Patent GB-936888-A (GB)
Title: Manufacture of phenolic resins
Inventor: LERER MOISE
IPC: C08G8/28
Filed: 1961-12-06
Abstract: Resins derived from phenols by reaction with the heavy residues produced in the manufacture of diolefines by condensation of formaldehyde and monoolefines (see Group IV(a) abridgment), are dissolved in hydrocarbons (toluene) with cobalt octanoate as drier, coated on to wood, metal or glass, and dried in air at room temperature or 100 DEG C.ALSO:Phenols are reacted with the "heavy residues" which are a by-product of the manufacture of diolefines from olefines by condensation with formaldehyde.  In this manufacture of diolefines, a two-step process may be used, the metadioxane intermediate being isolated by distillation before conversion to diolefine, the residue after said distillation being used as a "heavy residue" in the present invention, or the metadioxane may be converted to diolefine in situ, the diolefine distilled off, then remaining metadioxane removed by distillation, the residue again being used as "heavy residue" in the present invention. Fractions of these residues separated by distillation or solvent extraction may also be used.  During the reaction with phenol, diolefines and intermediates such as metadioxanes or pyrans are given off and may be recovered.  The products may be rendered thermosetting by addition of aldehydes or hexamethylene tetramine either during or after the reaction.  It is advantageous if the aldehyde is added after reaction, to neutralize and concentrate the product of the first step before adding aldehyde and reacting further.  Suitable phenols are phenol; cresols; xylenols; butyl-, amyl-, benzyl-, phenyl-, cyclohexyl-phenols; resorcinol or bis-phenols.  The ratio of phenol to residue by weight is for example 0,1-5, preferably 0,2-1.  The reaction is normally carried out at 50 DEG -200 DEG C., preferably 70 DEG -130 DEG C.  Catalysts may be added, e.g. sulphuric, phosphoric or toluene-sulphonic acids, boron fluoride, aluminium, zinc or ferric chlorides, or antimony pentachloride.  At the beginning of or during the reaction, various modifiers may be added, e.g. unsaturated alcohols; ketones; carbohydrates; alkyl, aryl or alkaryl halides, dioxolanes, or metadioxanes.  The reaction may be carried out dry or in the presence of water.  The products may be esterified by the addition, before or after the reaction, of olefinic acids or their derivatives such as anhydrides, acid chlorides, esters, amides or imides, suitable acids being monocarboxylic, e.g. oleic, linoleic or ricinoleic, polycarboxylic, e.g. maleic or fumaric, acyclic or cyclic, e.g. colophony or the acids it contains.  The products formed when the reaction of phenol and heavy residue is carried out in the absence of water and with removal of water formed during the reaction, e.g. by simple distillation if necessary under reduced pressure, azeotropic distillation or use of a dehydrating agent, is more soluble in hydrocarbons and has better drying properties than those made by other procedures and therefore more suitable for use in paints.  In Example 5, the resin produced is heated with styrene and cobalt octanoate to give a solid resin.  In Examples 2 and 11, the resins are used to bind sawdust and glass fibres, respectively.ALSO:20 gm. of sawdust ore mixed with a solution in 20 gm. of ethanol of 20 gm. of resin and the ethanol evaporated; 2 gm. of hexamethylenetatramine are then added and the mixture compressed and heated to 130 DEG C. for three hours.  The resin is formed by reacting phenol with the heavy residue remaining after reacting formaldehyde with isobutane and removal of the 4, 4-dimethylmetadioxane formed.