Patent GB-799708-A (GB)
Title: Metal complexes of anthraquinone derivatives and materials dyed therewith
IPC: C09B1/515
Filed: 1955-07-19
Abstract: The invention comprises compounds in which chromium, cobalt, copper, iron, manganese, nickel or vanadium is in complex combination with an anthraquinone derivative of the formula <FORM:0799708/IV (b)/1> where R is alkyl of 1-4 carbon atoms, hydroxyalkyl of 2-4 carbon atoms, alkoxyalkyl of 3-4 carbon atoms, a b -hydroxy-b -ethoxyethyl group, a b  - hydroxy - b  - ethoxy - b  - ethoxyethyl group or a monocyclic aryl nucleus of the benzene series substituted or not.  They are made by reacting an anthraquinone compound of the formula given with a salt of one of the metals listed.  The compounds may be used to colour cellulose alkyl carboxylic acid esters, acrylonitrile polymers, and natural materials, either in the form of textile materials, or of fibres or yarns, and for this purpose the textiles or fibres may be treated with the compounds as such or separately in either order with the metal salts and with anthraquinone compounds of the above formula.  In the case of cellulose esters and acrylonitrile polymers, the compounds or the two reactants may be added to the dope for spinning or casting.  Cellulose esters specified are the acetate, propionate, butyrate, acetate - propionate, and acetatebutyrate. Acrylonitrile polymers specified are homo-, co-, and ter-polymers, and also graft polymers containing at least 5 per cent of combined acrylonitrile grafted on to the preformed polymer molecule, wherein the preformed polymer (which may be line or isolated) is a homopolymer of vinyl pyridine, an acrylamide, a maleamide, a fumaramide, an acrylate, a methacrylamide, a methacrylate, an itaconamide, a citraconamide, a fumaramate, an itaconamate, a citraconamate, a maleamate, or a vinyl ester, or an interpolymer of two or more such or one such with one or more different monoethylenic monomers characterized by a -CH=C< group such as styrene, acrylonitrile, substituted styrenes, vinyl or vinylidene chloride, vinyl ethers, dialkyl maleates, alkenyl ketones, dialkyl fumarates, acrylic acid, methacrylic acid, substituted acrylonitriles, fumaronitrile, and ethylene.  Textiles are dyed by a conventional dispersion process. Metal salts specified include the halides, sulphates, acetates, cyanides and thiocyanates.  In examples: (1) nickelous acetate is reacted with 1,8-dihydroxy-5-nitro-4-anilino- or p-toluidino- or b -hydroxyethylaminoanthraquinone and cobaltous chloride is reacted with 1,8-dihydroxy-4-(m-methylol anilino)-5-nitro-anthraquinone; (2) a cellulose acetate fabric was dyed with 1,8-dihydroxy-4-(p-(b -hydroxyethyl) anilino) - 5 - nitroanthraquinone and the dyed fabric was treated with cobalt or chromium thiocyanate; (3) a cellulose acetateviscose check was dyed with 1,8-dihydroxy-4-(p - (m - methylol) anilino) - 5 - nitroanthraquinone and then padded with nickel thiocyanate solution, and a cellulose acetate fabric was similarly dyed, followed by padding with a copper sulphate preparation; (4) a cellulose acetate tricot fabric was dyed with 1,8-dihydroxy - 4 - (m - (C - methylmethylol) anilino) - 5 - nitroanthraquinone, followed by padding with ferrous or ferric thiocyanate; (5) a cellulose acetate taffeta was printed through a screen with a printing paste containing 1,8-dihydroxy - 4 - (p - (b  - hydroxyethyl) - anilino) - 5 -nitroanthraquinone or the corresponding 4-(p-toluidino) body and nickel thiocyanate; (6) a dope consisting of cellulose acetate in acetone was mixed with the following metallised dyes and ground, using sand as grinding aid: (a) the product from nickelous acetate and 1,8-dihydroxy-4-anilino or p-toluidino-5-nitro-anthraquinone, (b) the product from copper acetate and 1,8 - dihydroxy - 4 - (p - (b  - hydroxyethyl)-anilino) -5-nitroanthraquinone; (c) the product from chromium thiocyanate and 1,8-dihydroxy-5 - nitro - 4 - n - butylaminoanthraquinone; (7) a cellulose acetate yarn spun from a dope containing cupric bromide was dyed with 1,8-dihydroxy-4-anilino-5-nitroanthraquinone; (8) a graft polymer was prepared by copolymerizing acrylonitrile and N-methyl methacrylamide in aqueous emulsion containing potassium persulphate and tertiary-dodecyl mercaptan, and an aqueous dope of copolymer so obtained is further polymerized with acrylonitrile and a little N-methyl methacrylamide in presence of water, potassium persulphate and metabisulphite, phosphoric acid, and tertiary dodecyl mercaptan, and reference is made to the dyeing of fibres of such a graft polymer with the compounds of the invention.  Specification 716,333, 716,564, 716,937, [764,296, 764,297, 764,298 and 781,435, [all in Group IV (a)]], are referred to.ALSO:The invention comprises compounds in which chromium, cobalt, copper, iron, manganese, nickel or vanadium is in complex combination with an anthraquinone derivative of the formula <FORM:0799708/IV (a)/1> where R is alkyl of 1-4 carbon atoms, hydroxyalkyl of 2-4 carbon atoms, alkoxyalkyl of 3-4 carbon atoms, a b  - hydroxy - b  - ethoxyethyl group, a b  - hydroxy - b  - ethoxy - b  - ethoxyethyl group or a monocyclic aryl nucleus of the benzene series, substituted or not.  They are made by reacting an anthraquinone compound of the formula given with a salt of one of the metals listed.  The compounds may be used to colour cellulose alkyl carboxylic acid esters; the compounds or the two reactants may be added to the dope for spinning or casting.  Cellulose esters specified are the acetate, propionate, butyrate, acetate-propionate, and acetate-butyrate.  Metal salts specified include the halides, sulphates, acetates, cyanides and thiocyanates.  In examples, a dope consisting of cellulose acetate in acetone is mixed with the following metallized dyes and ground, using sand as grinding aid: (a) the product from nickelous acetate and 1.8-dihydroxy-4-anilino or p-toluidino-5-nitro-anthraquinone; (b) the product from copper acetate and 1.8-dihydroxy-4 - (p - hydroxyethyl) - anilino) - 5 - nitrothraquinone; (c) the product from chromium thiocyanate and 1.8 - dihydroxy - 5 - nitro-thraquinone; (c) the product from chromium thiocyanate and 1.8 - dihydroxy - 5 - nitro - 4-n - butylaminoanthraquinone.  Specifications 716,333, 716,564, 716,937, [all in Group IV (c)], 764,296, 764,297, 764,298 and 781,435 are referred to.