Process for preparing polymeric oxetanes using hydrocarbonaluminum chelates as catalysts

摘要

Chelated aluminium compounds of the structure in which R is hydrocarbon, Y is carbon or nitrogen, X is carbon, n is 0, 1 or 2, and Z is an oxygen atom capable of forming a co-ordinating bond with the aluminium, are prepared by contacting a trihydrocarbon aluminium, a dihydrocarbon aluminium hydride, or an alkali metal complex thereof, with a chelating agent and optionally with water. The chelating agent may be a diketone, ketoacid, ketoester, ketoaldehyde, hydroxyketone, hydroxyaldehyde, hydroxyester, dialdehyde, alkoxy acid, ketoxime, aldehyde oxime, hydroxamic acid, dioxime or nitro- or nitroso-compound. The formulae are given of the products of one mole of R3Al or R2AlH with one mole of acetyl acetone, one mole of hydroxyacetone and with one mole of ethoxy acetic acid. The compounds are used as catalysts in the polymerization of oxetanes (see Division C3).ALSO:Polymeric oxetanes, including certain novel homo- and co-polymers having weight average molecular weights of at least about 50,000, are obtained by contacting the monomers with a catalyst which is a chelated reaction product of a trihydrocarbon aluminium, a dihydrocarbon aluminium hydride, an alkali metal aluminium tetrahydrocarbon or an alkali metal aluminium trihydrocarbon hydride, with a chelating agent and optionally with water, the catalyst having the structure in which R is hydrocarbon, Y is carbon or nitrogen, X is carbon, n is 0, 1 or 2, and Z is an oxygen atom capable of forming a coordinating bond with the aluminium. Many examples of oxetanes are given including compounds containing unsaturated groups, halogens and nitrogen-, oxygen- and sulphur-containing groups. They may be copolymerized with each other and/or with three ring-membered epoxy compounds. Examples of the latter include alkylene oxides, epihalohydrins and other halogen-substituted epoxides, unsaturated epoxides, glycidyl ethers and esters and others, e.g. butadiene dioxide. The polymers containing unsaturated groups are elastomers vulcanizable by sulphur. In the catalyst, the hydrocarbon groups of the aluminium compounds may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl or aralkyl. The chelating agent may be a diketone, ketoacid, ketoester, ketoaldehyde, hydroxyketone, hydroxyalkehyde, hydroxy ester, dialdehyde, alkoxy acid, ketoxime, aldehyde oxime, hydroxamic acid, dioxime, or nitro- or nitroso-compound. Typical examples describe the polymerization of 3,3-bis-(chloromethyl) oxetane and unsubstituted oxetane, and the copolymerization of oxetane with alkyl glycidyl ether with and without propylene oxide, of 3,3-bis-(chloromethy)oxetene with propylene oxide, and of oxetane with epichlorohydrin, and the vulcanization of some of the copolymers. Typical catalysts are the chelates of triethyl aluminium of tri-isobutyl aluminium with 2,4-pentane-dione, with and without water.