Patent GB-1063331-A (GB)
Title: Chromium-organic acid-alcohol complexes
IPC: C08K5/00
Filed: 1964-03-17
Abstract: The invention comprises water-insoluble organo-chromium complexes in which an alcohol having at least 4 carbon atoms, except t-butanol, is co-ordinated to a chromium-monocarboxylic acid co-ordination compound of the Werner acidato-chromium type. The complexes are made by fusing a salt of chromium with a carboxylic acid and/or rosin to give the Werneracidato-chromium complex and heating this complex with the alcohol at a temperature of at least 80 DEG  C. for at least 15 minutes.  Numerous saturated and unsaturated, straight- and branched-chain aliphatic acids and substituted, e.g. by anino groups, aliphatic acids and saturated and unsaturated, mono- and poly-alcohols are specified.  The Werner complex is usually made by heating the chromium salt, e.g. chromium chloride hexahydrate, with the carboxylic acid at 120-250 DEG  C., generally in proportions such that the chromium atom: -COOH group ratio is from 1:4 to 10:1.  The fused mass may be ground prior to heating with the alcohol.  The Werner complex and alcohol are usually employed in proportions by weight ranging from 10:0.1 to 1:1000 and are preferably heated at the reflux temperature under atmospheric pressure.  The rosin-containing complexes are made by similar methods; when the complex contains rosin and an aliphatic acid, the chromium-aliphatic acid may be prepared as above and the rosin introduced together with the alcohol, i.e. by refluxing the mixture.  The novel co-ordination complexes are used in adhesive compositions (see Divisions B2 and C3).  The examples relate to chromium complexes prepared from acids selected from docosanoic, n-valeric, iso-valeric, sorbic, linoleic, octanoic, amino-acetic, 2-amino-octanoic, undecanoic, acids and rosin and from alcohols selected from n-amyl, n-hexanol, stearyl, oleyl, n-butanol, iso-octyl and 3-methyl-3-butyn-2-ol alcohols.ALSO:Water-insoluble chromium complexes, in which an alcohol having at least 4 carbon atoms (except tertiary butanol) is co-ordinated to a chromium-monocarboxylic acid co-ordination of the Werner acidato-chromium type (the carboxylic acid being an aliphatic acid and/or rosin), are added to polymeric materials in order to improve the adhesive properties thereof, and to solutions of polymeric materials to form adhesive coating compositions.  The chromium complexes, which are liquid, and may be used in hexane solution, are usually added in amounts of 0.25-10% by weight of polymeric material. Examples 12-21 describe adhesive compositions based on natural rubber, polyisobutylene, styrene/butadiene copolymers, butadiene/acrylobutrile rubber, polychloroprene, polyvinylmethyl ether, polyisoprene, polybutadiene, dimethyl polysiloxane, poly-n-butylmethacrylate, polystyrene, cellulose acetate butyrate, cellulose acetate, nitrocellulose, various rubbers (described as synthetic rubber-resin, pigmented natural and synthetic resin types), polyvinyl acetate, polyethylene and polyvinyl chloride.  Most of these compositions are based on toluene solutions of the polymeric material, but the cellulose compositions are in isopropyl acetate or acetone solution, the polyvinyl acetate in methanol solution, and the polyvinylchloride in a mixture of hexane and dioctyl phthalate.  In the examples the compositions are applied to paper and air dried to give an adhesive coating.ALSO:Adhesive coating compositions contain a water-insoluble chromium complex in which an alcohol having at least 4 carbon atoms (except t-butanol) is co-ordinated to a chromium-monocarboxylic acid coordination compound of the werner-acidato type (the acid being an aliphatic acid and/or rosin). The composition may be a simple solution of the complex or, preferably, also contains a polymeric material.  In the latter case, the chromium complex is usually employed in amounts of 0.25 - 10% by weight of polymeric material.  Example 7 describe the treatment of paper, by dipping and drying, with solutions of a complex dissolved in petroleum ether and in isopropanol.  Examples 12-20 relate to coating paper with adhesive solutions using an iron bar to make draw downs, and drying the paper either at room temperature or by heating. These Examples relate to compositions based on natural rubber, polyisobutylene, styrene/butadiene copolymers, butadiene/acrylobutrile rubber, polychloroprene, polyvinyl methyl ether, polyisoprene, polybutadiene, dimethyl polysiloxane, poly-n-butyl methacrylate, polystyrene, cellulose acetate butyrate, cellulose acetate, nitrocellulose, various rubbers (described as synthetic rubber-resin, pigmented natural and synthetic resin types), polyvinylacetate and polyethylene.  All p  these compositions are toluene based solutions except those containing cellulose derivatives (acetone or isopropyl acetate) and polyvinyl acetate (methanol). Example 21 relates to paper coated with an adhesive composition based on polyethylene which is subsequently coated with a second adhesive layer based on polyisobutylene or styrene-butadiene.