Patent GB-462967-A (GB)
Title: Manufacture of quaternary ammonium compounds
Filed: 1935-09-10
Abstract: Quaternary ammonium compounds containing a carboxylic amide group are obtained by reacting (a) a quaternary ammonium compound of the formula XN(Halogen)RCOOR<1>, where XN is a tertiary aliphatic amine, R is an aliphatic hydrocarbon radicle of 1--4 carbon atoms, and R<1> is an aliphatic hydrocarbon radicle, with (b) a compound of the formula HNXX<1>, where X is hydrogen or an aliphatic or carbocyclic hydrocarbon radicle, which may be substituted by halogen or an amino, hydroxy, sulphonic or carboxylic group, and X<1> is hydrogen or an aliphatic hydrocarbon radicle.  The quaternary ammonium compounds used as starting materials are obtainable by addition of tertiary aliphatic amines to esters of the formula (Halogen)RCOOR<1>, where R and R<1> are as above.  Suitable tertiary amines for use in making the starting materials are trimethylamine, tributylamine, butyldiethanolamine, amyldipropanolamine, triethanolamine, tripolyethanolamine, methyl - bis - (dihydroxypropyl)amine, tetramethylethylenediamine, tetraoxyethylethylenediamine, tertiary polyethylenepolyamines, dimethylglucamine, hexadecylmethylglucamine, dodecyldimethylamine, oleyldiethanolamine, and stearyldipolyethanolamine; suitable amines are also obtainable from the acids of oils, fats and waxes by converting them in known manner into primary amines, and alkylating, hydroxyalkylating or polyhydroxyalkylating the latter to the tertiary stage.  Suitable esters for use in making the quaternary starting materials are those of chloracetic, a - and b -chloropropionic, and a -bromobutyric acids.  The products are useful (a) as wetting, cleansing and emulsifying agents in the treatment of textiles, skins and leather, (b) as agents for softening, brightening, fulling or sizing artificial silk and other textiles; (c) as levelling, through-dyeing or fixing agents in the dyeing industry; (d) as additions to mercerizing lyes; and (e) as agents for stabilizing foam in flotation processes; the products may be used in the form of aqueous solutions or dispersions of their solutions in organic solvents.  In the examples: (1) the addition product of butyldiethanolamine and ethyl chloracetate is treated with butylamine; the addition product of methyldiethanolamine and methyl chloracetate, or of triethanolamine and butyl chloracetate, or of dipropanolbutylamine and butyl chloracetate, may be similarly treated; (2) the addition product of butyldiethanolamine and methyl chloracetate is treated with dodecylamine; the product is useful as an emulsifying agent for oils, fats and waxes; (3) the addition product of trimethylamine and methyl chloracetate is treated with oleylamine; the product may be used for improving the fastness of substantive dyeings to water and perspiration, and also for pretreating vegetable fibres and cellulose artificial silks, to impart to these materials an affinity for acid wool dyes; for the latter purpose, the freshly extruded threads may be treated with the product during coagulation, or the product may be added to viscose; (4) the addition product of palmnut oil dimethylamine and methyl chloracetate is treated with methylamine to yield a product useful for increasing the dye-absorbing capacity of wool; the product, however, is unsuitable for use in baths containing acid dyes, for which purpose a product prepared from a tertiary amine containing polyglycol ether radicles is preferable; thus, stearylamine may be converted into a tertiary amine by reaction with 10 mols. of ethylene oxide, and the product treated first with methyl chloracetate or b -chloropropionate and then with methylamine; palmnut oil amine or oleylamine may be used in place of stearylamine, and taurine or methyltaurine may replace methylamine; (5) the addition product of tetramethylethylenediamine and methyl chloracetate is treated with ethylenediamine, butylamine, dodecylamine, or stearylmethylamine; (6) the addition product of stearyldimethylamine and methyl chloracetate is treated with methyltaurine, sarcosine, or albumen degradation products; (7) the addition product of stearyldimethylamine and methyl g -chlorobutyrate is treated with dibutylamine; (8) the addition product of trimethylamine and ethyl b -chloropropionate is treated with oleylamine; the product may be used for treating cellulosic materials, to impart to them an affinity for acid wool dyes.ALSO:Quaternary ammonium compounds containing a carboxylic amide group, useful as emulsifying agents, are obtained by reacting (a) a quaternary ammonium compound of the formula XN (Halogen)RCOOR<1>, where XN is a tertiary aliphatic amine, R is an aliphatic hydrocarbon radicle of 1--4 carbon atoms, and R<1> is an aliphatic hydrocarbon radicle, with (b) a compound of the formula HNXX<1>, where X is hydrogen or an aliphatic or carbocyclic hydrocarbon radicle, which may be substituted by halogen or an amino, hydroxy, sulphonic or carboxylic group, and X<1> is hydrogen or an aliphatic hydrocarbon radicle.  