Patent GB-641439-A (GB)
Title: Wetting agents or detergents
Filed: 1947-07-08
Abstract: Improved wetting and detergent materials are prepared by extracting a petroleum hydrocarbon fraction with a preferential solvent for its aromatic constituents, separating the extract from raffinate and solvent, and alkylating it with an olefinic polymer boiling between 150 DEG  and 350 DEG  F. and prepared by the polymerization of one or more C3 to C4 olefines and sulphonating the alkylate.  The extract may be obtained from crude oil, lubricating oil, bright stock, kerosene or gasoline fractions which may be derived from naphthenic, aromatic, Pennsylvanian or other base stocks; the fractions should preferably have been freed of asphaltic and resinous substances, for example, by propane de-asphalting, sulphuric acid treating or clay treating; the base stock is generally one boiling above 200 DEG  C. Specified solvents for the extraction are phenol, sulphur dioxide, furfural, nitrobenzene and dichlorethyl ether.  The C3-C4 olefines may be derived from unsaturated refinery gases such as the C3 and/or C4 cut in a cracking operation.  The polymerization may be effected with the aid of a Friedel-Crafts catalyst or a polymerization catalyst of the type of sulphuric or phosphoric acid.  Condensation of the polymerized olefine and aromatic extract may be carried out by means of a Friedel-Crafts catalyst, e.g. aluminium chloride, boron fluoride, zinc chloride or tin tetrachloride, or sulphuric acid or similar condensation catalyst.  The product is normally washed to remove catalyst and the alkylate isolated, e.g. by distillation and colouring substances removed, if desired, by means of clay or charcoal.  The alkylate is then sulphonated at or below room temperature.  The resulting sulphonic and/or alkyl sulphuric acid may then be neutralized, e.g. with caustic soda, caustic potash, ammonia, onium bases such as sulphonium bases, or amines and the resulting salt recovered by extraction with alcohol and salting out.  The products so prepared may be employed as such or in combination with inorganic salts, e.g. MgSO4 or NaCl, fatty soaps, fatty alcohol sulphates, sulphonated aromatic hydrocarbons and the like.  In examples: (1) equimolecular proportions of di-isobutylene and a sulphur dioxide extract of a petroleum oil boiling above 200 DEG  C. are condensed in the presence of aluminium chloride, the catalyst hydrolysed, the mixture fractionated, a fraction B.P. 160-200 DEG  C. at 7 mm. pressure treated with 80-98 per cent sulphuric acid at 60-80 DEG  C. and the resulting product treated with water to separate free sulphuric acid, neutralized with sodium carbonate and extracted with alcohol; if desired, the soap formed may be salted out and extracted at the same time; (2) a propylene polymer B.P. 130-135 DEG  C. and consisting mainly of trimer is similarly reacted with a sulphur dioxide extract of a petroleum fraction of Coastal origin B.P. between 150 DEG  and 340 DEG  C. to yield a sodium sulphonate detergent.  The Specification as open to inspection under Sect. 91 relates to the production of wetting and detergent materials comprising extracting a petroleum hydrocarbon with a preferential solvent, condensing the extract with any olefinic hydrocarbon and sulphonating the condensate.  Reference is made to the use of such olefinic petroleum hydrocarbons as cracked gasolines, cracked distillates, cracked wax and cracked gases and especially olefinic polymers including polymers boiling above 350 DEG  F. such as polymerized cracked wax.  