Detergent aid



Patented Sept. 3, oni-mom Louis A. Mikeska, Westflld, N. ,J., assignor' to Standard Oil Development Company, a co l ration of Delaware No Drawing. This invention relates .to improved detergent" aids, more particularly to poly-alkyl phenol de-. rivatives of strong poly-basic .mineral acids in which at least two of the 'alkyl groups contain more. thanfour carbon atoms each, and pref-- erably'between-about 5 and 8 carbon atoms each. :It has already been proposed to prepare -wetting agents and detergents by reaction of olefines, phenol, and sulfuric acid. The products obtained by such reactions contain amixture of' monoand di-alkyY-phenol derivatives, even when the 'olefines are used substantially 'in excess of jthephenols. These sulfonates are not distillable, and the separation of the product into the separate mono-alkylated and di-' or poly-alky- 'lated-components is extremely difficult, usual-. 1y 8. practical impossibility. It has now been found that detergent aids. of greatly increased efiectiveness are obtained if the poly-alkyl phenol sulfonates- 'are prepared substantially free of mono-alkyl phenol su1fo-' nates. This isespecially true with alkyl .deriva-. tives in which the alkyl groups contain from 5 to about 8 carbon'atoms, preferably 5 or 6 'carbon atoms.', I V A .i a .One suitable method 'for preparing the improved detergent aids of this invention to react the corresponding p'oly-alk'yl phenol with a. strong poly-basic mineral acid, preferably a sulfonating agent, such as strong or fuming sulfuric. acid, chloro-sulfonic acid, and .the like. The resulting mineral acid derivatives may be used as obtained for uses in which acid detergent tion being an'even more effective wetting agent than the total salt, and the etherinsoluble fraction-beings, very'poor wetting agent. ' 00 grams of chlorosulfonic acid were then added 4 aids are desired." '-They may also be neutralized with suitable. bases, such as the alkali metal bases and nitrogen bases, suchas ammonia and the amines; and'the resulting salts have been found to beespecially active wetting agents. -.These salts have surprising characteristics in, thattheir wetting ability is substantially. great-'- er-in both hard water and in acid solutions than. in neutral aqueous solutions. I 7 that such reaction It has also been found products contain fractions which are separable by'extractlon with ether; the ether soluble frac- Thefollowing example presented as i1 trative'of r this invention and desc'ribesone suitable method for the preparation of the improved detergent aids described herein: --.Ea:dmple1 chanical'stirrer and-mercury seal, drop funnel and gas inlet tube}. and thermometer. and gas outlet tube .and was cooled therein .to 10 C. grams of di-amyli {1,3} phenol placedin a one liter, 'three-way'fiask, fitted with aime- Application January.2 9,138, 1 J SerialNo.187, 662 reclaims. (c1.- 26o 51'2)- dropwise while stirring and reaction temperature between 50 and-F. during aperiod of 40 minutes. After adding'all the acid, the cooling bath -[was removed and the reaction mixture was allowed to warm up -to-room temperature, air beingjblown through .the. reaccooling .to keep the tion mixture" for about 3" hours. The mixturewas thenneutralized with aqueous sodium Trydro'xide. Isopropy1 alcoholequa l to half the vol ume of the resulting mixture was added. This was followed by the addition -ofnaphtha and thorough shaking. The mixture .was then per mitted to settle into a' 1ower.Water-alcohol layer containing the desired product and-an "upper; naphtha layer containing the unreacted materials. The aqueous solution was drawn ofi. and. I was extracted several times with naphtha to remove additional unreacted materials. -The aqueous solution was thndried on a steam bath andthere was obtained 63.1 grams .of-pa light colored, ,solid product'representing a yield of more than of the theoretical.- m a 58 grams of this crude product were extracted with ethyl ether and the {ether extract .Was I evaporated to dryness. 77.3% .of the total prodnot was obtained as the ether'extract. - he characteristics oflthese,products-aswebting agents were determined by the method of Draves' and Clarkson, Proc. Am. Assoc. Textile Chem. Colorists 1931, 109, The wetting numbers of the crude product 'andof the ether extract and residue were obtained with. solutions containing 0.2% of the product in' distilled water, in hard water-containing 300 parts per mil lion of calcium, and in an aqueous solution containing,.0..3% of sulfuric acid. The wetting nun'1-' bers andappearance of these solutions are in-' dicated in the following table: .wrzrrmdlfiomsm shconns m Solutzon- 0.2%--of -wettmg agent, Wettin Ha'rd Appearanceof agent Water water A solution Crude product... 28 Clear solution, faint a 4 strawcolor. '9 Slightlyopalescent. - 12 Clear soluti0n Ether extract." 