Patent GB-465200-A (GB)
Title: Improvements in the manufacture and production of valuable condensation products containing nitrogen, phosphorus or sulphur
IPC: D06P1/613
Filed: 1935-08-26
Abstract: Products useful as assistants in the textile, paper, lacquer, tanning and rubber industries are obtained by introducing one or more ether or polyether radicles into quaternary ammonium or phosphonium compounds or ternary sulphonium compounds by condensing the latter with polyhydric alcohols or etherifying derivatives thereof having at most six carbon atoms or with polyether compounds containing atoms or groups such as halogen which react with the said quaternary ammonium or phosphonium or ternary sulphonium compounds.  Specified components are: ethylene and propylene oxides, glycide, epichlorhydrin, dichlorhydrin, dichlordiethylether, glycol, glycerol, polyglycerol, glycolchlorhydrin, polyglycerolchloride and a -chlor tetraethylene glycol.  The quaternary phosphonium and ammonium compounds and the ternary sulphonium compounds may contain hydroxyl, carboxylic, amino or mercapto groups which react with the second components.  The same products may also be produced from any compound containing nitrogen, phosphorus or sulphur by first introducing the ether group or groups and then converting the resulting ethers into quaternary ammonium or ternary sulphonium compounds.  Thus, diethylbutanolamine, asymdimethylethylenediamine or sarcosine may be treated with ethyleneoxide and quaternary ammonium compounds produced by a final treatment with dimethylsulphate, ethylbromide or benzylchloride.  The following starting materials which contain radicles of high molecular weight are advantageously employed: dodecyldimethyl hydroxyethylammoniumhydroxide, stearyltrihydroxyethyl ammoniumhydroxide, dimethyloxyethyldibutylammoniumhydroxide, the monooleicester of tetrahydroxyethylammoniumhydroxide, dodecyldimethylcarboxymethylammoniumchloride (from dodecyldimethylamine and chloracetic acid), the reaction product of ethylenediamine with octodecyldimethylchlorethylammoniumchloride (from octodecyldimethylamine and ethylenechloride), the reaction product of dimethyl sulphate with stearyldiethylenetriamine, the quaternary ammonium compounds of oleylpiperazine (from piperazine and oleylsulphuric ester), quaternary ammonium compounds obtained by adding on dodecyl bromide, dodecahydroxymethylchloride or dodecathio methylchloride to tetramethyl-b -hydroxypropylenediamine, oleyldihydroxyethylamineoxide (from oleylamine, ethyleneoxide and hydrogen peroxide), stearylamine, oleylamine, dodecylmethylamine, didodecylamine, octodecylethylenediamine, dodecylpropylenediamine, and polyether derivatives of oleic acid amides of ethylenediamine, triethylenetetramine or ethylene diaminosorbitol (from glucose and ethylenediamine followed by reduction) and polyether derivatives of the reaction product of triethylenetetramine or aminosorbitol with trichlorinated paraffin wax or of oleylamide of piperazine.  The high molecular radicle may however be introduced when the ethers are converted into quaternary ammonium or ternary sulphonium compounds. The products may be condensed with chlorethane sulphonic acid, chloracetic acid, fatty acid chlorides, chlorcarbonic esters, isocyanates or treated with phosphoric acid or sulphonating agents. The wetting, dispersing, levelling, washing and softening properties of the products make them useful in the following processes; bleaching, bucking, carbonizing, mercerizing, stripping, printing, mordanting, fulling, dressing, waterproofing, crease-proofing and combating pests.  They may also be added to artificial silk spinning solutions, lubricants, textile oils, shoe polishes, pharmaceutical products, cosmetics and flotation agents.  They may be used in dyeing with acetate artificial silk dyes, and with vat, acid, substantive and basic dyes.  The products may be used in association with soaps, sulphuric esters and sulphonic acids, condensation products of fatty acid chlorides with albumen degradation products, aminocarboxylic acids, condensation products of alkyleneoxides with hydroxy, carboxy, amino or mercapto compounds, starch, dextrine, cellulose derivatives, sulphite cellulose, ortho-, pyro- or meta-phosphates, Glauber's salts, glue, mucilages, resins, waxes, oils, fats, solvents, cyclohexanol, hydrogen peroxide and other per compounds and reducing agents such as sodium hydrosulphite.  