Patent GB-350425-A (GB)
IPC: C11C3/00
Filed: 1930-02-05
Abstract: Alkyl, aralkyl and aryl esters of sulphonated carboxylic acids, similar to the products of Specification 315,832, [Class 91, Oils &c.], and stated to be emulsifying and fat-splitting agents, are prepared (a) by treating aralkyl or aryl esters of aliphatic carboxylic acids containing at least 9 carbon atoms or alkyl, aralkyl or aryl esters of cyclic carboxylic acids not containing hydroxy groups, with intensive sulphonating agents, namely, oleum, sulphur trioxide, brom- or chlor-sulphonic acid, or with mixtures of anhydrous lower fatty acids or their anhydrides or chlorides with any sulphonating agent, and (b) by treating alkyl esters of aliphatic carboxylic acids containing at least 9 carbon atoms with oleum, sulphur trioxide or brom- or chlor-sulphonic acid.  In a further modification, the carboxylic acids themselves are treated with an intensive sulphonating agent or with said mixture of sulphonating agents and lower fatty acids &c., and a phenol or alcohol added to the reaction mixture or to one of the components before, during, or after the sulphonation.  The sulphonating agents may also be allowed to react with the lower fatty acids and the products, e.g. acetylsulphuric acid, used to sulphonate the carboxylic esters.  In examples: (1) ricinoleic n-butyl ester is sulphonated with oleum: (2) ricinoleic methyl cyclohexanol ester is sulphonated in ether with chlorsulphonic acid: (3) oleic benzyl ester is sulphonated with oleum: (4) ricinoleic iso-butyl ester is sulphonated with oleum in the presence of acetic anhydride: (5) b -naphthoic acid iso-propyl ester is sulphonated with chlorsulphonic acid: (6) ricinoleic fatty acid is sulphonated with oleum and iso-butyl alcohol then added: (7) 12-hydroxystearic acid is mixed with n-butyl alcohol and sulphonated below 0 DEG  C. with chlorsulphonic acid: (8) oleic acid is sulphonated with a mixture of oleum and acetic anhydride or acetyl sulphuric acid and iso-propyl alcohol added to the crude product: (9) b -naphthoic acid is sulphonated with chlorsulphonic acid and iso-propyl alcohol added to the sulphonated product: (10) butyl sulphuric acid chloride is used to sulphonate ricinoleic fatty acid. Specifications 282,626, 288,127, 293,690, and 296,999, [all in Class 2 (iii), Dyes &c.], also are referred to.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use of alkyl sulphuric acids as sulphonating agents, and includes the intense sulphonation of alkyl esters of aliphatic carboxylic acids, and of cyclic acids containing a carboxy group in the side chain for the production of emulsifying and fat-splitting agents.  This subject-matter does not appear in the Specification as accepted.ALSO:Alkyl, aralkyl, and aryl esters of sulphonated carboxylic acids are prepared (a) by treating aralkyl or aryl esters of fatty acids containing at least 9 carbon atoms, or alkyl, aralkyl, or aryl esters of cyclic carboxylic acids not containing hydroxy groups with per se intensive sulphonating agents, namely, oleum, sulphur trioxide, bromsulphonic acid or chlorsulphonic acid, or with mixtures of anhydrous lower fatty acids, their anhydrides or chlorides with any sulphonating agent, and (b) by treating alkyl esters of fatty acids containing at least 9 carbon atoms with the said per se intensive sulphonating agents.  In a further modification, the carboxylic acids themselves are treated with per se intensive sulphonating agents or with said mixture of sulphonating agents and lower fatty acids &c. and an alcohol or phenol is added to the reaction mixture or to one of the components before, during or after the sulphonation.  The sulphonating agents may also be allowed to react with the lower fatty acids and the products, e.g. acetylsulphuric acid, used to sulphonate the carboxylic esters.  