11 Clear solution, faint a straw color. a 3 O alescent. 7 1 4 0ear. Etherinsolublm. Above 600 Clear. Other poly-.alkylphenols suitable for use in preparing the improved detergent'aids of this invention by the process described in the above eXampie are those containing 5 to 8 or'more carbon atoms in ea'ch-alkyl group. The alkyl groups may 'be normal, iso, secondary', or tertiary, or .' even' cycli'c. Aryl derivativesof alkyl radicals are also contemplated-such. as benzyl, tolyl, eres i, phenyl, and. the like. The poly-alkyl phenols may be obtained by alkylating a phenol with suitable alkylating agents, such as alcohols, olefines; alkyl sulfates: and-alkyl halides, of .6 to 8 or more carbon atoms per'molecule. The alkylated phenols prepared from such olefines, or their corresponding alcohoLsulfate, or halide derivatives, contain branched carbon chains in the alkyl group, the carbon atom attached to the 10 aromatic ring being also connected to twoor pentenes and-hexenes, or narrower cut fractions containing only isomeric olefines of the same molecular weight suchfas the pentenes, may be used. The olefinesmay also be'polymers'of low molecular weight olefines, such asdimers, trimers, tetramers, etc., of olefines of preferably less than 5 carbonatoms per molecule, particularly of isobutylene. f The alkyl phenols. may be prepared by any suitable method such as the: methods described inU. S. Patents Nos. 1,954,985 and 2,045,749 'using preferably a large proportion of olefines v to phenols. The products obtained by such methads will contain mixtures of mono.-, di-, and possibly higher poly-alkyl phenols. These products should be separated by suitable methods, such derivatives thereof may also be used. Examples of these are cresol and other alkyl phenols, polyhydroxy-phenols such as resorcinol, hydro-quinone and the like, thio-phenols, or under some circumstances, crude commercial products con-. 5o taining substantial quantities of phenol or cresol, such as the crude phenol or cresol fractions obtained as coal-tar distillate 'fractions;'- the petroleurn phenols such as the phenolic compounds extracted from petroleum crudes and distillate 'fractions thereof by alcoholic alkali; also monoandpoly-hydroxy derivatives of poly-nuclei hydrocarbons, such as alpha and betanaphthol or aryl substituted phenols. The petroleum phenols mentioned above are preferably obtained from 50 kerosene and'gas oil distillates. They may be extracted with alcoholic sodium hydroxide. The extract. will contain oil and some naphthenic acids, if such are present in the oil being extracted. Dissolved hydrocarbon oil may be sepa- 05' rated from the alcoholic extract by washing it several times with naphtha or petroleum ether. Phenols may be separated from naphthenic acids in the extract bysaturating it with carbon dioxide, whereupon the phenols are liberated as a separate layer. 'Another method is to acidify'the alcoholic caustic extract with excess strong acid such as hydrochloric of sulfuric acid, whereupon both phenols and naphthenic acids separate as an oil layer. On removing this layerand washing it with aqueous sodium carbonate solution, the .The olefines may be obtained hydrogenated naphtha, if necessary. naphthenic' acids are dissolved, leaving the. phenols. As sulfonating agents, strong sulfuric acid (of to concentration), fuming sulfuric acid, or liquid sulfur trioxide, may bejused. Care 5 should be taken not to use the stronger agents under such conditions as to affect the alkyl- For example, fumingacids are preferablyavoided in sulfonating poly-alkyl phenols of which thealkyl groups are oleflne polymers or 1 contain long or highly branched carbon chains. Although sulfuric acid is preferred, it is possible to use other strong poly-basic mineral acids, such as phosphoric acid. Poly-alkyl phenol' phos phates may also be prepared by reaction of the 15 poly-alkyl phenol with phosphorous tri-chloride or with phosphorous oxy-chloride, followed by suitable hydrolysis to prepare the phosphoric acid derivative. Such phosphoric acids and their salts are used asdetergent' aids preferably in 20 neutral'or hardwater, in which they are very effective, Although the exact limitations-of the various factors involved in the preparation of detergent aids according to the present invention are not 25 known with absolute certainty, the following ranges and preferred conditions are believed to be sufficiently definite to guide those skilled in the art in carrying out this invention. The strength of the sulfuric acid to be used should 30 be between 85% H2504 and 20% oleum (fuming acid), and the stronger the acid the lower should be the temperature at which it is used, although generally, satisfactory. results are obtained by using the ordinary concentrated sulfuric acid 3 (95% H2804) at a temperature between 70 F. and F. 