Patent GB-1116919-A (GB)
Title: Unsaturated urethane drying oils
Inventor: ARGABRIGHT PERRY A
IPC: C08G71/00
Filed: 1966-12-16
Abstract: Unsaturated urethane drying oil compositions comprising unsaturated urethane compounds in which none of the nitrogen atoms of the urethane radicals are attached to aromatic rings, and which contain at least 0.1 mole per cent of isocyanurate groups based on the moles of nitrogen in the composition, may be obtained by reacting a hydroxyl-containing partial ester of an unsaturated fatty acid with an organic dihalide and a metal cyanate.  The reaction is preferably effected at a temperature of 25-300 DEG  C. at a pressure of from below one atmosphere to over 10,000 p.s.i.g., suitably in the presence of an aprotic solvent, e.g. N-alkyl pyrrolidones, dialkyl formamides, N,N-dimethyl-acetamide, acetonitrile, hexamethyl phosphoramide or tetramethylurea.  The organic radical in the organic dihalide starting material may be 2-butenylene, tetramethylene, pentamethylene, hexamethyelene, heptamethylene, octamethylene, m- or p-xylylene, or the methylene chains may be interrupted by cyclohexyl or naphthyl radicals; the organic dihalides may be further substituted by groups which are inert during the reaction.  The metal in the metal cyanate starting material may be Li, Na, K, Rb, Cs, Ag, Be, Ca, Mg, Pb or an organic radical which acts as a metal, e.g. the pyridinium or tetraalkylammonium radical,  The hydroxyl-containing unsaturated partial esters of fatty acids which are employed as starting materials may contain either primary or secondary hydroxyl groups and they may be prepared by transesterification of unsaturated fatty acid esters with a suitable polyol in the presence of a transesterification catalyst such as PbO, calcium naphthenate, NaOH, KOH or CaO; the number of free hydroxyl groups in the resulting partial esters may be controlled by varying the ratio of ester to polyol in the transesterification reaction.  Esters suitable for use in the transesterification reaction have the formula R1(OOCR)x where R1 is derived from a polyol, x is the valency of R1 and the RCOO group is derived from an unsaturated fatty acid such as those normally occurring in linseed oil, soybean oil, cottonseed oil, dehydrated castor oil, tung oil, safflower oil, peanut oil, fish oils, or from pure materials such as oleic, linoleic, palmitoleic or ricinoleic acids, and the oils may be modified by alkali refining, blowing or heat bodying.  The polyol employed to produce the partial ester starting material may be derived from a low molecular weight polyol such as ethylene glycol, glycerol, trimethylol propane, pentaerythritol, cyclohexane diol, p-xylylene glycol, 1,4-tetrahydronaphthalene diol or 1,4-dihydroxymethyl cyclohexane, or from a polymeric polyol, e.g. polyether polyols, polyester polyols, polychlorhydrins and polyurethane polyols, e.g. the polymer derived from hexamethylene diisocyanate and ethylene glycol or that derived from trimethylol propane and p-xylylene diisocyanate, and the polyols may be substituted by non-interfering groups.ALSO:Unsaturated urethane drying oil compositions comprising unsaturated urethane compounds in which none of the nitrogen atoms of the urethane radicals are attached to aromatic rings, and which contain at least 0.1 mole per cent of isocyanurate groups based on the moles of nitrogen in the composition, may be obtained by reacting a hydroxyl-containing partial ester of an unsaturated fatty acid with an organic dihalide and a metal cyanate.  The reaction is preferably effected at a temperature of 25-300 DEG  C. at a pressure of from below one atmosphere to over 10,000 p.s.i.g., suitably in the presence of an aprotic solvent, e.g. N-alkyl pyrrolidones, dialkyl formamides, N,N-dimethylacetamide, acetonitrile, hexamethylphosphoramide or tetramethylurea.  The organic radical in the organic dihalide starting material may be 2-butenylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, m- or p-xylylene, or the methylene chains may be interrupted by cyclohexyl or naphthyl radicals; the organic dihalides may be further substituted by groups which are inert during the reaction.  The metal in the metal cyanate starting material may be Li, Na, K, Rb, Cs, Ag, Be, Ca, Mg, Pb, or an organic radical which acts as a metal, e.g. the pyridinium or tetraalkyl ammonium radical. The hydroxyl-containing unsaturated partial esters of fatty acids which are employed as starting materials may contain either primary or secondary hydroxyl groups and they may be prepared by transesterification of unsaturated fatty acid esters with a suitable polyol in the presence of a transesterification catalyst such as PbO, calcium naphthenate, NaOH, KOH, or CaO; the number of free hydroxyl groups in the resulting partial ester may be controlled by varying the ratio of ester to polyol in the transesterification reaction. Esters suitable for use in the transesterification reaction have the formula R1(OOCR)x where R1 is derived from a polyol, x is the valency of R1 and the RCOO group is derived from an unsaturated fatty acid such as those normally occurring in linseed oil, soybean oil, cottonseed oil, dehydrated castor oil, tung oil, safflower oil, peanut oil, fish oils, or from pure materials such as oleic, linoleic, palmitoleic or ricinoleic acids and the oils may be modified by alkali refining, blowing or heat bodying.  The polyol employed to produce the partial ester starting material may be derived from a low molecular weight polyol such as ethylene glycol, glycerol, trimethylol propane, pentaerythritol, cyclohexane diol, p-xylylene diol, 1,4-tetrahydro-naphthalene diol or 1,4-dihydroxymethyl cyclohexane, or from a polymeric polyol, e.g. polyether polyols, polyester polyols, polyurethane polyols and polychlorhydrins, and the polyols may be substituted by non-interfering substituents.ALSO:Articles or objects may be coated with an unsaturated urethane drying oil composition comprising unsaturated urethane compounds in which none of the nitrogen atoms of the urethane radicals are attached to aromatic rings, and which contain at least 0.1 mole per cent of isocyanurate groups based on the moles of nitrogen in the composition.  The coatings may be brushed, rolled, sprayed or flow-coated onto substrates such as stone, metal, wood, plastics, glass, concrete and cinder block aggregates.  The substrates may be in the form of flat sheets, wires or architectural shapes.