Patent GB-791325-A (GB)
Title: Improvements in or relating to chelates and compositions containing the same
IPC: D06M13/332
Filed: 1954-09-01
Abstract: Solutions which may be dried to form films contain (a) an organic polyligand having m chelating structures in its molecule and (b) a chelate compound of a volatile chelating agent with a metal of valency n, wherein m and n are greater than 1 and together total at least 5.  A volatile chelating agent is defined as one boiling below 300 DEG  C. at 760 mm. press.  Some examples are acetylacetone, ethyl acetoacetate, 3-methyl-2,4-pentanedione, trifluoroacetylacetone, 2 - furoylacetone, 2 - thenoylacetone, salicyladehyde and methyl salicylate.  Any known polyvalent chelating metal may be employed. Most of them are mentioned. Any known chelating structure may be present in the polyligand. Many are listed.  Some of the polygligands mentioned are triethylenetetramine, glycylglycine, ethylenediamine N,N1-diacetic acid, tetramethylenediamine N,N, N1,N1 - tetracetic acid, b ,b ,b 1,b 1 - tetracetyldiethylbenzene, gluconic acid, tartaric acid, methane bis thioglycollic acid, methane bis salicylaldehyde, ethylene glycoldibenzoyl acetate, glyceryltriacetoacetate, polymeric 1,2-dioximes or 1,2-keto-oximes, condensates of salicylaldehyde with polymeric primary amines, polyethylenimine, polymeric alkyl 3-keto-4-pentenoates, b -ketoacylates of hydrolysed ethylene/vinyl acetate copolymers, b -ketoacylates of polyvinyl alcohol and polymers and copolymers of vinyl salicylate, p-acetoacetylstyrene or acrylylacetone. Particularly useful polyligands which form the subject of Specification 791,326 are b -ketomonocarboxylates of partial or complete esters of polyhydric alcohols with hydroxy acids, and b -ketomonocarboxylates of hydroxylcontaining polyester resins. Many examples of these preferred polyligands or of substances which may be used to prepare them are listed.  The film-forming solutions may contain aqueous or non-aqueous solvents especially when the polyligand is polymeric.  Many possible solvents are mentioned. Chelates which may be in the form of films are formed on air-drying or baking the solutions.  The products are useful for coating or impregnating compositions which may include conventional additions, e.g. zinc oxide, titanium oxide as pigments or magnesium silicate as extender.  In the examples: (I) polyallylacetoacetate (prepared from polyallal alcohol and ethyl acetoacetate or by polymerization of allyl acetoacetate) was mixed, in presence of toluene with or without ethanol or butanol, with bis-(methyl salicylate) beryllium, tris-(methyl salicylate) aluminium, bis-(butyl acetoacetate) copper, tris-(2.4-pentanediono) iron, bis-(ethylacetoacetato) beryllium, or tris-(ethyl acetoacetato) aluminium and films were cast from the solutions.  (II) The polyligand was a product prepared by heating ethyl acetoacete with a castor oil modified polyglyceryl phthalate. Many chelates with various metals and various volatile chelating agents are employed in this and subsequent examples to form films with the different polyligands described.  (III) and (IV) are similar using the polyacetoacetate of a coconut oil modified glycerol phthalate resin.  (V) The polyacetoacetate of a coconut oil modified polypentaerythrityl phthalate was employed as polyligand.  (VI) uses the polyacetoacetate of a hydrogenated castor oil polyglyceryl phthalate as polyligand.  (VII) The polyligand was prepared from a castor oil modified glycerol phthalate polyester reacted with diketen.  (VIII) Castor oil modified glycerol phthalate resin was reacted with ethyl trifluoroacetoacetate to form the polyligand. Other polyligands whose use is exemplified are: (IX) the product from a coconut oil modified pentaerythrityl phthalate and ethyl trifluoroacetate. (X) A benzoylacetate of a castor oil modified glyceryl phthalate. (XI) and (XII) The tris-acetoacetate of castor oil.  (XIII) Pentaerythrityl tetra-acetoacetate.  (XIV) A mixture of castor oil acetoacetate and pentaerythritol tetra-acetoacetate.  (XV) A mixed glyceryl ester of acetoacetic acid and of 12-acetoacetoxyoleic acid.  (XVI) A polymer with the recurring unit: <FORM:0791325/IV (a)/1> prepared by nitrosating an ethylene-carbon monoxide copolymer. (XVII) A polymer with the recurring unit: <FORM:0791325/IV (a)/2> prepared by reacting a nitrosated ethylenecarbon monoxide copolymer with hydroxylamine.  (XVIII) A polymer with the recurring unit: <FORM:0791325/IV (a)/3> prepared from salicylaldehyde and a polymer obtained by reductive amination of an ethylene-carbon monoxide copolymer.  (XIX) A vinyl acetate-vinyl salicylate copolymer.  (XX) A product obtained by refluxing a solution of a styrene-methyl acrylate copolymer with sodio acetone. (XXI) A polymer prepared by ester interchange between ethyl acetoacetate and a hydrolysed copolymer of ethylene and vinyl acetate.  Specifications 720,176 and 734,114 also are referred to.