Patent GB-608204-A (GB)
Title: Improvements in or relating to the production of infusible drying oil products
IPC: C04B26/12
Filed: 1946-02-18
Abstract: A drying or semi-drying oil, whose molecule has a conjugated system of carbon-to-carbon double bonds, or the corresponding fatty acid, is polymerized in presence of (i) an oxygen compound of boron and (ii) oxalic acid or an a -hydroxy aliphatic acid or an o-hydroxy aromatic acid or a derivative of one of these acids which yields the acid, e.g. upon hydrolysis or ester interchange. An infusible product which is resistant to chemicals and solvents and which can be formed in situ as a coating, impregnant or moulding material is obtained, the polymerization taking place at such a low temperature that it may occur on heat-sensitive surfaces or in the presence of heat-sensitive fibrous fillers. Drying oils of the conjugated type which may be employed are tung oil, oiticica oil, isomerized drying oils and dehydrated castor oil.  These may be used in admixture with drying oils of the non-conjugated type such as linseed or soya oil if desired. Oxygen compounds of boron mentioned are oxides of boron such as B2O3, acids of boron such as ortho- and meta-boric acids, saturated and unsaturated aliphatic and aromatic esters of boron acids such as monoboroglyceride, triamyl borate, triallyl borate and triphenyl borate, and salts of boron acids such as borax, sodium perborate, ammonium borate, copper borate and manganese borate.  The second ingredient of the polymerization catalyst may be hydrated or anhydrous oxalic acid, mesoxalic acid, citric acid, tartaric acid, hydroxy acetic acid, a -hydroxy-propionic acid, a -hydroxy-butyric acid, salicylic acid and the various cresotic acids having a hydroxyl group ortho to the carboxyl group.  The saturated and unsaturated aliphatic esters of these acids may alternatively be employed. Oil-soluble resins may be added to the oil to be polymerized and these resins may be of the permanently fusible type such as non-heat-hardenable p  oil-soluble phenolic resins, ester gum, cumarone resin, run congo resin or rosin or of the heat-reactive type such as heat-reactive oil-soluble phenolic resins, the fatty oil- or natural resin-modified ester-reaction products of polyhydric alcohols or the cyclopentadiene adduct of maleic anhydride.  Fillers which can be incorporated include cork, wood flour, asbestos, mica, textile fibres, graphite and abrasive grains.  Pigments and pigment extenders such as titanium pigments, Prussian blue, chromium oxide, barytes, silica, whiting, ochres, siennas, umbers and synthetic iron oxides may also be incorporated.  Waxes such as paraffin wax, carnauba wax or chlorinated naphthalene and plasticisers such as the phthalate esters of monohydric alcohols, aryl phosphates or phthalates or alkyl abietates may also be incorporated.  If desired, the polymerization may be carried out in the presence of solvents such as toluol, methyl ethyl ketone or aliphatic hydrocarbons.  In examples: (a) tung oil is polymerized in presence of triamyl borate together with hydrous oxalic acid, tartaric acid, citric acid or salicylic acid; (b) tung oil is polymerized in presence of boric acid and hydrated oxalic acid, diethyl oxalate, salicylic acid or lactic acid; (c) tung oil is polymerized in presence of B2O3 and anhydrous oxalic acid; (d) oiticica oil or a synthetic drying oil consisting of the pentaerythritol esters of conjugated linseed oil fatty acids is polymerized in presence of triamyl borate and oxalic acid; (e) isomerized linseed oil or a synthetic drying oil consisting of the pentaerythritol ester of conjugated soya bean oil fatty acid is polymerized in presence of orthoboric acid and oxalic acid; (f) tung oil having dispersed therein a paraphenyl-phenol-formaldehyde resin is polymerized in presence of oxalic acid and triamyl, tri allyl, methallyl, methylhexalin, trioctyl, triethyl or triphenyl borate. Specification 549,303, [Group IV], is referred to.ALSO:A drying or semi-drying oil, whose molecule has a conjugated system of carbon-to-carbon double bonds, or the corresponding fatty acid, is polymerized in presence of (i) an oxygen compound of boron and (ii) oxalic acid or an a -hydroxy aliphatic acid or an o-hydroxy aromatic acid or a derivative of one of these acids which yields the acid, e.g. upon hydrolysis or ester interchange. Oil-soluble resins may be added to the oil to be polymerized and these resins may be of the permanently fusible type, such as non-heat-hardenable oil-soluble phenolic resins, ester gum, cumarone resin, run congo resin or rosin or of the heat-reactive type such as heat-reactive oil-soluble phenolic resins, the fatty oil- or natural resin-modified ester reaction products of polyhydric alcohols or the cyclopentadiene adduct of maleic anhydride.  