifying agents: methanol (2, 3, 4, 5, 20, 21, 40, 42), /sB-butanol (7, 23, 24, 25), 2-octanol (8, 26, 27), borneol (9, 32), a -fenchylalcohol (10, 31), a -terpineol (11, 29), menthol (12,30), di-t-butyl-p-cresol (13,34), phenol (14), HCl (15, 35), HF (16, 36), HI (17, 18, 37, 38), isopropanol (22), cyclohexanol (28), trans - 1,2 - cyclohexanediol (33). The catalyst mixture used in the remaining examples was as follows tri-n-butylaluminium, water, dimethylglyoxime and t-butanol (43), tri-i-butylaluminium, water, 2,3-butanedionemonooxime, cyclohexanol (44), di-i-butylaluminium hydride, water, diethylmalonate, a -terpineol (45), and triethylaluminium, water, acetylacetone, borneol (46 and 47). The epoxides used were propylene oxide (1-18), cis-butene-2-oxide (19-38), a mixture of propylene oxide and allyl phenylglycidyl ether (39, 40), a mixture of propylene oxide and allyl glycidyl ether (41, 42) ethylene oxide (43, 44, 45) epichlorohydrin (46) and a mixture of epichlorohydrin and ethylene oxide (47).ALSO:A catalyst comprises (1) trialkyl aluminium and/or a dialkyl aluminium hydride and (2) .1 to 1.0 moles of water per mole of (1), and (3) .01 to 1.2 moles of a chelating agent per mole of (1), and (4) .5 to 1.5 moles of a modifying agent, which is an alcohol, phenol, or hydrogen halide, per mole of (1). Suitable chelating agents are diketones, keto- and aldooximes, dioximes, and the dicarboxylic acids and their mono- and diesters. Alcohols which may be used as modifying agents include aliphatic, cycloaliphatic, aralkyl and polyhydric alcohols. The catalysts are used for polymerising mono-oxirane compounds. In the examples, (1-42) the catalyst system used was triethyl aluminium/water/acetylacetone, with the following modifiers:-methanol (2-5, 20, 21, 40, 42) /sB-butanol (7, 23-25), 2-octanol (8, 26, 27), bomeol (9, 32), a -fenchyl alcohol (10, 31), a -terpineol (11, 29), menthol (12, 30), di-t-butyl-p-cresol (13, 34), phenol (14), H Cl (15, 35), HF (16, 36), HI (17, 18, 37, 38), isopropanol (22), cyclohexanol (28), and trans-1,2-cyclohexanediol (33). The catalyst mixtures used in the remaining examples were as follows:-tri-n-butyl aluminium/water/dimethyl glyoxime//sB-butanol (43), tri-i-butyl-aluminium/water/2,3-butane dione monooxime/cyclohexanol (44), di-i-butyl aluminium hydride/water/ diethyl malonate/a -terpineol (45), and triethyl aluminium/water/acetylacetone/bomeol (46 and 47).