In examples: (1) stearylamine is treated with ethylene oxide and a quaternary ammonium compound formed by means of dimethylsulphate; the product may be added to bottoming or developing baths in dyeing with azo dyestuffs: (2) ethylenediamine or b  : b -dibutyl ethylenediamine is treated with ethyleneoxide and a quaternary ammonium compound formed with octodecylbromide: (3) dodecyldimethylhydroxyethylammoniumhydroxide or stearyl trihydroxyethylammonium hydroxide is treated with ethylene oxide; a soap of stearylamine and stearic acid is treated with ethyleneoxide or a salt with stearic acid is formed from the quaternary ammonium base obtained from stearyltrihydroxyethylammonium hydroxide and ethylene oxide: (4) propylene oxide is reacted with tetrahydroxyethylammonium hydroxide: (5) methyldodecylamine is treated first with ethylene oxide and then with dimethylsulphate; the product may be used in dyeing with Naphthol AS. and as an assistant in association with oleylsarcosine in bleaching with sodium hydrosulphite: (6) quaternary ammonium compounds are obtained by treating with dimethylsulphate the products obtained from oleylamine and ethyleneoxide: (7) dimethylsulphate is added to the condensation product of oleylamine and ethylene oxide and the resulting quaternary salt sulphonated; the product may be used for dyeing mercerized calico with Hydronblau R: (8) stearylamine is treated first with ethyleneoxide and then with ethylene chlorhydrin; the product which may be used with enzyme preparations may be used for washing wool or cotton: (9) an amide obtained from ethylenediamine or phenylenediamine and oleic acid or dodecylpropylenediamine or paraaminophenol is treated with ethyleneoxide and a quaternary ammonium salt formed with dimethylsulphate.  Specification 420,066 is referred to.  Samples have been furnished under Sect. 2 (5) of products prepared as follows: (1) triphenylphosphine is heated with ethylenechlorhydrin in the presence of potassium iodide and a quaternary phosphonium base formed by treating with ethyleneoxide: (2) ethylenediamine is treated with ethylene oxide and high molecular residues of palm kernel oil introduced into the resulting quaternary base, which is finally sulphonated: (3) ethylenediamine is condensed with chloracetic acid, and the reaction product treated first with ethylene oxide and then with dimethylsulphate: (4) dodecylmercaptan is treated with ethyleneoxide and dimethylsulphate; a sulphonium base is obtained by boiling with caustic soda: (5) benzyl mercaptan is treated with ethyleneoxide and dimethylsulphate; a sulphonium base results on adding caustic soda.  Dodecylhydroxy- and dodecylthio-methylchloride are obtained by reacting dodecylalcohol or dodecylmercaptan with formaldehyde in the presence of hydrogen chloride.  Reference has been directed by the Comptroller to Specification 441,473.ALSO:Products stated to have dispersing properties are obtained by introducing one or more ether or poly ether radicles into quaternary ammonium or phosphonium compounds or ternary sulphonium compounds by condensing the latter with polyhydric alcohols or etherifying derivatives thereof having at most six carbon atoms or with polyether compounds containing atoms or groups such as halogen, which react with the said quarternary ammonium or phosphonium or ternary sulphonium compounds. Specified components are: ethylene and propylene oxides, glycide, epichlorhydrin, dichlorhydrin, dichlordiethylether, glycol, glycerol, polyglycerol, glycolchlorhydrin and polyglycerolchloride.  The quaternary phosphonium and ammonium compounds and the ternary sulphonium compounds may contain hydroxyl, carboxylic, amino or mercapto groups which react with the second components.  The same products may also be produced from any compound containing nitrogen, phosphorus or sulphur by first introducing the ether group or groups and then converting the resulting ethers into quaternary ammonium or ternary sulphonium compounds.  Thus, diethylbutanolamine, asym-dimethylethylenediamine or sarcosine may be treated with ethyleneoxide and quaternary ammonium compounds produced by a final treatment with dimethylsulphate, ethylbromide or benzylchloride.  The following starting materials which contain radicles of high molecular weight are advantageously employed: dodecyldimethylhydroxyethylammoniumhydroxide, stearyltrihydroxyethylammonium hydroxide, dimethyloxyethyldibutyl ammoniumhydroxide, the monooleic ester of tetrahydroxyethylammoniumhydroxide, dodecyldimethylcarboxymethylammoniumchloride, the reaction product of ethylenediamine with octodecyldimethylchloroethylammoniumchloride, the reaction product of dimethylsulphate with stearyldiethylenetriamine, the quaternary ammonium compounds of oleylpiperazine, quaternary ammonium compounds obtained by adding on dodecyl bromide, dodecahydroxymethylchloride or dodecathiomethylchloride to tetramethyl-b -hydroxypropylenediamine, oleyldi--hydroxyethylamineoxide, stearylamine, oleylamine, dodecylmethylamine, didodecylamine, octodecylethylenediamine, dodecylpropylene - diamine, and polyether derivatives of oleic acid amides of ethylenediamine, triethylenetetramine or ethylene diaminosorbitol and poly ether derivatives of the reaction product of triethylenetetramine or aminosorbitol with trichlorinated paraffin wax or of the oleylamide of piperazine.  The high molecular radicle may however be introduced when the ethers are converted into quaternary ammonium or ternary sulphonium compounds.  The products may be condensed with chlorethanesulphonic acid, chloracetic acid, fatty acid chloride, chlorcarbonic esters, isocyanates or treated with phosphoric acid o