Patent GB-949848-A (GB)
Title: Metal chelate containing polymers
Inventor: THORNTON DAVID ARTHUR
IPC: C08G79/00
Filed: 1960-10-18
Abstract: Bis (a -keto-oximes) or bis (1,2-dioximes) of formula: <FORM:0949848/C2/1> where R is an alkyl group, Z1 and Z2 either both represent an oximino group >NOH or Z1 represent an oximino group and Z2 represents an oxygen atom, and X represents a group of formula: <FORM:0949848/C2/2> where Y is a single bond, an oxygen atom, or a methylene or polymethylene group are made by the following series of reactions:-(1) A compound of formula: <FORM:0949848/C2/3> is reacted with a chloride or an anhydride of an acid of formula: <FORM:0949848/C2/4> in the presence of a Lewis acid catalyst to yield a product of formula: <FORM:0949848/C2/5> (2) This product is nitrosated, e.g. by reaction with (a) an inorganic nitrite and an acid, (b) nitrosyl chloride, (c) an alkyl nitrite in the presence of an alkali metal alkoxide or (d) an alkyl nitrite in the presence of hydrogen chloride; whereby bis (a -keto-oximes) are produced, (3) These bis (a -keto-oximes) are possibly reacted with hydroxylamine hydrochloride to produce bis (1,2-dioximes).  In examples, (A) a , b -bis[p-(2-oximinopropionyl) phenyl] ethane is made by reacting 4, 41-dipropionyldibenzyl with n-butyl nitrite in dry chloroform whilst passing hydrogen chloride through the reaction mixture; (B), (C), (D), (E) and (L); bis [p-(2-oximinopropionyl) phenyl] ether, bis [p-(2-oximinopropionyl) phenyl] methane, a , g - bis [p-(2-oximinopropionyl) phenyl] propane p, p1-bis (2-oximinopropionyl) diphenyl and 1, 4-dibenzoyl-1, 4-dioximinobutane are similarly prepared; (F) a , b -bis [p-(1, 2-dioximinopropyl) phenyl] ethane is made by reacting hydroxylamine hydrochloride dissolved in water with the product of Example (A) in methanol; (G), (H), (I), (J) and (K) bis [p-(1,2-dioximinopropyl) phenyl] ether, bis [p-(1,2-dioximinopropyl) phenyl] methane, a , g - bis [p-(1,2-dioximinopropyl) phenyl] propane, p, p1-bis (1,2-dioximinopropyl) diphenyl and 1, 6-diphenyl-tetra-oximinohexane are similarly prepared.  The oximes are reacted with metal salts to yield polymeric co-ordination compound (see Division C3).ALSO:The invention comprises polymeric co-ordination compounds containing recurring units of formula: <FORM:0949848/C3/1> or of formula: <FORM:0949848/C3/2> where M represents an atom of a metal which is capable of forming a chelate structure with a ligand containing an oximino group, R is an alkyl group and X is a group of formula: <FORM:0949848/C3/3> where Y represents a single bond or an atom of oxygen or a methylene or polymethylene group. The polymers are made by reacting a salt (e.g. the acetate) of the metal M with a bis-(a -ketooxime) or a bis-(1,2-dioxime) of formula: <FORM:0949848/C3/4> where Z1 and Z2 either both represent the oximino group >NOH or Z1 represents the oximino group and Z2 represents an oxygen atom, and X represents a group of formula III. Suitable metal ions are Ni11, Co11, Fe11, Pb11 and Cu11. The terminal oxime groups of the polymers may be reacted with epichlorhydrin (e.g. in aqueous sodium hydroxide solution) to form epoxy resins.  The epoxy resins may be hardened by aliphatic or aromatic primary, secondary or tertiary amines (including Mannich bases), amino-alcohols, guanidine, phenylguanidine, dicyandiamide, aniline-formaldehyde resins, polyaminostyrenes and polyamides derived from polymeric fat acids. The curable composition may also contain a mono- or poly-glycidyl ether of a mono- or poly-hydric alcohol or phenol, a polyglycidyl ester of a polycarboxylic acid, or the dehydrohalogenation product of the reaction product of epichlorhydrin with a primary or secondary amine.  Fillers, plasticisers or colouring agents may also be added.