In additional examples: (3) a furfural extract of a lubricating oil is condensed in presence of boron fluoride with polymerized olefines, B.P. between 10 DEG  and 120 DEG C., prepared by treating a C3-C4 fraction from cracked petroleum with phosphoric acid on clay at about 120 DEG  C. and 200 lbs./sq. inch pressure, and the condensate is then sulphonated with sulphuric acid; (4) a phenol extract of a lubricating oil, A.P.I. gravity 13.9, aniline point 55 DEG  C. and initial B.P. 204 DEG  C., is mixed with a cracked petroleum fraction containing isobutane, isobutylene, a -butylene, b -butylene and n-butane, and the mixture treated with 90 per cent sulphuric acid and the sulphonation mixture is diluted, free sulphuric acid separated, neutralized and extracted with alcohol. Also, in example (1) above, tri- or tetra-isobutylene may replace the di-isobutylene. A propylene polymer is obtained by contacting the propylene with clay at elevated temperature or by thermal polymerization alone. This subject-matter does not appear in the Specification as accepted.ALSO:Wetting and detergent materials comprise the products obtained by extracting a petroleum hydrocarbon fraction with a preferential solvent for its aromatic constituents, separating the extract from raffinate and solvent and condensing it with an olefinic polymer, boiling between 150 DEG  and 350 DEG  F., and prepared by the polymerization of one or more C3-C4 olefines, and sulphonating the alkylate and, generally, neutralizing the product (see Group IV (b)).  The product may be employed in conjunction with inorganic salts, e.g. magnesium sulphate and sodium chloride, fatty soaps, fatty alcohol sulphates, sulphonated aromatic hydrocarbons and the like.  The examples describe products obtained (1) by alkylating an SO2 extract of a petroleum oil B.P. over 200 DEG  C. with di-isobutylene, sulphonating, neutralizing with sodium carbonate and extracting with alcohol, and (2) by alkylating an SO2 extract of a coastal oil B.P. 150-340 DEG  C. with a propylene polymer B.P. 130-135 DEG  C. and sulphonating.  The Specification as open to inspection under Sect. 91 relates to wetting and detergent materials obtained as above from any olefinic hydrocarbon including cracked wax, cracked gasolines, cracked distillates and cracked gases and especially olefinic polymers, including those boiling above 350 DEG F., such as polymerized cracked waxes, the latter yielding products which have emulsifying properties.  Further examples describe products obtained: (3) as in (1) above, substituting tri- or tetra-isobutylene for di-butylene; (4) by alkylating a furfural extract of a lubricating oil with polymerized C3-C4 olefines from a cracked petroleum and sulphonating and (5) by alkylating a phenol extract of a lubricating oil with a cracked petroleum fraction containing isobutane, isobutylene, a -butylene, b -butylene and n-butane and proceeding as in (1) above.  This subject-matter does not appear in the Specification as accepted.ALSO:Detergent compositions comprise the products obtained by extracting a petroleum hydrocarbon fraction with a preferential solvent for its aromatic constituents, separating the extract from raffinate and solvent and condensing it with an olefinic polymer boiling between 150 DEG  and 350 DEG  F. and prepared by the polymerization of one or more C3 to C4 olefins and sulphonating the resulting alkylate and, generally, neutralizing the product (see Group IV (b)), in admixture with inorganic salts, e.g. magnesium sulphate and sodium chloride, fatty soaps, fatty alcohol sulphates, sulphonated aromatic hydrocarbons and the like. Products mentioned are those obtained (1) by alkylating a sulphur dioxide extract of a petroleum oil with di-isobutylene, sulphonating and neutralizing with sodium carbonate, and (2) by alkylating a sulphur dioxide extract of a coastal oil with a propylene polymer B.P. 130-135 DEG  C. and sulphonating.  The Specification as open to inspection under Sect. 91 refers to the use of the products obtained as above but from any olefinic hydrocarbon including polymeric olefines of B.P. greater than 350 DEG  F., such as polymerized cracked wax.  Further examples of suitable products are (3) products obtained as in (1) above, substituting tri- and tetra-isobutylene for the di-isobutylene; (4) a product obtained by alkylating a furfural extract of a lubricating oil with polymerized C3-C4 olefines from a cracked petroleum and sulphonating the product, and (5) a product obtained as in (1) from a phenol extract of a lubricating oil and a cracked petroleum fraction containing isobutane, n-butane, isobutylene, a -butylene and b -butylene.  This subject-matter does not appear in the Specification as accepted.