Patent GB-570367-A (GB)
Title: Improvements in or relating to the manufacture of resinous compositions
IPC: C08G8/28
Filed: 1943-03-15
Abstract: A process for the preparation of an oil modified resin comprises reacting at a temperature between 115 DEG  C. and 215 DEG  C. (preferably between 130 DEG  C. and 175 DEG  C.) a potentially heat-reactive phenol-aldehyde resin (i.e. one prepared from a phenol and less than an equimolecular proportion of aldehyde in the presence of an acid condensing agent and requiring addition of hardening agent, e.g. hexamethylenetetramine, in proportion of 3-15 per cent of the weight of the resin) with fatty oils, or oxidized, heat-polymerized, dehydrated, or hydrogenated fatty oils or fatty acids, having at least 7 carbon atoms to the molecule, the reaction being carried out in the presence of an added acid catalyst consisting of sulphuric acid, phosphoric acid or a sulphonic acid of the formula RSO3H when R is halogen, alkyl, aryl, or aralkyl.  Ethyl sulphuric acid or compounds which give rise to acid under the reaction conditions may also be used, e.g. sulphur trioxide, CaSO4.H2SO4, or dimethyl sulphate.  The weight of catalyst employed is preferably 4 per cent or less of the weight of resin.  The catalyst may be added as a solution in a solvent for the resin modifying agent.  The product of the reaction may be dehydrated or partially dehydrated. For moulding compositions the proportion of oil in the resin may vary from 10 to 60 per cent.  For coating compositions more oil is used.  When employing a high content of oil, the quantity of added acid catalyst is reduced.  The product of the mixture mixed with hardening agents may be used with fillers as moulding compositions, e.g. for brake linings and grinding wheels. They may also be used as thermosetting adhesives for plywood and for coating compositions.  Resinous materials such as colophony may be added to the compositions.  In the examples: (1) a potentially heat reactive resin is prepared from phenol containing 10 per cent of o-cresol, and less than 1 mol. of formaldehyde in presence of phosphoric acid.  To the molten dehydrated resin were added sulphuric acid dissolved in ethyl alcohol and soya bean oil and the mixture was maintained at 160 DEG  C. for 15-30 minutes.  (2) In this example a slightly higher proportion of formaldehyde was employed, the oil was blown soya bean oil and in one case the catalyst was phosphoric acid while in the other it was sulphuric acid.  Example (3) employs blown grape-fruit seed oil.  Example (4) employs a high viscosity heat bodied linseed oil.  Example (5) employs a slightly different resin with blown soya bean oil. Example (6) employs alkali-refined fish oil as the modifying agent and p-toluene sulphonic acid dissolved in alcohol as the catalyst. Example (7) employs dehydrated castor oil with sulphonic acid. Example (8) employs a high proportion of blown soya bean oil with alcoholic p-toluene sulphonic acid as the catalyst.  Example (9) describes the mixing of sulphonic acid dissolved in ethyl alcohol with raw soya bean oil followed by addition of the resin and heating.  Example (10) employs alcoholic sulphonic acid and linseed oil fatty acids.  Example (11) describes the treatment of a resorcinol-formaldehyde resin with blown soya bean oil and sulphonic acid dissolved in acetone.  Example (12) employs alcoholic sulphonic acid and cotton seed oil approximately 80 per cent hydrogenated.  Example 13 employs alcoholic dimethyl sulphate as catalyst.  This is believed to methylate the resin, liberating sulphonic acid to act on the catalyst.  Specifications 511,511 and 533,582 are referred to.