Patent GB-671353-A (GB)
Title: Manufacture of surface-active agents
IPC: C07C309/31
Filed: 1947-05-12
Abstract: Surface active agents are prepared by a method comprising reacting benzene or a monoalkyl benzene containing less than 5 carbon atoms in the alkyl group in the presence of a liquid acid alkylation catalyst with a long chain mono-olefinic hydrocarbon reactant boiling between 160 DEG  and 320 DEG  C. and consisting of propylene polymers at least predominantly having from 12 to 18 carbon atoms per molecule, reacting the resultant alkyl benzene hydrocarbons at least predominantly having an alkyl group of from 12 to 18 carbon atoms per molecule with a sulphonating agent containing sulphuric acid to substantially sulphonate the same and neutralizing the resultant alkyl benzene sulphonic acids with a basic compound whereby surface-active alkyl benzene sulphonates are obtained.  The mono-olefinic hydrocarbon reactant is a mixture which, in general, contains not more than 10 per cent propylene trimer, at least about 50 per cent tetramer, about 20-30 per cent pentamer and hexamer and not more than 10 per cent of higher propylene homologues, the proportions being such that not more than 20 per cent of the whole consists of hydrocarbons having more than 15 carbon atoms; preferably, the mixture consists substantially of C12 to C18 olefines.  The polymerized olefines may be obtained by subjecting the olefines to polymerization in the presence of such catalysts as a calcined composite of phosphoric acid and a siliceous carrier sulphuric acid, activated clays or silica-alumina compounds. Alkylation may be effected using 90-100 per cent sulphuric acid, generally at below about 30 DEG  C. for a period less than 90 minutes, or by means of 90-100 per cent HF at from about -30 DEG  C. to about +40 DEG  C. Other catalysts for the alkylation are the hydrocarbon (sludge) complexes or the "ansolvo" acid complexes of boron trifluoride and aluminium chloride with or without promoters such as hydrogen halide.  Sulphonation may be effected with 80 to 115 per cent sulphuric acid at about 10-80 DEG  C. for a residence time less than two hours.  A mixture of sulphuric acid and BF3 may also be used.  The sulphonation product may be settled to separate a mixture of alkyl benzene sulphonic acids and sulphuric acid from unreacted hydrocarbons, which mixture is neutralized with an aqueous solution of a base to form a solution of salts of the sulphonic and sulphuric acids which may be evaporated to dryness. Preferably, the separated mixture of acids is treated with a water-insoluble neutral organic liquid solvent which boils below 150 DEG  C., is stable towards sulphuric acid and has a preferential solubility for the sulphonic acids whereby an extract of these acids free from sulphuric acid is obtained which is neutralized with an aqueous solution of a basic compound and an aqueous layer containing alkyl benzene sulphonates is separated from the resulting mixture.  The selective extractant may be a non-olefinic or halogenated hydrocarbon such as benzene, toluene or chloroform. Settling of the sulphonation product may result in formation of three layers, unreacted hydrocarbons separating above a middle layer of sulphonic acids, especially if water or aqueous sulphuric acid be added.  The middle layer is then separated and used in the extraction.  The hydrocarbon layer may be used in subsequent sulphonations.  The extract may be decolourized before the neutralization, e.g. with activated charcoal, kieselguhr or diatomaceous earth.  The aqueous solution of neutralized alkyl benzene sulphonic acids may be evaporated to dryness, following which the dry material may be extracted with methanol, ethanol or other alcohol and the extract, if desired, after a decolourizing treatment as above evaporated to dryness to yield the sulphonates free from inorganic impurities.  Suitable neutralizing agents are alkali metal hydroxides, ammonia and amino compounds such as methyl amine, ethylamine, propylamine and hydroxy analogues, e.g. ethanol amine.  A continuous process for the production of alkyl benzene sulphonates is described.  The products may be used as detergents (see Group III), and wetting agents (see Group IV (c)). In examples: (1) benzene is monoalkylated with a mixture of propylene polymers of boiling range 180-270 DEG  C. using sulphuric acid as catalyst at 0-5 DEG  C. sulphonation of the alkylate being effected by raising the temperature to 50 DEG  C., following which the product is settled, forming three layers, the upper layer of unreacted hydrocarbons is removed, sulphonated and settled, the middle layers of both sulphonation products are extracted with benzene, the alkyl benzene sulphonic acids therein neutralized with aqueous NaOH and the resulting aqueous solution of sulphonates removed and evaporated to dryness; (2) the method of (1) is repeated using a mixture of propylene polymers of boiling range 180-308 DEG  C.  