Patent GB-415789-A (GB)
Title: The manufacture of new reaction products from natural or synthetic waxes of the ester type
IPC: C11C3/00
Filed: 1933-03-03
Abstract: Natural or synthetic waxes of the ester type are heated to a temperature not exceeding 200 DEG  C. with a nitrogenous base containing one or two nitrogen atoms and at least one hydrogen atom attached to each nitrogen atom.  Specified waxes are carnauba wax, beeswax, wool fat, sperm oil and synthetic waxes obtainable by the catalytic reduction of higher fatty acids or by the oxidation of paraffin hydrocarbons; mixtures of the waxes with one another or with glycerides, higher fatty acids or higher alcohols may also be treated.  Specified bases are ammonia and primary or secondary aliphatic, cycloaliphatic aromatic-aliphatic or aromatic amines such as methylamine, mono-and dibutylamine, undecylamine, mono- and dibenzylamine, 1-amino-2 : 3-propanediol and the corresponding secondary amine, mono- and diethanolamine, mono- and dicyclohexylamine, aniline, toluidines, naphthylamines, phenylenediamines, ethylenediamine, methylaniline, and piperidine. The reaction products are mixtures containing carboxylic amides and wax alcohols.  The properties of the products may be modified by any of the following after-treatments:--(a) treatment with substituted or unsubstituted alkylene oxides or halogenhydrins, e.g. with ethylene oxide, glycide, epichlorhydrin, glycol chlorhydrin, glycerol mono- or di chlorhydrin, or polyglycerol chlorhydrin; (b) alkylation; (c) conversion into salts with organic or inorganic acids; (d) reaction with inorganic polybasic acids such as sulphuric or phosphoric acid or their chlorides, anhydrides, esters or amides; this treatment may be applied also to the products obtained as under (a) above.  Any of the products obtainable as above may be decolourized by treatment with oxidizing agents, such as peroxides or hypochlorites, or with adsorbents.  According to the reagents selected, products of varying degrees of solubility in water are obtained.  The products which are relatively soluble in water are useful as soap substitutes or as emulsifying agents, e.g. for oils, fats and hydrocarbons.  The products may be used alone or mixed with one another or with appropriate additions, e.g. soaps; turkey red oils; sulphonated mineral oils or fatty alcohols; glue; water-soluble gums; mucilages; alcohols; ketones; and hydrocarbons.  In examples, (1) sperm oil is heated to 140--150 DEG  C. with ethanolamine containing a little water to give a product useful for dispersing fatty oils or for dispersing water in paraffin hydrocarbons with the formation of salves; (2) a product obtained from sperm oil and ethanolamine, as in example 1, is sulphonated in carbon tetrachloride with a mixture of sulphuric and chlorsulphonic acids, to yield a product useful as a dispersing agent; (3) wool fat is heated to 160--170 DEG  C. with ethanolamine containing a little water; if the product is treated with ethylene oxide at 60--100 DEG  C. in the presence of aqueous alkali, a product useful for preparing oleic acid emulsions is obtained.  Specification 296,145, [Class 91], is referred to.  The Specification as open to inspection under Sect. 91 states that the following after-treatments may be applied to the reaction products of the wax and the nitrogenous base:--(a) condensation with aldoses or ketoses, such as glucose, mannose or maltose; (b) treatment with alkylating or aralkylating agents containing a sulpho group, e.g. chlorethanesulphonic acid, vinylsulphonic acid, acetaldehydesulphonic acid, or benzaldehydesulphonic acids; (c) reaction with carbonic or dithiocarbonic acid or their chlorides, anhydrides, esters or amides; (d) sulphonation in the presence of an aromatic hydrocarbon or a phenol; (e) acylation with sulphonic or carboxylic acids, e.g. sulphoacetic, sulphophthalic, lactic, salicyclic or gluconic acid. More than one after-treatment may be applied; for example, a product prepared from a wax and an alkylene diamine may be treated with chlorethanesulphonic acid and then alkylated, or a product prepared from a wax and diethanolamine may be treated with an aldehyde and a hydrogen halide and then converted into a sulphonic acid by reaction with a sulphite or thiosulphate.  The Specification states also that the products may be used in association with condensation products of higher fatty, naphthenic or resin acids with hydroxy- or amino-alkylsulphonic acids, albumins and their decomposition products, derivatives or conversion products of sulphite liquor, halogenated hydrocarbons, enzymes, and salts such as soda, sodium sulphate, and soluble phosphates and borates.  