Patent GB-351945-A (GB)
Title: Improvements in the manufacture and production of resinous materials
IPC: C09F1/00
Filed: 1929-12-16
Abstract: Oily or solid resinous products are obtained by esterifying alcohols containing more than three hydroxyl groups, but excluding carbohydrates, with difficultly volatile monobasic aliphatic carboxylic acids of cyclic or open chain structure, and simultaneously with resinic acids.  It is preferred to take a quantity of alcohol corresponding to at least 6 hydroxyl groups per quantity of acids corresponding to 5 carboxyl groups, the ratio of resinic acid to aliphatic acid being variable to any extent.  The esterification may be carried out by heating the whole of the reaction components to an elevated temperature, if desired with the application of pressure or vacuum, or of a current of gas or vapour passed through the reaction mass, with or without the use of condensing agents such as gaseous hydrochloric acid, zinc chloride, or boric acid; or the esterification may be carried out by using a glyceride of the aliphatic carboxylic acid instead of the acid itself, glycerol being split off during the reaction.  The temperatures of working are generally between 120 DEG  and 300 DEG C., the range 150 DEG -280 DEG  C. being preferred.  The resulting products may be modified by subjecting them to an after treatment e.g. they may be blown with air or oxygen, if desired at elevated temperatures and/or in the presence of oxygen transferrers such as siccatives, or they may be vulcanized with the aid of sulphur or agents furnishing sulphur, or they may be polymerized by heat and/or condensing agents such as zinc chloride or boric acid.  They may be bleached with decolourizing agents, e.g. carbon, fuller's earth, or sulphur dioxide.  The products containing radicles of drying oil acid may be employed for coating purposes in combination with solvents and, preferably, with siccatives.  These coating compositions may also be worked up with body colours or fillers.  Cellulose esters may also be incorporated with solutions of the esters prepared according to the present invention.  The condensation products containing residues of non-drying acids are useful as softening agents e.g. for synthetic resins such as polymerization products of vinyl compounds or the product of condensation of formaldehyde with a phenol or a urea, or for cellulose derivatives, as homogeneous solutions with cellulose esters, especially nitrocellulose, may be obtained. Examples of the polyhydric alcohols which may be used are pentaerythritol, sorbitol, mannitol and dulcitol; suitable aliphatic acids are linoleic acids or the mixture of acids arising from the saponification of linseed oil, tung oil fatty acids, ricinoleic acid, oleic acid, stearic acid, China wood oil acids, soya bean oil acids, naphthenic acids and montanic acids; suitable resinic acids are colophony and copal acid.  Examples are given in which (1) linoleic acid, colophony and sorbitol are heated to 260 DEG  C. under reduced pressure in the presence of boric acid while passing carbon dioxide therethrough.  A little benzoyl peroxide is added and air blown through the reaction product at 110 DEG -120 DEG  C. A coating composition is obtained by dissolving the product in suitable solvents e.g. aromatic hydrocarbons, solvent naphtha, benzene, esters, ketones, higher alcohols or mixtures thereof. (2) The product of a condensation similar to that of example (1) may be worked up into coating preparations e.g. with oil of turpentine.  The product may be vulcanized with sulphur at elevated temperatures, e.g. in the presence of diphenyl guanidine. (3) Ricinoleic acid, colophony and dulcitol are heated in the presence of gaseous hydrochloric acid. The product may be worked up with nitrocellulose, dyestuffs and solvents into nitrocellulose lacquers.  (4) Pentaerythritol, linoleic acid, and colophony or copal acid are heated with boric acid.  The product may be blown with air, preferably with the addition of a little lead-manganese linoleate or similar salt.  (5) The product of a condensation similar to that of example (1) is soluble in liquefied or oily paraffin wax, and may be used in oil varnishes.  The resin may be bleached with sulphur dioxide, A priming composition is obtained by mixing 15 parts of the resin in a hopper mill with 60 parts of a filler consisting of 25 per cent of iron red, 30 per cent of talc, 25 per cent of slate meal and 20 per cent lithopone, and with 25 parts of solvent naphtha.  (6) Sorbitol, colophony, montanic acid and linoleic, stearic, oleic or ricinoleic acid are esterified in the presence of boric acid or zinc chloride, the water vapour formed being removed by suction.  The product may be employed as an adhesive for driving belts.  (7) The product obtained from sorbitol, montanic acid and colophony is soluble in the solvents referred to in example (1), and may be worked up into matte varnishes.  (8) Sorbitol is esterified with colophony, linoleic acid and China wood oil acids. The product may be employed as an oil varnish.  (9) Sorbitol is esterified with colophony and the acids of China wood and soya bean oils.  (10) Linseed oil is treated with colophony and sorbitol. Glycerol is liberated.  The product has the same properties as in example (1). (11) Sorbitol is esterified with colophony and naphthenic acids. Elastic coatings may be obtained by evaporation of a solution of this resin in benzene.  Specifications 306,452 and 306,453, [both in Class 2 (iii), Dyes &c.], are referred to.ALSO:Oily or solid resinous products are obtained by esterifying alcohols containing more than three hydroxyl groups, but excluding carbohydrates, with difficulty volatile monobasic aliphatic carboxylic acids of cyclic or open chain structure, and simultaneously with resinic acids.  It is preferred to take a quantity of alcohol corresponding to at least 6 hydroxyl groups per quantity of acids corresponding to 5 carboxyl groups, the ratio of resinic acid to aliphatic acid being variable to any extent.  The esterification may be carried out by heating the whole of the reaction components to an elevated temperature, if desired with the application of pressure or vacuum, or of a current of gas or vapour passed through the reaction mass, with or without the use of condensing agents such as gaseous hydrochloric acids, zinc chloride, or boric acid; or the esterification may be carried out by using a glyceride of the aliphatic carboxylic acid instead of the acid itself, glycerol being split off during the reaction.  The temperatures of working are generally between 120 and 300 DEG  C., the range 150-280 DEG  C. being preferred.  The resulting products may be modified by subjecting them to an after treatment, e.g. they may be blown with air or oxygen, if desired at elevated temperatures and/or in the presence of oxygen transferrers such as siccatives, or they may be vulcanized with the aid of sulphur or agents furnishing sulphur, or they may be polymerized by heat and/or condensing agents such as zinc chloride or boric acid.  They may be bleached with decolourizing agents, e.g. carbon, fuller's earth, or sulphur dioxide.  The products containing radicles of drying oil acids may be employed for coating purposes in combination with solvents and, preferably, with siccatives.  These coating compositions may also be worked up with body colours or fillers.  Cellulose esters may also be incorporated with solutions of the esters prepared according to the present invention.  The condensation products containing residues of non-drying acids are useful as softening agents, e.g. for synthetic resins such as polymerization products of vinyl compounds or the product of condensation of formaldehyde with a phenol or a urea, or for cellulose derivatives, as homogeneous solutions with cellulose esters, especially nitrocellulose, may be obtained.  Examples of the polyhydric alcohols which may be used are pentaerythritol, sorbitol, mannitol and dulcitol; suitable aliphatic acids are linoleic acids or the mixture of acids arising from the saponification of linseed oil, tung oil fatty acids, ricinoleic acid, oleic acid, stearic acid, China wood oil acids, soya bean oil acids, naphthenic acids, and montanic acids; suitable resinic acids are colophony and copal acid. Examples are given in which (1) linoleic acid, colophony, and sorbitol are heated to 260 DEG  C. under reduced pressure in the presence of boric acid while passing carbon dioxide there-through.  A little benzoyl peroxide is added and air blown through the reaction product at 110-120 DEG  C.  A coating composition is obtained by dissolving the product in suitable solvents, e.g. aromatic hydrocarbons, solvent naphtha, benzine, esters, ketones, higher alcohols or mixtures thereof.  (2) The product of a condensation similar to that of Example (1) may be worked up into coating preparations, e.g. with oil of turpentine.  The product may be vulcanized with sulphur at elevated temperatures, e.g. in the presence of diphenyl guanidine.  (3) Ricinoleic acid, colophony and dulcitol are heated in the presence of gaseous hydrochloric acid. The product may be worked up with nitrocellulose, dyestuffs and solvents into nitrocellulose lacquers.  (4) Pentaerythritol, linoleic acid, and colophony or copal acid are heated with boric acid.  The product may be blown with air, preferably with the addition of a little lead-manganese linoleate or similar salt.  (5) The product of a condensation similar to that of Example (1) is soluble in liquefied or oily paraffin wax, and may be used in oil varnishes. The resin may be bleached with sulphur dioxide.  A primary composition is obtained by mixing 15 parts of the resin in a hopper mill with 60 parts of a filler consisting of 25 per cent of iron red, 30 per cent of talc, 25 per cent of slate meal and 20 per cent lithopone, and with 25 parts of solvent naphtha.  (6) Sorbitol, colophony, montanic acid and linoleic, stearic, oleic or ricinoleic acid are heated in the presence of