In examples: (1) ricinoleic n-butyl ester is sulphonated with oleum; (2) ricinoleic methyl cyclohexanol ester (prepared by heating the acid with methyl cyclohexanol under reflux in the presence of hydrochloric acid) is sulphonated in ether with chlorsulphonic acid; (3) oleic benzyl ester is sulphonated with oleum; (4) ricinoleic iso-butyl ester is sulphonated with oleum in the presence of acetic anhydride: (5) b -naphthoic acid iso-propyl ester (prepared in the usual manner from the acid and the alcohol) is sulphonated with chlorsulphonic acid; (6) ricinoleic fatty acid is sulphonated with oleum and iso-butyl alcohol then added; (7) 12-hydroxystearic acid is mixed with n-butyl alcohol and sulphonated below 0 DEG  C. with chlorsulphonic acid; (8) oleic acid is sulphonated with a mixture of oleum and acetic anhydride or acetyl sulphuric acid and iso-propyl alcohol added to the crude product; (9) b -naphthoic acid is sulphonated with chlorsulphonic acid and iso-propylalcohol added to the sulphonated product; (10) butyl sulphuric acid chloride is used to sulphonated ricinoleic fatty acid.  The products exhibit to an enhanced extent the properties of the products of Specification 315,832, [Class 2 (iii), Dyes &c.], and may be used as wetting, penetrating, foaming, and dispersing agents in the textile and leather industries.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use of alkyl sulphuric acids as sulphonating agents, and includes the intense sulphonation of alkyl esters of aliphatic carboxylic acids, and of cyclic acids containing a carboxy group in the side chain.  This subject-matter does not appear in the Specification as accepted.  Specifications 282,626, 288,127, 293,690, and 296,999, [all in Class 2 (iii), Dyes &c.], also are referred to.ALSO:Alkyl, aralkyl and aryl esters of sulphonated carboxylic acids, which are similar to the products of Specification 315,832, [Class 82 (ii), Washing granular &c.], and may be used as wetting agents in etching and corrosive baths for metals, and for wetting metal and other powders are prepared (a) by treating aralkyl or aryl esters of aliphatic carboxylic acids containing at least 9 carbon atoms or alkyl, aralkyl or aryl esters of cyclic carboxylic acids not containing hydroxy groups, with intensive sulphonating agents, namely, oleum, sulphur trioxide, brom- or chlor-sulphonic acid, or with mixtures of anhydrous lower fatty acids or their anhydrides or chlorides with any sulphonating agent, and (b) by treating alkyl esters of aliphatic carboxylic acids containing at least 9 carbon atoms with oleum, sulphur trioxide or brom- or chlor-sulphonic acid.  In a further modification, the carboxylic acids themselves are treated with an intensive sulphonating agent or with said mixture of sulphonating agents and lower fatty acids &c. and a phenol or alcohol is added to the reaction mixture or to one of the components before, during, or after the sulphonation. The sulphonating agents may also be allowed to react with the lower fatty acids and the products, e.g. acetylsulphuric acid, used to sulphonate the carboxylic esters.  In examples: (1) ricinoleic n-butyl ester is sulphonated with oleum; (2) ricinoleic methyl cyclohexanol ester is sulphonated in ether with p  chlorsulphonic acid; (3) oleic benzyl ester is sulphonated with oleum; (4) ricinoleic iso butyl ester is sulphonated with oleum in the presence of acetic anhydride; (5) b -naphthoic acid iso propyl ester is sulphonated with chlorsulphonic acid; (6) ricinoleic fatty acid is sulphonated with oleum and iso butyl alcohol then added; (7) 12-hydroxystearic acid is mixed with n-butyl alcohol and sulphonated below 0 DEG  C. with chlorsulphonic acid; (8) oleic acid is sulphonated with a mixture of oleum and acetic anhydride or acetyl sulphuric acid and iso propyl alcohol added to the crude product; (9) b -naphthoic acid is sulphonated with chlorsulphonic acid and iso-propylalcohol added to the sulphonated product; (10) butyl sulphuric acid chloride is used to sulphonated ricinoleic fatty acid.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use of alkyl sulphuric acids as sulphonating agents, and includes the intense sulphonation of alkyl esters of aliphatic carboxylic acids, and of cyclic acids containing a carboxy group in the side chain for the production of similar wetting agents.  This subject-matter does not appear in the Specification as accepted.  Specifications 282,626, 288,127, 293,690, and 296,999, [all in Class 2 (iii), Dyes &c.], are referred to.