US2702819A - Guanidine alkyl aryl sulfonates - Google Patents

Description

United States Patent 2,702,519 GUANIDINE ALKYL ARYL SULFONATES No Drawing. Application July 23, 1951, Serial No. 238,190

21 Claims. (Cl. 260-501) This invention relates to guanidine sulfonates as new compositions. In one embodiment this invention relates to novel guanidine salts of synthetic alkyl aryl sulfonic acids. In another embodiment this invention relates to guanidine salts of petroleum sulfonic acids as new compositions.

This application is a continuation-m-part of our copending application Serial No.- 217,669, filed March 26, 1951, now Patent Number 2,660,562, which is itself a continuation-in-part of our copending application Serial No. 44,575, filed August 16, 1948, now abandoned.

An object of our invention is to provide as new compositions guanidine salts of petroleum sulfonic acids, having especial utility as lube oil detergents, and as gelatio i agents in the manufacture of greases. Another ob ect is to provide as new compositions guanidme salts ofsynthetic alkyl aryl sulfonic acids, having especial utility as lube oil detergents, and as gelation agents in the manufacture of greases. Another object is to provide oil-soluble guanidine petroleum sulfonates. Another object is to provide guanidine alkyl aryl sulfonates, having a total of from to carbon atoms in the alkyl groups. Another object is to provide guanidine petroleum sulfonates containing from 20 to 70 carbon atoms in the molecule. Other objects will be apparent to those skilled in the art from the accompanying discussion and disclosure.

Certain of our guanidine alkyl aryl sulfonates are oilinsoluble and disperse readily in mineral oil as gelation agents to form improved greases of the ashless type, while others, of relatively high molecular weight are oil-soluble, and when dissolved in a lube oil base stock impart valuable detergent properties to itthus forming improved lubricating oils. Certain of our guanidine petroleum snlfonates are oil-soluble and when dissolved in a base lube oil stock impart valuable detergent properties to it, while other guanidine petroleum sulfonates differing from the detergent types principally in molecular weight and/ or degree of sulfonation, have pronounced activity as g elation agents when dispersed in the oil, and may be utilized to advantage in the preparation of greases.

Our guanidine alkyl aryl sulfonates particularly suitable as grease gelation agents contain from 17 to 35 carbon atoms in the molecule, although those containing from 24 to 34 carbon atoms can serve also as detergents in oil systems, particularly when so utilized in relatively small concentrations in the lubricating oil. Preferably our guanidine alkyl aryl sulfonates when utilized as oil detergents contain from 40 to 70 carbon atoms per molecule or higher. When employing our guanidine petroleum sulfonates as oil detergents we have found that they should contain at least 40 carbon atoms in the molecule generally up to as high as 70. Our guanidine petroleum sulfonates suitable as gelation agents in the manufacture of greases contain more than 20 and up to 40 carbon atoms in the molecule, preferably from 22 to 35. Also, guanidine petroleum dior poly-sulfonates derived from heavy petroleum fractions containing over about 40 to as high as about 80 or more carbon atoms in the molecule are excellent gelation agents. These latter compositions have such a molecular weight that the molecule contains one sulfonate group per 20 to 25 carbon atoms.

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sulfonate compositions as gel-forming agents in the manufacture of greases, the resulting grease contains generally from 5 to as high as weight per cent of the gelation agent. In general, the lubricantfwhich term denotes either a lubricating grease or a lubricating oil incorporated with a guinadine sulfonate of our invention, generally contains from 0.1 to 60 weight per cent of the guanidine sulfonate added.

In accordance with one-method of preparing our guanidine alkyl aryl sulfonates, a synthetic alkyl aryl sulfonic acid is neutralized with guanidine'or a basic guanidine salt. The synthetic alkyl aryl sulfonic acid can be prepared in any suitable manner. Any suitable alkylation procedure for alkylating an aromatic hydrocarbon with an olefin can be utilized in the formation of the synthetic alkyl aromatic, which can then be sulfonated to produce the desired synthetic alkyl aryl sulfonic acid. In carrying out such an alkylation a catalyst is generally preferred exemplary of which is sulfuric acid, hydrofluoric acid, boron trifluoride, or the like.

Aromatic hydrocarbons from which our guanidine alkyl aryl sulfonates are derived generally contain from 1 to 3 rings in the aromatic nucleus illustrative of which are benzene, naphthalene, diphenyl or anthracene, or their alkyl derivatives.

