Patent GB-449169-A (GB)
Title: A process of preparing improved wetting agents and detergents, and products thereof
IPC: C07C303/00
Filed: 1934-12-20
Abstract: Wetting, emulsifying, and detergent agents are prepared by neutralizing the products obtained by treating the mixtures containing olefines having more than six carbon atoms resulting from the cracking of paraffin wax or petrolatum with oxygen containing mineral acids, e.g. chlorsulphonic or phosphoric acid. In examples: (1) a fraction containing olefines prepared by the destructive distillation of petrolatum or paraffin wax is sulphated with oleum, neutralized with sodium hydroxide and treated with isopropyl alcohol to separate sodium sulphate; after removal of the alcohol, ammonia or other alkali is added to neutralize any acid which may be produced during the drying of the soap; (2) a fraction containing olefines, prepared by cracking paraffin wax is sulphated with 96 per cent sulphuric acid and neutralized with sodium hydroxide; sodium sulphate is separated by means of ethyl alcohol and the residue treated with methyl alcohol; (3) a cleansing agent for wool and silk is prepared by mixing a product obtained as in example 1 or 2 with magnesium sulphate or other salt such as the sulphate, bisulphate, carbonate, phosphate, chlorate, tartrate, or benzoate of metals such as calcium, strontium, barium, aluminium, boron, zinc, cadmium, mercury, or tin. Wetting and cleansing agents may also be added, such as sludge sulphonates, fatty alcohol sulphates and soaps.  For the preparation of toilet preparations, soap powders, liquid soaps and dry cleaner soaps, soda, ammonia, fillers, abrasives, dyes, perfumes and solvents may be present.  The cracking is conducted under conditions whereby polymerization is avoided and olefines containing more than six carbon atoms in the molecule are produced.  The cracking process may be effected continuously, e.g. in a series of stills of progressively higher temperature.  Temperatures of 650--750 DEG  F. are suitable when the cracking is performed in the liquid phase and 1000--1100 DEG F. in the gaseous phase.  To avoid polymerization, the olefinic products are preferably cooled quickly.  The content of olefines may be increased by treating with preferential solvents such as aniline, sulphurdioxide, phenol, furfural, ethyl alcohol, triethylcitrate, ethyleneglycoldiacetate, dimethylsulphate and dimethylphthalate.  The olefines may be subjected to a de-waxing treatment, e.g. by sweating, cold settling, filtration or centrifugal separation, with or without the use of solvents or diluents, such as liquid hydrocarbons.  The same diluents, e.g. ethane, propane or butane may be used in both the de-waxing and subsequent acid treating processes, the diluent in the latter process acting as a refrigerant.  The petrolatum, paraffin wax or the cracked products may be purified before the treatment with mineral acid by means of clay, active carbon or sulphuric acid so as to remove diolefines, asphaltic matter and sulphur compounds. p Specification 360,602 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the treatment of any cracked paraffins and includes the following features: (a) the use of oleum in continuous excess for the treatment of the cracked products, e.g. by passing the latter into a stream of oleum; (b) employing such a short time of treatment that colour bodies and polymerization products are avoided; the use of narrow streams flowing between externally cooled walls and of turbo mixers is referred to; (c) the rapid reduction of the concentration of excess sulphuric acid while preventing rise of temperature; (d) the removal, by hydrolysis, of the dialkylsulphates from the products and sulphating the resulting alcohols; (e) the manufacture of a product which does not develop acid on drying by the addition of buffers such as salts of organic acids with alkali metals, alkaline earth metals, ammonia or with organic bases, e.g. sodium acetate and sodium oleate; (f) the treatment of the cracked products first with a mild sulphating agent and then with a stronger agent.  In order to secure a stable product, organic bases, e.g. hydroxyalkyl amines, sodium or magnesium carbonate, hydroxide or oxide may be added before drying.  The cracked products may be sulphated in the presence of fats, fatty alcohols, oxidized petroleum hydrocarbons, ethers, esters, aldehydes, ketones, phenols, naphthenic acids, polymerized animal and vegetable oils, resins, terpenes, amines, sulphur compounds, chlorinated wax, naphthalene, diphenyl and diphenyloxide.  This subject-matter does not appear in the Specification as accepted.ALSO:Emulsifying and detergent agents are prepared by neutralizing the products obtained by treating the mixtures containing olefines having more than six carbon atoms resulting from the cracking of paraffin wax or petrolatum with oxygen containing mineral acids, e.g. chlorsulphonic or phosphoric acid.  In examples (1) a fraction containing olefines prepared by the destructive distillation of petrolatum or paraffin wax is sulphated with oleum, neutralized with sodium hydroxide and treated with isopropyl alcohol to separate sodium sulphate; after removal of the alcohol, ammonia or other alkali is added to neutralize any acid which may be produced during the drying of the soap; (2) a fraction containing olefines, prepared by cracking paraffin wax is sulphated with 96 per cent sulphuric acid and neutralized with sodium hydroxide; sodium sulphate is separated by means of ethyl alcohol and the residue treated with methyl alcohol; (3) a cleansing agent for wool and silk is prepared by mixing a product obtained as in example 1 or 2 with magnesium sulphate or other salt such as the sulphate, bisulphate, carbonate, phosphate, chlorate, tartrate, or benzoate of metals such as calcium, strontium, barium, aluminium, boron, zinc, cadmium, mercury, or tin.  Wetting and cleansing agents may also be added such as sludge sulphonates, fatty alcohol sulphates and soaps.  For the preparation of toilet preparations, soap powders, liquid soaps and dry cleaner soaps, soda, ammonia, fillers, abrasives, dyes, perfumes and solvents may be present.  The cracking is conducted under conditions whereby polymerization is avoided and olefines containing more than six carbon atoms in the molecule are produced.  The cracking process may be effected continuously, e.g. in a series of stills of progressively higher temperature. Temperatures of 650--750 DEG  F. are suitable when the cracking is performed in the liquid phase and 1000--1100 DEG F. in the gaseous phase.  To avoid polymerization, the olefinic products are preferably cooled quickly.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of a product which does not develop acid on drying by the addition of buffers such as salts of organic acids with the alkali metals, alkaline earth metals, ammonia or with organic bases, e.g. sodium acetate and sodium oleate; or by removal of the dialkylsulphates by hydrolysis.  In order to secure a stable product, organic bases, e.g. hydroxylalkyl amines, sodium or magnesium carbonate, hydroxide or oxide may also be added before drying.  The cracked products may be sulphated in the presence of fats, fatty alcohols, oxidized petroleum hydrocarbons, ethers, esters, aldehydes, ketones, phenols, naphthenic acids, polymerized animal and vegetable oils, resins, terpenes, amines, sulphur compounds, chlorinated wax, naphthalene, diphenyl and diphenyloxide.  This subject-matter does not appear in the Specification as accepted.