'With stronger acid, the temperature may be lowered to 32 F. or even 15 or -5 F., using inert diluent, such as a straight run or The con- 40 ditions of the reactions should be preferably maintained so as to produce primarily monoalkali metal sulfonates and preferably no disulfonates. ' Proportions of the primary reactants, i. e.', the 45 alkyl phenols and the sulfuric acid, may be varied considerably, but ordinarily the ratio of sulfuric acid to phenol shouldbe between the approximate limits of3 to 1 andlto 1. The acid serves both as a reagent and a dehydrating agent, hence the 50 stronger acids are used in smaller proportions. The time'of contact will, of course, vary inversely with the temperature and concentration of acid, but ordinarily will be between the approximate limits of 10 minutes and 1 or 2 hours. Extremely 55 short times of contact, e. g., substantially less than 1 minute, may be used with relatively concentrated sulfuric acid and at relatively elevated temperature. ' Although sulfuric acid has been described above '50 as the. treating agent for effecting the combination of the olefine polymers with the phenols-and also for attaching an inorganic radical which imparts good wetting properties to the compound, other strong poly-basic mineral acids e. e5 the leather, to improve the penetration of 006- 76 including among others: scouring 70- metics, the wetting of glue, with Portland cement to get better mixing, finishing pastes, for removing grease from steel, in lubricating oils, in lacquer emulsions, in paper manufacture to give the paper better absorption qualities, in combination with derris and pyrethrum for use in sprays, to get best coverage and toxic action, and may be used with lead arsenate in sprays, in oil and water emulsion sprays, and in miscible oils for the preparation of emulsions. This invention is not to be limited by any of the specific examples given, nor any theories advanced as to the mechanism of the operation of the invention, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as broadly as the prior art permits. I claim: 1. Sodium poly-alkyl phenol sulfonate in which the said alkyl groups each contain more than 4 carbon atoms. 2. Sodium di-amyl phenol sulfonate. 3.'Improved detergent aid comprising. essentially an alkali metal salt of a strong poly-basic mineral acid derivative of a poly-alkyl phenol in which at least two of the alkyl groups each contain more than 4 carbon atoms. 4. Improved detergent aid comprising essentially an alkali metal salt of a strong poly-basic mineral acid derivative of a di-alkyl phenol in which the said alkyl groups are both branched and each contains from 5 to 8 carbon atoms. 5. Improved detergent aid comprising essentially an alkali metal saltof a strong poly-basic mineral acid derivative of a di-tertiary alkyl phenol in which each of the alkyl groups contains from 5 to 6 carbon atoms. 6. Improved detergent air comprising essentially an alkali metal salt of a sulfonated di-amyl phenol. '7. Improved detergent aid comprising essentially an alkali metal salt of a sulfonated di-alkyl phenol in which the said alkyl groupseach contain more than 4 carbon atoms, the said salt being substantially completely soluble in ether. 8. Improved detergent aid comprising essentially an alkali metal salt of a sulfonated di-amyl phenol, the said salt being substantially completely soluble in ether. 9. Process for preparing improved detergent aids comprising sulfonating a di-alkyl phenol having more than 4 carbon atoms in each of the alkyl groups. .10. Process for preparing improved detergent aids comprising sulfonating di-amyl phenol and neutralizing the resulting product with an alkali. 11. Process for preparing improved detergent aids comprising sulfonating di-amyl phenol, neutralizing the resulting product with an alkali, and separating from the neutralized reaction product the fraction soluble in ether. 12; An alkali-metal salt of a mono-sulfonic acid of di-tertiary-amyl phenol. 13. Poly-alkyl phenol sulfonic acid in which the said alkyl groups each contain more than 4 carbon atoms. 14. Di-amyl phenol sulfonic acid. 15. 'A strong poly-basic mineral acid derivative of a poly-alkyl phenol in which at least two of the alkyl groups each contain more than'4 carbon atoms. 16. A sulfonic acid derivative. of a di-alkyl phenol in which the said alkyl groups are bothbranched and each contains from 5 to 8 carbon atoms. LOUIS A. MIKESKA.



Download Full PDF Version (Non-Commercial Use)

Patent Citations (0)

    Publication numberPublication dateAssigneeTitle

NO-Patent Citations (0)


Cited By (1)

    Publication numberPublication dateAssigneeTitle
    US-5330664-AJuly 19, 1994Chevron Research And Technology CompanyNeutral and low overbased alkylphenoxy sulfonate additive compositions derived from alkylphenols prepared by reacting an olefin or an alcohol with phenol in the presence of an acidic alkylation catalyst