The quaternary ammonium compounds used as starting materials are obtainable by addition of tertiary aliphatic amines to esters of the formula (Halogen)RCOOR<1> where R and R<1> are as above.  Suitable tertiary amines for use in making the starting materials are trimethylamine, tributylamine, butyldiethanolamine, amyldipropanolamine, triethanolamine, tripolyethanolamine, methyl-bis-(dihydroxypropyl)amine, tetramethylethylenediamine, tetraoxyethylethylenediamine, tertiary polyethylenepolyamines, dimethylglucamine, hexadecylmethylglucamine, dodecyldimethylamine, oleyldiethanolamine, and stearyldipolyethanolamine suitable amines are also obtainable from the acids of oils, fats and waxes by converting them in known manner into primary amines, and alkylating, hydroxyalkylating or polyhydroxyalkylating the latter to the tertiary stage.  Suitable esters for use in making the quaternary starting materials are those of chloracetic, a - and b -chloropropionic, and a -bromobutyric acids.  In the examples, (1) the addition product of butyldiethanolamine and ethyl chloracetate is treated with butylamine the addition product of methyldiethanolamine and methyl chloracetate, or of triethanolamine and butyl chloracetate, or of dipropanolbutylamine and butyl chloracetate, may be similarly treated; (2) the addition product of butyldiethanolamine and methyl chloracetate is treated with dodecylamine; the product is useful as an emulsifying agent for oils, fats and waxes; (3) the addition product of trimethylamine and methyl chloracetate is treated with oleylamine; (4) (a) the addition product of palmnut oil dimethylamine and methyl chloracetate is treated with methylamine; (b) stearylamine is converted into a tertiary amine by reaction with 10 mols of ethylene oxide, and the product treated first with methyl chloracetate or b -chloropropionate and then with methylamine; palmnut oil amine or oleylamine may be used in place of stearylamine, and taurine or methyltaurine may replace methylamine; (5) the addition product of tetramethylethylenediamine and methyl chloracetate is treated with ethylenediamine butylamine, dodecylamine, or stearylmethylamine; (6) the addition product of stearyldimethylamine and methyl chloracetate is treated with methyltaurine, sarcosine or albumen degradation products; (7) the addition product of stearyldimethylamine and methyl #c-chlorobutyrate is treated with dibutylamine; (8) the addition product of trimethylamine and ethyl b -chloropropionate is treated with oleyamine.ALSO:Quaternary ammonium compounds containing a carboxylic amide group, useful as agents for stabilizing foam in flotation processes, are obtained by reacting (a) a quaternary ammonium compound of the formula XN(Halogen)RCOOR1, where XN is a tertiary aliphatic amine, R is an aliphatic hydrocarbon radicle of 1-4 carbon atoms, and R1 is an aliphatic hydrocarbon radicle, with (b) a compound of the formula HNXX1, where X is hydrogen or an aliphatic or carbocyclic hydrocarbon radicle, which may be substituted by halogen or an amino, hydroxy, sulphonic or carboxylic group, and X1 is hydrogen or an aliphatic hydrocarbon radicle.  The quaternary ammonium compounds used as starting materials are obtainable by addition of tertiary aliphatic amines to esters of the formula (Halogen)-RCOOR1 where R and R1 are as above.  Suitable tertiary amines for use in making the starting materials are trimethylamine, tributylamine, butyldiethanolamine, amyldipropanolamine, triethanolamine, tripolyethanolamine, methyl-bis-(dihydroxypropyl)amine, tetramethylethylenediamine, tetraoxyethylethylenediamine, tertiary polyethylenepolyamines, dimethylglucamine, hexadecylmethylglucamine, dodecyldimethylamine, oleyldiethanolamine, and stearyldipolyethanolamine; suitable amines are also obtainable from the acids of oils, fats, and waxes by converting them in known manner into primary amines, and alkylating, hydroxyalkylating or polyhydroxyalkylating the latter to the tertiary stage.  Suitable esters for use in making the quaternary starting materials are those of chloracetic, a  and b -chloropropionic, and a -bromobutyric acids.  The products may be used in the form of aqueous solutions or dispersions of their solutions in organic solvents.  In the examples, (1) the addition product of butyldiethanolamine and ethyl chloracetate is treated with butylamine; the addition product of methyldiethanolamine and methyl chloracetate, or of triethanolamine and butyl chloracetate, or of dipropanolbutylamine and butyl chloracetate, may be similarly treated; (2) the addition product of butyldiethanolamine and methyl chloracetate is treated with dodecylamine; the product is useful as an emulsifying agent for oils, fats and waxes; (3) the addition product of trimethylamine and methyl chloracetate is treated with oleylamine; (4) (a) the addition product of palmnut oil dimethylamine and methyl chloracetate is treated with methylamine; (b) stearylam