The examples given above are amplified as follows:--(1) in example 1, wool fat or mixtures thereof with sperm oil, with or without glycerides such as coconut oil, palm oil, soya bean oil, or cotton seed oil may be used as starting materials, and instead of ethanolamine there may be used diethanolamine, 1-amino-2 : 3-propanediol or the corresponding secondary amine, ammonia, or alkylanilines; (2) in example 2, a product obtained from sperm oil and ethanolamine, as in example 1, is treated with ethylene oxide and then sulphonated, or sulphonated in the presence of naphthalene, products of increased dispersing capacity being obtained; similar products are obtained if the wax is heated with ammonia, and the product treated with ethylene oxide and then sulphonated; if sulphuric acid in this example is replaced by phosphoric or pyrophosphoric acid or their anhydrides or chlorides, products useful for stabilizing solutions containing peroxides are obtained; if the product of example 1 is treated with ethylene oxide in the presence of caustic alkali, products useful as emulsifying agents for fatty acids or mineral oils, alone or with organic solvents such as carbon tetrachloride are obtained.  The following examples are also given:--(1) a reaction product from wool fat or sperm oil and ammonia or a primary or secondary alkylolamine is treated with up to three times the quantity of ethylene oxide; products useful as emulsifying agents are obtained; (2) wool fat, sperm oil, or a wax obtained by catalytic reduction of soya bean oil, is heated to 120--160 DEG  C. with ethylenediamine; solutions of the products in fats yield emulsions in water; if the products are alkylated, e.g. with dialkyl sulphates, alkyl halides, diazomethane, or halogenhydrins, products useful as emulsifying agents are obtained; alkylation with alkylene oxides in the presence of water or alkali also yields products useful as emulsifying agents; (3) a reaction product of wool fat, sperm oil or a synthetic wax and mono- or di-ethanolamine or a mixture thereof is converted into salts of dithiocarbonic acid by treatment with alkali and carbon disulphide; a reaction product of wool fat and ethylenediamine, or a product from wool fat and ammonia, (or a primary or a secondary alkylolamine) after-treated with an alkylene oxide, may be similarly treated; the products are useful as dispersing agents for vat dyes or naphthols; (4) a reaction product of ethylenediamine and a wax obtained by reducing soya bean oil is treated at 100--150 DEG  C. with chlorethanesulphonic acid (as sodium salt), this yielding a product useful as an emulsifying agent; the products may be alkylated, e.g. with dimethyl sulphate or an alkylene oxide, or acylated, e.g. with acetic anhydride or sulphuric or chlorsulphonic acid, products of similar properties being obtained; instead of chlorethanesulphonic acid there may be used benzylchloridesulphonic acids, b -chlorhydroxypropanesulphonic acids, or vinylsulphonic acid; (5) a reaction product of sperm oil and mono- or di-ethanolamine, 1-amino-2 : 3-propanediol, or the corresponding secondary amine, is heated with sodium ethylsulphoacetate, or with sodium sulphoacetate (NaO3SCH2COOH) or the corresponding salt of sulphopalmitic acid, products useful as emulsifying agents being obtained.  This subject-matter does not appear in the Specification as accepted.ALSO:Natural or synthetic waxes of the ester type are heated to a temperature not exceeding 200 DEG  C. with a nitrogenous base containing one or two nitrogen atoms and at least one hydrogen atom attached to each nitrogen atom.  The reaction may be accelerated by a metallic catalyst, e.g. nickel or cobalt or their oxides or salts. Specified waxes are carnauba wax, beeswax, wool fat, sperm oil and synthetic waxes obtainable by the catalytic reduction of higher fatty acids or by the oxidation of paraffin hydrocarbons; mixtures of the waxes with one another or with glycerides, higher fatty acids or higher alcohols may also be treated.  Specified bases are ammonia and primary or secondary aliphatic, cycloaliphatic, aromatic-aliphatic or aromatic amines such as methylamine, mono- and di-butylamine, undecylamine, mono- and di-benzylamine, 1-amino-2 : 3-propanediol and the corresponding secondary amine, mono- and di-ethanolamine, mono-and di-cyclohexylamine, aniline, toluidines, naphthylamines, phenylene-diamines, ethylenediamine, methylaniline and piperidine. The reaction products are mixtures containing carboxylic amides and wax alcohols.  The properties of the products may be modified by any of the following after-treatments : (a) treatment with substituted or unsubstituted alkylene oxides or halogenhydrins, e.g. with ethylene oxide, glycide, epichlorhydrin, glycol chlorhydrin, glycerol mono- or di-chlorhydrin, or polyglycerol chlorhydrin; (b) alkylation; (c) conversion into salts with organic or inorganic acids; (d) reaction with inorganic polybasic acids such as sulphuric or phosphoric acid or their chlorides, anhydrides, esters or amides; this treatment may be applied also to the products obtained as under (a) above.  Any of the products obtainable as above may be decolourized by treatment with oxidizing agents, such as peroxides or hypochlorites, or with adsorbents.  According to the reagents selected, products of varying degrees of solubility in water are obtained.  T