Patent GB-653501-A (GB)
Title: Manufacture of synthetic resins from phenols and aldehydes and of polyphenols therefor
IPC: C08G8/28
Filed: 1947-03-31
Abstract: Synthetic resins are prepared from an aldehyde and a polyphenol having at least three phenolic nuclei per molecule of which at least three have between each adjacent pair thereof a chain containing at least five atoms and having no phenolic nuclei attached to intermediate positions in such chains or a mixture of phenols containing sufficient of such a polyphenol for the average number of phenolic nuclei per molecule to be at least 2.2, the said polyphenol or mixture having an acid value not above 50, a saponification value not above 90 and a hydroxyl value of at least 90.  Suitable polyphenols may be prepared (see Group IV (b)) by reacting phenols in presence of Friedel-Craft type catalysts with a suitable unsaturated carboxylic acid.  Examples 1-6 describe preparation of phenols.  In example 7 a polyphenol from m-cresol and linseed oil acid in presence of zinc chloride or the product of reducing such a polyphenol by Clemmensen's process is reacted with paraformaldehyde in presence of butanol and ammonia.  The resin is soluble in toluene and films may be prepared from the solution.  Example 8 reacts a condensation product from oleic acid and phenol in presence of zinc chloride with paraformaldehyde in ethanol.  In example (9) a condensation product from linseed oil acid, cresol and zinc chloride-aluminium chloride is reacted with formaldehyde and caustic potash at room temperature and then acidified to separate the resol which, dissolved in toluene yields a stoving lacquer.  In example (10) the resol of example (9) is hardened, reacted with wood oil and dissolved in toluene.  In example 11, the hardened resol of example 10 is used to make a moulding powder.  A novolac prepared according to the invention may also be used for this purpose.  In example 12, the resol of example 9 is fused with resin ester, boiled with stand-oil, dissolved and mixed with a dryer to yield a lacquer.  In example (13) the condensation product from phenol soya oil acid and BF3 is condensed with formalin and caustic potash.  Water is distilled off under vacuum, lactic acid being added during this process.  A thick syrup soluble in toluene or toluene/alcohol mixture is obtained.  It is stated that by sulphonating the polyphenols before condensation with the aldehyde or by sulphonating the resinous condensation products, tanning and textile auxiliaries may be prepared.  Specification 467,817, 558,813 and U.S.A. Specification 2,114,121 are referred to.ALSO:Polyphenols having at least three phenolic nuclei per molecule of which at least three have between each adjacent pair thereof a chain containing at least five atoms and having no phenolic nuclei attached to intermediate points in such chains are prepared by reacting in presence of a Friedel-Crafts catalyst, e.g. zinc chloride, boron trifluoride, sulphuric acid, or mixtures of zinc chloride and aluminium chloride, a phenol with a carboxylic acid having suitably spaced double bonds and carboxylic acid groups. Reaction takes place at the COOH group as well as the double bonds and the products are keto-phenols.  They may be reduced at the keto-group by Clemmensen's process.  Acids mentioned are linseed oil acid; oiticica fatty acid; eleaostearic acid; ricinoleic acid, oleic acid and tall oil fractions containing fatty acids and oleic acid.  Phenols mentioned are phenol, m-cresol and resorcinol.  The products have an acid value not exceeding 50, a saponification value not exceeding 90 and hydroxyl value of at least 90. Examples describe the preparation of polyphenols from (1) linseed oil fatty acids, phenol and zinc chloride; (2) linseed oil fatty acid, m-cresol and zinc chloride; (3) linseed oil fatty acid, cresol and a mixture of zinc chloride and aluminium chloride; (4) oleic acid, phenol and sulphuric acid, followed by a further treatment with phenol and zinc chloride; (5) soya fatty acid, phenol and boron trifluoride; (6) oleic acid, phenol and zinc chloride, followed, if desired, by addition of aluminium chloride. The polyphenols or products obtained by condensing them with aldehydes may be sulphonated to produce tanning and textile auxiliaries.  Specifications 467,817, 558,813 and U.S.A. Specification 2,114,121 are referred to.  The Specification as open to inspection under Sect. 91 includes preparation of polyphenols by reacting a phenol in presence of a Friedel-Crafts type catalyst with a polyolefine, a low molecular weight polyvinyl chloride, a low molecular weight polybutadiene, a polycarboxylic acid or an unsaturated ketone.  This subject-matter does not appear in the Specification as accepted.