Patent GB-956334-A (GB)
Title: Method for the production of poly (aromatic ether) resins
IPC: C07C43/263
Filed: 1962-04-25
Abstract: Solid poly(aromatic ether) resins are prepared by heating a hydroxymethylated diaryl oxide or its aliphatic ether in presence of a catalyst. Specified diaryl oxides are diphenyl oxides containing 1 to 4 hydroxymethyl groups or ethers thereof, the ether group being alkyl having 1 to 4 carbon atoms, allyl or 2-methyl allyl. Such diaryl oxides may contain one or two halogen, aryl, alkyl or alkoxy groups. A mixture of homologues or isomers having the same or different number of reactive groups per molecule may be used. Additional diaryl oxides free from reactive groups may be used, the average functionality being 1.2 reactive groups per molecule. Specified catalysts are ferric chloride; stannic chloride, stannous chloride, BF3, ZnC12, P2O5, H3PO4, H2SO4, HF, HC1, HBr, organic sulphuric acids, alkali metal and ammonium hydroxides and carbonates. The temperature is preferably below 400 DEG C. Specified inert fillers which may be added are mineral and synthetic fibres, asbestos, fly ash, blast furnace and power house slags, mica flour, wood flour, wood particles and similar fibrous or granular substances. In examples (1) poly(methylol) diphenyl oxide compositions of varying functionality are condensed with phosphoric acid at 185 DEG C.; (2) a poly(methylol) diphenyl oxide is condensed with a number of catalysts to produce thermoset products insoluble in acetone, benzene and toluene and having resistance to water, alkalis and acids; (3) a solution of a poly(methylol) diphenyl oxide in acetone to which phosphoric acid has been added is mixed with wood flour and spread on paper to evaporate off acetone thus forming a coating of poly(aromatic ether) resin on the wood flour; (4) monomethoxymethyl diphenyl oxide is mixed with phosphoric acid and condensed at 190 DEG C. which on cooling gave a yellow solid of molecular weight approximately 1650; and (5) alkoxymethyl diphenyl oxide mixtures containing chlorine are polymerised with phosphoric acid at 200 DEG C. to provide solid thermoplastic resins, resistant to fire.  Specifications 902,620 and 956,335 are referred to.ALSO:A non-ionic surface active agent comprising a mixture of non-ionic surface active compounds containing, in the molecule, a chain of ethylene oxide groups, is separated into fractions differing in surface active characteristics by adding to a solution of the surface active agent in an organic solvent, a precipitating agent in which the surface active agent is only partially soluble, the precipitating agent being a liquid miscible with the solvent, whereby part of the surface active agent is thrown out of solution to form a precipitated fraction which is recovered.  The precipitated fraction contains an increased proportion of compounds having relatively long ethylene oxide chains compared with the compounds remaining in solution.  A plurality of precipitated fractions may be obtained by progressive additions of the precipitating liquid or by progressively lowering the temperature.  The surface active agents may be prepared by reaction of ethylene oxide with a suitable organic compound containing an -OH or -SH group, for example a fatty acid, resin acid, alcohol, alkylated phenol or mercaptan.  The mixture so obtained may be fractionated as described above, and after removal of the precipitated fractions, the solution may be distilled to remove solvent and precipitating agent to give the residue comprising compounds with short ethylene oxide chains which may be recycled to the reaction mixture comprising ethylene oxide and the organic compound.  Specified solvents are ethanol, acetone, benzene, toluene, cyclopentane, cyclohexane, carbon tetrachloride and chloroform, cyclohexane being preferred. Specified precipitating agents are iso- or normal-pentane or hexane or heptane and iso-octane, iso-hexane being preferred.  In examples, a liquid non-ionic surface active agent of formula R-A-O-(CH2-CH2-O)n-CH2-CH2-OH wherein R is an alkyl group of, on average, 8 carbon atoms, A is a benzene ring and n is approximately 12, is dissolved in cyclohexane and two-thirds thereof is precipitated in two fractions by the progressive addition of iso-octane, the remainder being recovered after distillation of the solution.  The fractions are reacted with urea as described in Specification 697,315 and the solid products obtained compared with the corresponding product from the unfractionated material.