Patent GB-1049091-A (GB)
Title: Catalyst suitable for use in polymerizing epoxy compounds
IPC: C08G65/12
Filed: 1963-06-11
Abstract: Epoxy compounds containing 2-20 carbon atoms are polymerized in the presence of a catalyst which comprises the product of reacting a metal chelate, other than an acetylacetonate, of the formula <FORM:1049091/C3/1> (wherein M is a transition metal from Group IV to VIII which may be attached to one or more oxygen atoms or lower alkoxy groups, D1 and D11, which may be the same or different, are oxygen, sulphur or nitrogen, R is an organic radical and p is an integer of at least 1 and is at most equal to the valency of M) with an organo metallic compound M1R1nXm (wherein M1\h is a metal of Groups I to III, R1 is a lower alkyl group, X is halogen, n is at least 1 and n + m equals the valency of M1), in an inert organic reaction medium under an atmosphere of an inert gas, the molar ratio of the metal chelate to the organo metallic compound being between 1:1 and 1:10.  The preferred transition metals are Ti, V, Cr, Fe, Co, Ni, and Mo.  Numerous chelating agents are specified, including b -keto-acid esters, b -diketones, o-hydroxy-phenyl-carbonyl compounds, b -keto-acid amides, aldehyde imines, oxy-azo compounds, aldoximes, dioximes, phenanthrolines, thiolactic acid, o-amino-benzene thiol and dithiobenzoic acid. The preferred organo-metallic compounds are LiR1, MgR12, ZnR12, AlR13, AlR12X and AlR1X2 where X and R1 are as above, e.g. butyl, lithium, diethyl zinc, triethyl aluminium, diethyl aluminium monochloride and ethyl-aluminium dichloride.  The catalyst is normally prepared by heating the transition metal chelate and organometallic compound together in an inert diluent.  Suitable epoxy compounds which may be polymerized or copolymerized are alkylene oxides, e.g. ethylene oxide, propylene oxide and isobutylene oxide, arylene oxides, e.g. styrene oxide, halogenated alkylene oxides, e.g. epichlorhydrin and b -methyl epichlorhydrin, diene monoepoxides, e.g. butadiene monoxide, saturated and unsaturated glycidyl ethers, e.g. allyl glycidyl ether and octyl glycidyl ether, alicyclic epoxides, e.g. cyclohexane oxide and phenyl glycidyl ethers which may be substituted in the phenyl group by H, halogen, a nitro group or a lower alkyl or aryl group.  Usually the catalyst is used in an amount corresponding to 0.2-10 mol per cent of transition metal chelate based on the epoxy compound.  Example I describes the preparation of a catalyst from triethylaluminium and (a) bis-(salicylaldehyde imine) cobalt (II) and (b) bis-(dimethyl-glyoxime) nickel (II).  In Examples 2-37 epoxy compounds of the types exemplified above are polymerized alone using as catalysts complex compounds prepared from triethyl aluminium and bis-(dibenzoyl methane) Co (II), bis-(salicylaldehyde) Co (II), bis-(salicylaldehyde imine) Co (II), bis-(dimethyl-glyoxime) Ni (II), bis-(salicylaldehyde)-oxy vanadium, tris-(dimethyl glyoxime) Co (III), bis-(salicylaldoxime) Ni (II), bis-(cyclohexane dionedioxime) Ni (II), bis-(a -benzyl dioxime) Ni (II), and bis-(8-hydroxyquinoline) Co (II). In Examples 36-38 phenyl glycidyl ether and epichlorhydrin are copolymerized in the presence of AlEt3/bis-(dimethyl glyoxime) Ni (II) catalyst.  The polymers and copolymers are used to form crystalline films and fibres.  Those derived from phenyl glycidyl ether may be vulcanized or cross-linked.ALSO:The invention comprises a catalyst which is the reaction product of a metal chelate, other than an acetyl acetonate, <FORM:1049091/B1-B2/1> wherein M is a transition metal of Group IV to VIII and which may be attached to 1 or more O atoms of lower alkoxy groups, D1 and D11 are the same or different and are O, N or S, R is an organic radical and f is at least 1 and at most equals the valency of M, with an organo metallic compound M1Rn1 x m, wherein M1 is a metal of Group I to III, R1 is a lower alkyl group, X is halogen and n is at least and n + m equals the valency of M1, the chelate and the organs metallic compounds being reacted in an inert organic medium under an inert atmosphere and in the molar ratio 1:1 to 1:10.  The terms 'lower alkyl' and 'lower alkoxy' are defined as groups having 1-4 carbon atoms.  Specified values of M and Ti, V, Cr, Fe, Co, Ni and Mo, and of M1, Li, Mg, Zn and Al.  A large number of chelating ligands-D1-R-D11-are specified.  The catalysts are used in the polymerization of epoxy compounds to give polyethers.