Patent GB-667384-A (GB)
Title: Manufacture of new partial esters of sulphides of polybasic carboxylic acids
Filed: 1949-03-17
Abstract: Partial esters of sulphides of polybasic carboxylic acids are prepared by reacting an aliphatic mercaptocarboxylic acid or a salt thereof with an ester of an unsaturated aliphatic carboxylic acid containing in at least one ester group the residue of a cycloaliphatic alcohol or an aliphatic hydroxy compound containing a chain of at least six carbon atoms, optionally in the presence of an alkaline accelerator.  Especially suitable accelerators are substances of alkaline reaction such as alkali hydroxides, alkali alcoholates or organic bases such as piperidine.  Room temperature or elevated temperature may be employed.  When using a salt of a mercapto carboxylic acid the presence of a solvent such as an alcohol and water mixture is advantageous.  Mercapto carboxylic acids mentioned are thioglycollic acid, thiolactic acid and b -mercapto-butyric acid.  The ester starting materials are derived from aliphatic unsaturated mono- or dibasic carboxylic acids including among others acrylic, methacrylic, maleic, fumaric, citraconic, itaconic and mesaconic acids and cycloaliphatic alcohols or aliphatic hydroxy compounds containing a chain of at least six carbon atoms representative of which are hexyl alcohols, octyl alcohols, lauryl and oleyl alcohols, hydroxyalkyl ethers of these aliphatic alcohols, for example mono-ethers with ethylene glycol or poly-glycols, hydroxyalkyl esters or N-hydroxyalkylamides of fatty acids having at least 12 carbon atoms representative of which are stearic acid b -hydroxyethyl ester, stearic acid diglyceride and oleic acid N-(b -hydroxyethyl)-amide, esters or amides of hydroxycarboxylic acids including glycollic acid octadecyl ester and ricinoleic acid methyl ester, cycloaliphatic alcohols such as methyl cyclohexanol, terpene alcohols and alcohols corresponding to resin acids such as di-and tetra-hydro-abietyl alcohol or mixtures thereof. The products may be used as textile assistants, softening, foaming, washing or emulsifying agents (see Group IV (c)).  In examples: (1-4) Thioglycollic acid is heated, with oxygen excluded, with diesters derived from maleic acid and oleic acid N-(b -hydroxyethyl)-amide, stearic acid-N-(b -hydroxyethyl)-amide, (2-ethyl hexyl) alcohol and (2-ethyl butyl) alcohol respectively, the products in alcoholic solution being neutralized with sodium hydroxide.  The maleic acid diester starting material in example (1) is prepared by treating oleic acid N-(b -hydroxy ethyl)-amide with maleic anhydride, benzene and sulphuric acid until water is no longer split off. The reaction product is neutralized and benzene is distilled off. The diester starting material in example 2) is similarly prepared.ALSO:Partial esters of sulphides of polybasic carboxylic acids containing in at least one ester group the residue of a cycloaliphatic alcohol or an aliphatic hydroxy compound containing a chain of at least six carbon atoms are employed as textile assistants, softening or foaming, or washing agents.  The esters are derived from mercapto-carboxylic acids such as thioglycollic, thiolactic and b -mercapto-butyric acids and ester starting materials derived in turn from aliphatic unsaturated mono- or di-basic carboxylic acids such as acrylic, methacrylic, maleic, fumaric, citraconic, itaconic or mesaconic acids and cycloaliphatic alcohols or aliphatic hydroxy compounds containing a chain of at least six carbon atoms representative of which are hexyl alcohols, lauryl alcohol, oleyl alcohol, hydroxyalkyl ethers of these aliphatic alcohols such as the monoethers of the said alcohols with ethylene glycol or polyglycols, hydroxyalkyl esters of N-hydroxyalkylamides of fatty acids having at least six carbon atoms such as stearic acid b -hydroxyethyl ester, stearic acid diglyceride, oleic acid N-(b -hydroxyethyl)-amide, esters or amides of hydroxycarboxylic acids such as glycollic acid octadecyl ester, cycloaliphatic alcohols such as methylcyclohexanol, terpene alcohols and alcohols corresponding to resin acids such as dihydroor tetrahydro-abietyl alcohol or mixtures thereof.  The water soluble salts of the products may be used as textile assistants and the alkali salts are water soluble. Those products which contain, for example, two ester groups having alcohol residues of 6-10 carbon atoms, especially the residues of branched chain alcohols possess a good wetting action whilst those containing longer aliphatic chains, especially 16-18 carbon atoms and in particular two chains of 16 carbon atoms are suitable as softening agents for textile fibres. The products may be used alone or together with other salts or dispersing agents such as salts of sulphonated benzimidazoles substituted at the m -carbon atom by an alkyl group having at least 15 carbon atoms, mono-carboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols or fatty alcohol sulphonates or condensation products of higher fatty acids with aliphatic hydroxy- or amino-sulphonic acids.  In examples: (1) the sodium salt of the partial ester obtained by reacting thioglycollic acid with the diester of maleic acid with oleic acid N-(b -hydroxyethyl)-amide, for example, in admixture with the disodium salt of N - benzyl - m  - heptadecyl - benzimidazole disulphonic acid is used as a softening agent for cellulose fibres; (2) the sodium salt of the partial ester obtained by reacting thioglycollic acid with the diester of maleic acid with stearic acid - N - (b  - hydroxyethyl) - amide, advantageously in admixture with the disodium salt of N - benzyl - m - heptadecyl - benzimidazole disulphonic acid is used as a softening agent for cellulose fibres or wool; (3) and (4) sodium salts of partial esters obtained by reacting thioglycollic acid with maleic di-(2-ethylhexyl) ester and di-(2-ethyl-butyl) ester respectively are stated to be wetting agents; (5) viscose artificial silk is softened by treating with a solution of the softening mixture described in (1); (6) viscose p  crepe is softened and rendered crease-resistant by treatment with a mixture containing dimethyl urea, ammonia, ammonium chloride and the softening mixture described in (2); (7) chlorinated wool is softened by treatment with a solution of the softening mixture described in (1).ALSO:Partial esters of sulphides of polybasic carboxylic acids containing in at least one ester group the residue of a cycloaliphatic alcohol or an aliphatic hydroxy compound containing a chain of at least six carbon atoms are employed as emulsifying agents.