Patent GB-355281-A (GB)
Title: Improvements in the manufacture and production of artificial resins
IPC: C08G63/48
Filed: 1930-05-12
Abstract: Lead salts of the products obtained by condensing American root resin or French colophony with maleic anhydride are obtained by dissolving in aqueous caustic soda and adding lead nitrate.  The products may first be heated with zinc chloride to reduce their acid value.ALSO:Synthetic resins; carboxylic acids and their salts; esters; ester-acids.-Resins of an unsaturated character, especially those containing conjugated double bonds such as natural resins or artificial resins prepared from unsaturated resinifiable substances containing such double bonds, are heated with a -b -unsaturated-a -b -polycarboxyliccompounds containing at least three oxygen atoms connected to two carbon atoms such as polycarboxylic acids, their anhydrides, neutral or acid esters including compounds which under the reaction conditions are converted into the acids or their derivatives.  Suitable compounds are malic acid, maleic acid, maleic anhydride, maleic monoalkylester, aconitic acid, citric acid and fumaric acid. Suitable resinous materials are colophony or the acids contained in different types of colophony, ester gum or other derivatives of colophony or the acids contained therein such as salts, anhydrides, amides or anilides.  Artificial resins containing colophony or the like such as resinous condensation products of phenols with formaldehyde and colophony or of phthalic acid with polyhydric alcohols or with esters or ethers thereof containing at least two hydroxyl groups and colophony or similar unsaturated resins which also contain monocarboxylic acids or oils containing the same or their esters such as linoleic acid, ricinoleic acid or acids of other fatty oils may also be employed.  Other natural resins such as dammar or yellow gum acaroides may be employed so far as they are unsaturated, the unsaturation being determined by the colouration of their solution in acetic anhydride by the addition of concentrated sulphuric acid.  The resulting compounds may be further treated; in so far as they contain free carboxyl groups they may be neutralized for example with lime, alkyl or alkylolamines or aromatic bases or esterified with hydroxyl bearing organic substances such as mono- or polyhydric aliphatic alcohols, phenols or hydroxycarboxylic acids; in so far as esters are present they may be re-esterified by heating with linseed oil. The products may be soluble in ethyl alcohol, benzene, benzine, linseed oil or turpentine oil, and the reaction, which may be carried out under a reduced pressure, may be carried out in organic solvents such as chlorbenzenes, solvent naphtha, alkylbenzenes or like inert organic solvents.  In examples (1) American root resin is heated with maleic anhydride to give a resin soluble in sodium borate or soda solutions and which is precipitated therefrom by addition of strong acid.  The product may be esterified with glycerine or the initial condensation may be carried out in the presence of linseed oil, linoleic acid, cinnamic acid, hydrogenated colophony or like hydrogenated resin acid.  Products are obtained which are easily esterified with hydroxyl-bearing organic compounds. These additions may be introduced directly before esterification with glycerol or a like polyhydric alcohol.  (2) French colophony and maleic anhydride are dissolved in o-dichlorbenzene and then heated. The o-dichlorbenzene is steam distilled off and any excess maleic anhydride distilled off and the condensation product may be purified by extraction with benzine hydrocarbons or by redissolution in glacial acetic acid or ethyl alcohol if desired in the presence of a small quantity of a mineral acid such as hydrochloric acid.  The resins from examples 1 or 2 may be heated with zinc chloride to give resins of a low acid value and these, or the untreated products may be dissolved in aqueous caustic soda and a heavy metal salt, such as lead nitrate added to give the heavy metal salt of the resin.  The resin prepared according to example 1 or the first part of example 2 may be heated with trihydroxystearic acid, if desired in the presence of a little glycerol or sorbitol to give a resin similar to shellac. (3) A glycerol or sorbitol ester of American colophony is heated with maleic anhydride to give a resin not soluble in aqueous alkalies but in benzene.  Preheated linseed oil can be added to the hot resin and after cooling solvents such as turpentine oil and siccatives such as lead manganese resinate naphthenate may then be added to give a lacquer.  (4) Maleic anhydride or citric acid is heated with gum dammar to give a resin soluble in aqueous soda solutions.  (5) French colophony and maleic mono- or diethylester or the iso- or n-butyl ester is heated and distilled in vacuo and the product may be esterified by heating under reduced pressure with glycerol.  (6) Colophony and maleic anhydride are condensed together and glycerol added to give a resin soluble in ethyl alcohol or a mixture of ethyl alcohol and benzene.  (7) Colophony and maleic anhydride are condensed together and heated with glycerol or a mixture thereof with sorbitol or mannitol, to give a resin soluble in benzene or ethyl alcohol or mixtures thereof or butanol.  Protracted heating to 250 DEG  C. gives an infusible resin insoluble in organic solvents which can be rendered soluble in oils, fats or benzene by heating to 340 DEG  C. or by introduction into fused resins.  (8) Phenol and paraldehyde are condensed together in the presence of hydrochloric acid and then mixed with colophony and fused with maleic anhydride. If desired cresol and formaldehyde may be condensed and heated with the condensation products obtained according to examples 1, 2 or 3 if desired in the presence of glycerol.  (9) The coumarone-indene fraction of coal tar is polymerized with the aid of acid such as borofluoroacetic acid and heated with maleic anhydride.  (10) Colophony, glycerine and phthalic anhydride are heated together and then heated with maleic anhydride or acid.  (11) Abietic acid hydroxyethylester is heated with maleic anhydride.  (12) Aconitic acid and colophony are heated together.  (13) Castor oil and the condensation product from example 1 or 2 are heated together with glycerine to give a resin soluble in benzene, turpentine oil, butanol and butyl acetate.  (14) The condensation product of examples 1, 2 or 3 is dissolved in benzene or toluene and heated with ethylene oxide. The product can be treated with colophony, hydrogenated colophony, carboxylic acids or the condensation products of examples 1, 2, or 3. (15) American colophony is heated with fumaric acid.  (16) Swedish tall oil (derived from the production of paper pulp with the aid of the sulphite process) is heated with maleic anhydride and then esterified with glycerine. (17, 18, 19) Abietic anhydride, amide or anilide is heated with maleic anhydride to give a resin soluble in ethyl alcohol. Specifications 289,794, 310,816, 317,225, 320,041, and 328,190, [all in Class 2 (iii), Dyes &c.], are referred to.  Abietic acid hydroxyethyl ester is obtained by treating abietic acid with ethylene oxide.  Abietic anhydride is obtained by heating French colophony with acetic anhydride.  Abietic amide is obtained by saturating a solution of abietic anhydride in benzene with gaseous ammonia.  Abietic anilide is obtained by heating abietic anhydride with aniline and washing with aqueous caustic soda and dilute hydrochloric acid.