Patent GB-334572-A (GB)
Title: Artificial masses as bases for coatings, impregnating agents, binders and the like and process for making the same
IPC: C08G8/28
Filed: 1929-05-08
Abstract: 334,572. H÷nel, H. May 8, 1929. Phenol-aldehyde condensation products; ester condensation products; chlorinated phenols. - Thin or thick oils, or gelatinous, resinous or rubber-like substances suitable for use in moulding and for use as bases for coatings, impregnating agents, binders, and the like, are obtained by reaction of an ester with a primary condensation product of low molecular weight obtained by the aid of an alkaline contact agent from formaldehyde and a phenol in which not more than two of the reactive positions o, o and p to the phenolic group or groups are unsubstituted, no solvent or dispersing agent being present during the reaction with the ester. Water is evolved during the reaction. The phenolformaldehyde condensation product is such as would, in the case where the phenol contains two such unsubstituted positions, become infusible on heating by itself. Phenols in which all the reactive positions are unsubstituted are unsuitable, and those having only one position unoccupied are less suitable than those with two free positions, but may be used in admixture therewith; such mixtures may be obtained by chlorination of phenols. The substituents may be an alkyl, aryl, aralkyl, hydroaromatic, or oxyalkyl radicle or chlorine. One or both m positions may also be occupied. Examples of suitable phenols are : o and p cresol, xylenols, carvacrol, thymol, p-tertiary butyl phenol and amyl phenol, p-benzyl phenol, the corresponding derivatives of m-cresol, guaiacol, o- and p-chlorphenol, and o- and p-chlor m-cresol. Derivatives of dioxybenzenes are not economical in use, but derivatives of p p' dioxydiphenylmethane are advantageous. They may be obtained by the condensation of 2 molecular proportions of a phenol with formaldehyde, acetone, or homologues; cyclohexanone and methyl cyclohexanone may be used. For this reaction o-cresol is suitable, or phenol may be the starting material, two atoms of chlorine being introduced into the di-phenylol compounds obtained. alpha- and #-naphthol behave similarly to phenols having only one of the reactive positions free. The phenol-aldehyde condensation product must be soluble in the ester. When the esters contain aromatic, hydroaromatic, oxy fatty, or low molecular aliphatic acid residues in sufficient amount, the phenols may contain only low-molecular substituents, but in the case of esters of high-molecular fatty acids, a higher aliphatic or other substituent group may occupy one reactive position in the phenol or the meta-position. The esters used may be of various kinds. Lowmolecular crystalloid esters, such as those of benzoic acid and monovalent alcohols, yield thin or viscous oils or gelatinous masses. Esters of the same alcohols with polybasic acids give gelatinous products with less of the phenol-formaldehyde compound. More suitable are fusible esters of fairly high molecular weight obtained from mixtures of polybasic and monobasic carboxylic acids and a polyvalent alcohol such as glycerine, or from a polybasic acid, with or without a monobasic acid, and a mixture of polyvalent and monovalent alcohols. These are often convertible into rubber-like products by very small quantities of the phenol-formaldehyde compound. The monobasic acids may be replaced by their glycerides in making these mixed esters, or such glycerides may be added to the mixed esters. The acids used may contain alcoholic or phenolic hydroxygroups. Fats, oils, and waxes are suitable. Esters of phenols with inorganic acids may also be employed. In the preparation of the phenolformaldehyde condensation compound, the constituents with at least sufficient alkali hydroxide to produce a clear solution, if necessary with the aid of alcohol, are left for a considerable time at room temperatures or slightly higher. The product is precipitated by acids or salted out. Formaldehyde in excess of the molecular proportion is preferably employed. In combining the ester with the phenol-formaldehyde compound, so much of the latter may be taken that an insoluble substance would result on continual heating; in this case the process is stopped at an intermediate stage, and the product, with or without a. siccative, dissolved to form a coating material suitable for stoving; the intermediate product is also useful as a moulding composition. Alternatively, less phenol-formaldehyde compound may be used so that the end-product does not attain the rubber-like condition, and is also suitable for paints and varnishes. If one of the acid components of the ester is derived from a drying or semi-drying oil, a siccative may be added. Some of the products are suitable for adding to cellulose varnishes. Wood oil with only a small quantity of the phenol-formaldehyde compound gives a good quick-drying varnish. Examples are given in which the phenol of the phenol-formaldehyde compound and the ester employed are respectively (1) p-tertiary-amyl-phenol and beeswax, (2) p-tertiary-butyl-m-cresol and beef tallow, (3) p-cresol and castor oil; the product is soluble in benzene-alcohol, and may be mixed with a siccative or with siccative-free varnishes, (4) p-tertiary-butyl phenol and wood oil, (5) thymol and a boiled mixture of wood oil and linseed oil, (6) ortho-cresol and tricresyl phosphate, (7) p-chlorphenol and an ester product from succinic and lactic acids and glycerine, (8) pchlor-m cresol and an ester product from succinic and salicylic acids and glycerine, (9) p-cresol and an ester product from citric, ricinoleic, and salicylic acids and glycerine, (10) ortho-cresol and an ester product from phthalic anhydride, oleic acid, and ethylene glycol, (11) 1: 4: 5-xylenol and an ester product from d-tartaric acid, benzoic acid, and glycol; the resin is elastic like rubber, (12) and (13) a compound obtained by the action of hydrochloric acid on a mixture of o-cresol and methyl-ethyl ketone; the ester is prepared from phthalic anhydride, stearic acid, and glycerine. (14) guaiacol and an ester product from sebacic and abietic acids and glycerine, (15) a compound from o-cresol and methyl cyclohexanone and an ester product from camphoric and abietic acids and glycerine; the product gives clear films with nitro-cellulose, (16) a compound from benzyl chloride and commercial m-cresol by the action of zinc chloride, and an ester product from manila, colophony, and glycerine, (17) p-tertiarvbutyl phenol and an ester product, from phthalic anhydride, linoleic acid or linseed oil, colophony. and glycerine, (18) mono-chlorinated m-cresol and an ester product from phthalic anhydride. ricinoleic acid, and mannite; the m-cresol is dissolved in glacial acetic acid and treated with the calculated quantity of chlorine with ice cooling, the p-chlor compound being mainly produced: if cooling or the quantity of acetic acid is inadequate, additional chlorine may be used to allow for the partial formation of the dichlor compound, and a larger quantity of formaldehyde added to compensate for the presence of a phenol with only one reactive position; sulphuryl chloride gives almost pure p-chlor m-cresol, (19) di-chlordiphenylol-propane and an ester product from phthalic anhydride, methyl cyclohexanol. and givrerine. the diphenylol-propane being chlorinated by sulphuryl-chloride in ether solutinn, (20) the chlorinated m-cresol referred to in (18), and an ester product by heating benzyl alcohol with citric acid and then with oleic acid and glycerine. Specification 316,858 is referred to.