Specification 539,281 is referred to.  The Specification as open to inspection under Sect. 91 relates to the production of surface-active salts of alkyl aryl sulphonates wherein aromatic hydrocarbons such as the benzene hydrocarbons mentioned above and naphthalene, phenanthrene and anthracene hydrocarbons are alkylated with mono-olefinic hydrocarbons, generally having from 10 to 20 carbon atoms and which may be derived from any source, e.g. polymerized olefines having, as monomers, less than 10 carbon atoms such as propylenes and butylenes, cracked gasoline fractions and other olefinic fractions generally of boiling range about 160-320 DEG  C., the alkylation being effected with any alkylation catalyst, e.g. boron trifluoride or aluminium chloride, the resultant alkylated aromatic hydrocarbons are sulphonated, e.g. with chlorsulphonic acid and the products are worked up as above.  According to a further feature any alkyl aromatic hydrocarbon may be sulphonated, a liquid layer comprising alkyl aromatic sulphonic acid and sulphonating agent recovered from the reaction product and the liquid layer treated as above with the selective solvent to remove the alkyl aromatic sulphonic acids which are worked up to yield detergent salts.  This subject-matter does not appear in the Specification as accepted.ALSO:Surface-active agents comprise alkyl benzene sulphonates obtained by condensing benzene or a mono-alkyl benzene containing p  less than 5 carbon atoms in the alkyl group with a mono-olefinic hydrocarbon reactant boiling between 160 DEG  and 320 DEG  C. and consisting of propylene polymers at least predominantly having from 12 to 18 carbon atoms in the molecule, sulphonating the resultant alkyl benzene hydrocarbons at least predominantly having an alkyl group of from 12 to 18 carbon atoms and neutralizing the product (see Group IV (b)).  They may be used, in the form of their ammonium, amine or alkali metal salts, as wetting agents or detergents alone or in conjunction with sodium sulphate, sodium benzene sulphonate, sodium carbonate, trisodium phosphate, sodium pyrophosphate and like detergent assistants.  They may be used in washing, scouring, sizing, and dyeing and in the tanning industry.  An example indicates the detersive efficiency of a sodium sulphonate prepared in polymer boiling from benzene and a propylene polymer boiling in the range of 180 DEG  to 270 DEG  C. Potassium, methylamine, ethylamine, propylamine and hydroxyamine, e.g. ethanolamine salts are mentioned.  Specification 539,281 is referred to.  The Specification as open to inspection under Sect. 91, includes surface active sulphonates derived from alkyl aromatic hydrocarbons in general which may be obtained by alkylation of benzene, naphthalene, phenanthrene and anthracene hydrocarbons with mono-olefinic hydrocarbons having from 10-20 carbon atoms and derived from, for example, polymerization of such olefines as propylene and butylene or cracked gasoline.  This subject-matter does not appear in the Specification as accepted.ALSO:Detergents comprise alkyl benzene sulphonates obtained by condensing benzene or a mono-alkyl benzene containing less than 5 carbon atoms in the alkyl group with a mono-olefinic hydrocarbon reactant boiling between 160 DEG  and 320 DEG C and consisting of propylene polymers at least predominantly having from 12 to 18 carbon atoms in the molecule, sulphonating the resulting alkyl benzene hydrocarbons at least predominantly having an alkyl group of 12 to 18 carbon atoms and neutralizing the product (see Group IV(b)).  The sulphonates may be the alkali metal, ammonium or amine salts, and they may be used in conjunction with sodium sulphate, sodium benzene sulphonate, sodium carbonate, trisodium phosphate, sodium pyrophosphate and like detergent assistants.  An example indicates the detersive efficiency of a sodium sulphonate prepared in specified manner from benzene and a propylene polymer boiling in the range 180 DEG  to 270 DEG C.  Potassium, methylamine, ethylamine, propylamine and hydroxyamine, e.g. ethanolamine salts, are also mentioned.  Specification 539,281, [Group IV], is referred to.  The Specification as open to inspection under Sect. 91 includes as detergents sulphonates derived from alkyl aromatic hydrocarbons which may be obtained by alkylation of benzene, naphthalene, phenanthrene and anthracene hydrocarbons with mono-olefinic hydrocarbons having from 10-20 carbon atoms and derived from, for example, polymerization of such olefines as propylene and butylene or from cracked gasoline.  This subject-matter does not appear in the Specification as accepted.