Patent GB-499879-A (GB)
Title: Manufacture of capillary-active compounds
Filed: 1937-04-27
Abstract: Products suitable as emulsifying agents in the textile, leather and paper industries are obtained by rendering soluble in water compounds having the formula RXR1XR2 wherein R and R2 are alkyl, cycloalkyl, alkaryl or aralkyl hydrocarbon radicles containi at least one aliphatic chain of at least three carbon atoms, the aliphatic chains together containing not more than 20 carbon atoms, X is an ether or a carboxylic ester group and R1 is an aliphatic radicle having less than ten carbon atoms which may be interrupted by heteroatoms and carries at least one OH, NH2 or NH group.  Solubility is effected by treating the compounds with alkylating and/or acylating agents which either contain or react with the starting materials to form groups which impart solubility to the products.  The latter groups are the sulphuric acid ester and other inorganic poly-basic acid ester groups, the sulphonic acid, carboxylic acid, quaternary ammonium, betaine, oxyalkyl and poly(oxyalkyl) groups.  When the starting materials contain a hydroxy group in the radicle R1, they are treated (a) with sulphonating agents; (b) with sulpho-carboxylic acids or their halides, e.g. sulpho-acetic acid chloride, sulphobenzoic acid chloride or a halogen sulphonic acid such as bromethane sulphonic acid, benzyl chloride sulphonic acid or chlorpropanedisulphonic acid; (c) with anhydrides of polybasic carboxylic acids, e.g. succinic, maleic, phthalic, diglycollic and thiodiglycollic acids; (d) with halogen carboxylic acids, e.g. chloracetic or propionic acid; (e) with alkyleneoxides such as ethyleneoxide or glycide followed if desired by treatment with halogen sulphonic or carboxylic acids or with polycarboxylic acid anhydrides; (f) with phosgene followed by reaction with sarcosine, methyltaurine, methyl glycamine or albumen degradation products. When the starting materials contain an amino or imino group they are converted into quaternary ammonium salts or are treated (a) with sulphonating agents; (b) with halogenalkyl or halogenaralkylsulphonic acids; (c) with polycarboxylic acid anhydrides; (d) with halogen carboxylic acids or halogensulphonic acids followed, if desired, by conversion into betaines; (e) with aminoacids, hydroxyacids, polyhydroxy compounds or aminopolyhydroxy compounds after conversion of the amino group into the carbamic acid chloride or isocyanate.  The starting materials containing two ether groups may be derived on the one hand from aliphatic polyhydric alcohols or polyhydroxyamines, e.g. polyglycerine, trimethylolpropane, pentaerythritol, mannitol, sorbitol, diethanolamine, triethanol-amine, 1 : 3-dihydroxyaminopropane or dimethylglucamine and on the other from alcohols such as propyl, dodecyl and naphthene alcohols, abietinols, menthol, borneol, methylpentylcarbinol and dipentylcarbinol or from diisopropylphenol. Alcohols obtained by the oxidation of paraffins or catalytic hydrogenation of carbon monoxide may also be used.  The starting materials containing two carboxylic ester groups may be made (a) by esterifying the hydroxyalcohols or hydroxyamines with butyric, hexylic, isododecylic, undecylenic, naphthenic or isobutylphenoxyacetic acids, or (b) by esterifying the above-mentioned alcohols with aliphatic hydroxy or amino polycarboxylic acids, e.g. malic, tartaric, citric, iminodiacetic, iminodipropionic and nitroloacetic acids.  In examples: (1) a  : g -di(b -ethylhexyl) glycerine ether, di - a  : g  - (p - iso - octylphenyl) glycerine ether, a -ethyl hexyltartronic acid ester and 1 : 3-glycerinedicaprylic acid ester are sulphonated; (2) a  : g -di(isobutylphenyl) ester of glycerine is sulphonated; (3) glycerine a  : g -diisobutyl phenyl ether and a  : g -di(isooctylcyclohexyl) glycerine ether are reacted with ethylene oxide; (4) a  : g -di(isooctylphenyl) glycerine ether is treated with ethyleneoxide and sulphonated; (5) di(a  - ethyl - hexyl) glycerine ether and 1 : 3-glycerine di-capric acid ester are treated with diglycollic anhydride; (6) diisoheptylglycerine ether is treated with sulphoacetic acid or m-sulphobenzoic acid chloride; (7) a  : g -diisoamylether of glycerine is condensed with sodium chloracetate in the presence of sodium butylate; (8) the ether obtained from ethyleneoxide and a  : g -di(b -ethylhexyl) glycerine ether is treated first with phosgene and then with the sodium salt of methyltaurine.  The following starting materials and products are also mentioned: the diether from sodium isohexyl alcoholate (2 mols.) and di(b -chlorethylamine (1 mol.) or diethanolamine sulphuric ester (1 mol.), the oxyethylation product of di(isohexyl diethanolamine ether and the sodium salt of the diisoamylether of dihydroxyethyltaurine.  The products may be used in association with soap, mucilage, glue, water soluble cellulose derivatives, starch, bentonite, butanol, xylenylglycol, Glauber's salt, soda, sodium meta and pyrophosphate, trisodium phosphate, sodium borate and hypochlorite.  