An infusible product which is resistant to chemicals and solvents and which can be formed in situ as a coating, impregnant or moulding material is obtained, the polymerization taking place at such a low temperature that it may occur on heat-sensitive surfaces or in the presence of heat-sensitive fibrous fillers.  Drying oils of the conjugated type which may be employed are tung oil, oiticica oil, isomerised drying oils and dehydrated castor oil.  These may be used in a mixture with drying oils of the non-conjugated type such as linseed or soya oil if desired.  Oxygen compounds of boron mentioned are oxides of boron such as B2O3, acids of boron such as ortho- and meta-boric acids, saturated and unsaturated aliphatic and aromatic esters of boron acids such as monoboroglyceride, triamyl borate, triallyl borate and triphenyl borate, and salts of boron acids such as borax, sodium perborate, ammonium borate, copper borate and manganese borate.  The second ingredient of the polymerization catalyst may be hydrated or anhydrous oxalic acid, mesoxalic acid, citric acid, tartaric acid, hydroxy-acetic acid, a -hydroxy-propionic acid, a -hydroxybutyric acid, salicylic acid and the various cresotic acids having a hydroxyl group ortho to the carboxyl group.  The saturated and unsaturated aliphatic esters of these acids may alternatively be employed. Fillers which can be incorporated include cork, wood flour, asbestos, mica, textile fibres, graphite and abrasive grains.  Pigments and pigment extenders such as titanium pigments, Prussian blue, chromium oxide, borytes, silica, whiting, ochres, siennas, umbers and synthetic iron oxides may also be incorporated.  Waxes such as paraffin wax, carnauba wax or chlorinated naphthalene and plasticisers such as the phthalate esters of monohydric alcohols, arylphosphates or phthalates or alkyl abietates may also be incorporated.  If desired, the polymerization may be carried out in the presence of solvents such as toluol, methylethyl ketone or aliphatic hydrocarbons.  In examples: (a) tung oil having dispersed therein a paraphenyl-phenol-formaldehyde resin is polymerized in presence of oxalic acid and triamyl, triallyl, methallyl, methylhexalin, trioctyl, triethyl or triphenyl borate; (b) the tung oil-resin mixture of (a) is polymerized in the presence of oxalic acid and triamyl borate, asbestos fibres being added to give a composition suitable for brake linings, clutch facings, stair treads and the like; dried cork flour or wood flour is substituted for the asbestos fibres to give a composition suitable for floor coverings; abrasive grains such as sand, garnet or synthetic abrasives are substituted for the asbestos fibres to give a composition suitable for stair treads; (c) a printing ink is obtained by polymerizing a mixture of tung oil, oil-soluble substituted phenol-aldehyde resin and carbon black in the presence of orthoboric acid and oxalic acid, and (d) a coating composition is obtained by polymerizing a mixture of tung oil, paraphenyl-phenol-formaldehyde resin and Solvesso No. 1 ("Solvesso" is a Registered Trade Mark) in the presence of orthoboric acid and oxalic acid.  Specification 549,303 is referred to.  The Specification as open to inspection under Sect. 91 contains an additional example in which tung oil, oil-soluble paraphenyl-phenol-formaldehyde resin and low-molecular weight oil-soluble liquid polystyrene resin, together with iron oxide, paraffin or Aloxite abrasive grains ("Aloxite" is a Registered Trade Mark), is polymerized in the presence of triamyl borate and oxalic acid to obtain coating compositions.  This subject-matter does not appear in the Specification as accepted.ALSO:A fibrous composition suitable for use in brake linings, clutch facings, stair treads and the like consists of tung oil, oil-soluble paraphenyl - phenol - formaldehyde resin, anhydrous oxalic acid, triamyl borate and asbestos fibres.  A composition suitable for floor coverings may be obtained by replacing the asbestos fibres with cork flour or wood flour.