Patent GB-672820-A (GB)
Title: Improvements in unsymmetrical diphenylol methanes
IPC: C07C39/16
Filed: 1950-01-26
Abstract: Diphenylol-methanes of the formula <PICT:0672820/IV (a)/1> where n is 1-4, X is alkyl, cycloalkyl, aryl, alkenyl, alkoxy or hydroxy, and the hydroxy group shown in the right-hand ring is in the 2-, 4- or 6-position with respect to the methylene group, form heat-hardenable resins with hexamethylene tetramine, formaldehyde or other "methylene-engendering" compound, or another aldehyde such as benzaldehyde, furfural, butyraldehyde, valeraldehyde or acetaldehyde. The hardening speed is less than that of resins derived from compounds where X is hydrogen.  In the examples, the following substituted diphenylmethanes are heated with hexamethylene tetramine and with formaldehyde: 2 : 21 - dihydroxy - 31 - methyl, 2 : 21 - dihydroxy - 51 - methyl, 2 : 21 - dihydroxy - 61 - methyl, 2 : 41 - dihydroxy - 21 - methyl, 2 : 21 - dihydroxy-41-methyl, 2 : 21-dihydroxy-4 : 61 - dimethyl, 2 : 41 - dihydroxy - 21 : 61 - dimethyl, 2 : 21 - dihydroxy - 51 - tert.-butyl, 2 : 21 - dihydroxy - 41 - methoxy, 2 : 21 - dihydroxy - 61 - methoxy, 2 : 41 - dihydroxy - 21 - methoxy, 2 : 21 : 61 - trihydroxy, 2 : 21 : 61 - trihydroxy - 41 - methyl, 2 : 21 : 51 - trihydroxy, 2 : 21 - dihydroxy - 31 - crotyl and 2 : 21 - dihydroxy - 51 - cyclohexyl. Also, 2 : 21-dihydroxy-51-phenyldiphenylmethane is heated with hexamethylene tetramine.  In a further example, cardanol is heated with saligenin to give a mixture of a substituted diphenylmethane and polymers thereof; this mixture is heated with hexamethylene tetramine and with formaldehyde.  Compositions of the above resins with fatty oils (e.g. tung oil) are suitable as varnishes and other coating compositions. In an example, saligenin is condensed with o-cresol and the product heated with hexamethylene tetramine or formaldehyde.  The resulting resin is dissolved in tung oil and thinned with a varsolxylene solvent as necessary; driers consisting of lead naphthenate, cobalt octoate and manganese naphthenate are then added.ALSO:The invention comprises diphenylol-methanes of the formula <FORM:0672820/IV (b)/1> where n is 1-4, X is alkyl, cycloalkyl, aryl, alkenyl, alkoxy or p hydroxy, and the hydroxy group shown in the right-hand ring is in the 2 -, 4 - or 6 - position with respect to the methylene group, and their production by condensing saligenin with the appropriately-substituted phenol.  By-products are compounds of the formul  <FORM:0672820/IV (b)/2> and <FORM:0672820/IV (b)/3> where y is 1 to about 40.  Preferably the phenol is used in excess (3 : 1 to 10 : 1 molar ratio) and the reaction is carried out between 100-200 DEG  C. at a pH of 4-7.  Hydroxides, oxides and organic acid salts of alkali metals, alkaline earth metals, zinc and aluminium may be added to maintain the correct pH.  The desired product may be isolated by crystallization and/or vacuum distillation.  Crude saligenin may be used, as obtained by condensing formaldehyde with excess of phenol. Examples show the production of the following substituted diphenyl - methanes: 2 : 21 - dihydroxy - 31 - methyl, 2 : 41 - dihydroxy - 31-methyl, 2 : 21 - dihydroxy - 51 - methyl, 2 : 21 dihydroxy - 61 - methyl, 2 : 41 - dihydroxy-21 - methyl, 2 : 21 - dihydroxy - 41 - methyl, 2 : 21 - dihydroxy - 41 : 61 - dimethyl, 2 : 41-dihydroxy - 21 : 61 - dimethyl, 2 : 21 - dihydroxy - 51 - tert. butyl, 2 : 21 - dihydroxy-41 - methoxy, 2 : 21 - dihydroxy - 61 - methoxy, 2 : 41 - dihydroxy - 21 - methoxy, 2 : 21 : 61-trihydroxy, 2 : 21 : 61 - trihydroxy - 41-methyl, 2 : 21 : 51 - trihydroxy, 2 : 21 - dihydroxy - 31 - crotyl, 2 : 21 - dihydroxy - 51-cyclohexyl and 2 : 21 - dihydroxy - 51 - phenyl.  In a further example, cardanol is heated with saligenin to give a mixture of a diphenylmethane and polymers thereof.  Other suitable phenols are listed.  The products give resins with formaldehyde, hexamethylene tetramine and similar compounds (see Group IV (a)).  Substituted xanthenes are obtained by heating the above products which contain hydroxy groups in the 2 : 21-positions, e.g. 2-methyl-, 4-methyl- and 2 : 4-dimethyl-xanthenes.ALSO:Diphenylol - methanes of the formula <FORM:0672820/III/1> where n is 1-4, X is alkyl, cycloalkyl, aryl, alkenyl, alkoxy or hydroxy, and the hydroxy group shown in the right-hand ring is in the 2-, 4- or 6- position with respect to the methylene group, are dissolved in fatty oils to give oleo-resinous coating compositions.  Suitable oils are linseed oil, soya bean oil and tung oil.