Patent GB-898306-A (GB)
Title: Improvements in or relating to polymerization of epoxy compounds
IPC: C08G65/12
Filed: 1959-05-29
Abstract: 898,306. Polymers of epoxides. HERCULES POWDER CO. May 29, 1959 [May 29, 1958(8); May 11, 1959(2)], No. 18425/59. Class 2(5) New, high molecular weight polymers of epoxides are among those obtained by polymerizing one or more mono- or poly-epoxides using as catalyst a reaction product of an organoaluminium compound with a chelating agent and/or water. The new products are: (I) amorphous poly(epihalohydrin) having reduced specific viscosities of at least about 0À5 as measured on a 0À1% solution in α-chloronaphthalene at 100‹C.; (2) a solid rubber-like copolymer of an epihalohydrin and an ethylenically unsaturated epoxide; (3) a crystalline polymer of 2,3-epoxybutane; (4) an amorphous rubber-like copolymer of an epihalohydrin and an alkylene oxide; (5) a crystalline polymer of styrene oxide having an RSV of at least 0À4 measured at 135‹C.; (6) a solid polymer of allyl glycidyl ether, polymerization having occurred only through the epoxy groups; and (7) a water-insoluble, rubber-like copolymer of allyl glycidyl ether and an alkylene oxide. Many of these may be cross-linked or vulcanized. The preferred organoaluminium compounds are the trialkyls, tricycloalkyls and triaryls, the alkyl hydrides, halides, alkoxides and aroxides, and their complexes, e.g. with alkali metals or tetrahydrofuran. The chelating agent has two functional groups, one being OH or SH, the other containing oxygen, nitrogen or sulphur which forms a co-ordinate bond with the aluminium. Examples are diketones, e.g. acetylacetone, trifluoroacetyl acetone, acetonyl acetone, benzoyl acetone, furoyl acetone, thenoyl trifluoroacetone, dibenzoyl methane, 3-methyl- and 3-benzyl-2,4-pentane dione; ketoacids, e.g. acetoacetic acid; ketoesters, e.g. ethyl acetoacetate; ketoaldehydes, e.g. formylacetone; hydroxy ketones, e.g. hydroxyethyl methyl ketone, hydroxyacetone, ohydroxyacetophenone, 2,5-dihydroxy-p-benzoquinone; hydroxyaldehydes; e.g. salicylaldehyde; hydroxyesters, e.g. ethyl glycollate; dicarboxylic acids and esters; dialdehydes, e.g. malonaldehyde; alkoxy acids; ketoximes, e.g. 2,3-butanedione-monoxime; dialdehyde monoximes; hydroxamic acids; dioximes; nitro compounds, e.g. 1,3-nitroalcohols and nitroketones, 2-nitroacetic acid, 1,2-nitroso-oximes; bis(1,3-diketones), bis(1,2-ketoximes), bis(1,2-dioximes). If used alone, the mol. ratio of chelating agent to aluminium compound is 0À1:1 to 2:1; if used with water, the mol. ratio is 0À1:1 to 1À5:1 and H 2 O to Al compound is 0À1:1 to 1À5:1. If water is used alone, the mol. ratio is 0À1:1 to 1À5:1. Reaction with water may be effected at any stage, including in situ with the epoxide. Some of the reaction products of aluminium compound and water are believed to be of the formula R 2 Al-O-AlR 2  and [-Al(R)O-] n . Polymerization may be carried out in an inert diluent, e.g. ethers, hydrocarbons and halohydrocarbons, and temperatures may be from -80‹ to 250‹C. Many epoxides are specified, including alkylene oxides, halo-substituted alkylene oxides, cycloaliphatic mono- and di-oxides, glycidyl ethers and esters, diene mono- and di-oxides, epoxy stearates and epoxy amino and ammonium compounds. The polymers of epihalohydrins may be cross-linked with polyamines or their salts, together with conventional, vulcanization additives, e.g. carbon black, silica &c. A dithiocarbamate may be added to the polyamine. The polymers derived from unsaturated compounds may be vulcanized by the standard rubber methods, or, when they are copolymers with epihalohydrins, by the above methods. Uses: Lubricating oil and wax additives, caulking compounds, adhesives, gaskets, hoses, films, fibres and coatings.