Samples have been furnished under Sect.2(5) of products prepared as follows: (1) the dinonylester of diethanolamine is rendered soluble by treatment with diglycollic acid; (2) esters derived from polyglycerine and a carboxylic acid mixture obtained by the oxidation of paraffin are treated with ethyleneoxide. Specification 395,853 is referred to.  According to the Provisional Specification, X in the formula given above may be any ester group and compounds containing two sulphonic ester groups are mentioned.ALSO:Products suitable as wetting, emulsifying, penetrating and levelling agents in the textile, leather and paper industries, e.g. in mercerizing and dyeing are obtained by rendering soluble in water compounds having the formula RXR1XR2 wherein R and R2 are alkyl, cycloalkyl, alkaryl or aralkyl hydrocarbon radicles containing at least one aliphatic chain of at least three carbon atoms, the aliphatic chains together containing not more than 20 carbon atoms, X is an ether or a carboxylic ester group and R1 is an aliphatic radicle having less than ten carbon atoms which may be interrupted by heteroatoms and carries at least one OH, NH2 or NH group.  Solubility is effected by treating the compounds with alkylating and/or acylating agents which either contain or react with the starting materials to form groups which impart solubility to the products. The latter groups are the sulphuric acid ester and other inorganic polybasic acid ester groups, the sulphonic acid, carboxylic acid, quaternaryammonium, betaine, oxyalkyl and poly(oxyalkyl) groups. When the starting materials contain a hydroxy group in the radicle R1, they are treated (a) with sulphonating agents, e.g. in the presence of dimethylether, dichlormethane, dichlorethane, carbon tetrachloride or pyridine; (b) with sulphocarboxylic acids or their halides, e.g. sulphoacetic acid chloride, sulphobenzoic acid chloride or a halogen sulphonic acid such as bromethane sulphonic acid, benzyl chloride sulphonic acid or chlorpropanedisulphonic acid; (c) with anhydrides of polybasic carboxylic acids, e.g. succinic, maleic, phthalic, diglycollic and thiodiglycollic acids; (d) with halogen carboxylic acids, e.g. chloracetic or propionic acid; (e) with alkyleneoxides such as ethyleneoxide or glycide followed, if desired, by treatment with halogen sulphonic or carboxylic acids or polycarboxylic acid anhydrides; (f) with phosgene followed by reaction with sarcosine, methyltaurine, methyl glucamine or albumen degradation products. When the starting materials contain an amino or imino group they are converted into quaternary ammonium salts or are treated (a) with sulphonating agents; (b) with halogenalkyl or halogenaralkylsulphonic acids; (c) with polycarboxylic acid anhydrides; (d) with halogen carboxylic acids or halogensulphonic acids followed, if desired, by conversion into betaines; (e) with amino acids, hydroxy acids, polyhydroxy compounds or aminopolyhydroxy compounds after conversion of the amino group into the carbamic acid chloride or isocyanate. The starting materials containing two ether groups may be derived on the one hand from aliphatic polyhydric alcohols or polyhydroxyamines, e.g. polyglycerine, trimethylolpropane, pentaerythritol, mannitol, sorbitol, diethanolamine, triethanol-amine, 1 : 3-dihydroxyaminopropane or dimethylglucamine and on the other from alcohols such as propyl, dodecyl and naphthene alcohols, abietinols, menthol, borneol, methylpentylcarbinol and dipentylcarbinol or from di-isopropylphenol.  Alcohols obtained by the oxidation of paraffins or catalytic hydrogenation of carbon monoxide may also be used. Instead of the hydroxy alcohols or hydroxyamines, their halogenhydrins, sulphuric esters or alkylene oxide derivatives may be used for the manufacture of the diethers. The starting materials containing two carboxylic ester groups may be made (a) by esterifying the hydroxyalcohols or hydroxyamines with carboxylic acids, e.g. butyric, hexylic, isododecylic, undecylenic, naphthenic or isobutylphenoxyacetic acids, or (b) by esterifying the above-mentioned alcohols with aliphatic hydroxy or amino polycarboxylic acids, e.g. malic, tartaric, citric, iminodiacetic, iminodipropionic and nitroloacetic acids.  In examples: (1) a  : g -di(b -ethylhexyl) glycerine ether, di-a  : g -(p-isooctylphenyl) glycerine ether, a -ethyl hexyltartronic acid ester and 1 : 3-glycerinedicaprylic acid ester are sulphonated; (2) a  : g -di(isobutylphenyl) ester of glycerine, prepared from glycerine dichlorhydrin and sodium isobutylphenolate is sulphonated; (3) glycerine a  : g -diisobutylphenylether and a  : g -di(isooctylcyclohexyl) glycerine ether are reacted with ethylene oxide; (4) a  : g -di(isooctylphenyl) glycerine ether is treated with ethyleneoxide and sulphonated; (5) di(a -ethyl-hexyl) glycerine ether and 1 : 3-glycerine dicapric acid ester are treated with diglycollic anhydride; (6) diisoheptylglycerine ether is treated with sulph