One specific method of preparing guanidine alkyl aryl sulfonates suitable for use as gelation agents in the manufacture of greases, comprises the steps of alkylating an aromatic hydrocarbon of the type described in the presence of a suitable alkylation catalyst with an olefin or olefin fraction boiling in the range of l90315 (3., the olefin being selected so that the total number of carbon atoms in the alkyl groups does not exceed 20. The resulting aromatic-olefin alkylation product is then sulfonated employing any suitable sulfonation agent, as for example fuming sulfuric acid, sulfur trioxide or the like to produce the alkyl aryl sulfonic acid. The synthetic sulfonic acid thus formed is then dissolved in a low boiling alcohol such as for example isopropyl alcohol to which resulting solution is added a molar excess of guanidine generally as a concentrated aqueous guanidine solution or as a basic guanidine salt as for example aqueous guanidine carbonate. The resulting reaction solution separates into an alcohol layer containing the guanidine alkyl aryl sulfonate. The alcohol layer is then isolated after which the alcohol is evaporated to recover the guanidine alkyl aryl sulfonate product. I

In the preparation of guanidine petroleum sulfonates as oil detergents, we prefer to employ a deasphalted and solvent refined bright stock fraction in the sulfonation step, such as a petroleum fraction having a viscosity range 7 between about 80 and 700 SUS at 210 F. Such a pctroleum stock particularly preferred for this purpose, i. e., for sulfonation and subsequent neutralization with guanidine, is a propane-fractionated solvent refined dewaxed Mid-Continent oil having a viscosity of from about 200 to 230 SUS at 210 F., and having a viscosity index of about -95 or higher. It will be appreciated by those skilled in the art that by the term propane-fractionated is meant fractionation of the oil or bright stock with propane to efiect deasphaltization and also separation of oil components on basis of viscosity and that by solvent refining is meant the removal by solvent extraction of 'the more highly aromatic fractions from the deasphalted bright stock. In the latter step any suitable selective solvent can be employed, among which are included phenol, cresylic acids, chlorinated ethers such as chloroethyl ether, nitrobenzene, furfural, and the like. The deasphalted and solvent refined oil is generally dewaxed prior to sulfonation although dewaxing can be dispensed with if com- 'plete segregation of sulfonic acids from the waxy oil is carried out at temperatures above the solution temperature of the wax. In any case prior deasphalting and extraction is definitely required. In general, lube stocks lighter than about 80 SUS at 210 F. are unsatisfactory for use in the manufacture of our guanidine petroleum sulfonate oil detergents since the guanidine petroleum sulfonates so produced are not sufficiently soluble in oil to serve as detergent additives. p

A feature of our success in producing high molecular weight petroleum sulfonic acids, for neutralization with Patented Feb. 22, 5

.in a continuous flow system or in batch agitators.

guanidine to form guanidine petroleum sulfonate detergents, isthe em loyment of stabilized liquid sulfur trioxide as the sul onating agent. Our procedure for sulfonating with this reagent iswell known in the art and involves dissolving the anyhdrous liquid SO: in from 2 to times its weight of dry ethylene chloride to provide an easily manipulated sulfonation reagent. bon sulfonation stock may likewise be dissolved in ethylene chloride or any other suitable non-reactive solvent such as carbon tetrachloride, chloroform, pentane, hexane, or the like.

Sulfonation of the hydrocarbon 011 can be carried oFt n either case we prefer to employ SO: as the sulfonating agent, and the quantity of S0: added 1s ord1n ar1ly adjusted to give a molar ratio of S0: to sulfonationstock of between about 1:1 and 3:1. The reaction between The hydrocar- I the hydrocarbon and S03, even in the case of extremely viscous bright stocks having molecular weights in the range of 800 to 900, is very rapid and exotherrmc. Su lfonation temperatures are ordinarily controlled within the range of about 50 to 200' F. with a preferred operating range between 80 and 130' F. Lower temperatures may be employed without seriously slowing down reaction rates, but no particular advantage accrues therefrom. At temperatures above about 200' F. excessive oxidationwith liberation of sulfur dioxide occurs.

On completion of the sulfonation reaction suflicrent aqueous guanidine carbonate solution is added to brmg both the oil and water phases to a pH value withm the range of 6 to 8 as determined on a pH meter. I he aqueous phase is separated and water-soluble reaction products such as guanidine sulfate,'sulfite, carbonate and certain polysulfonates are washed from the oil phase with water or water containing some isopropyl alcohol if serious-emulsion ditficulties are encountered. Separation of oil-insoluble and oil-soluble sulfonates is accomplished by extracting the water-washed oil solution and/ or dispersion with an anhydrous alcohol. We have found that petroleum sulfonates of poor oil solubility character istics are more soluble in anhydrous alcohols such as 1sopropyl alcohol than are the oil-soluble sulfonates. Since the guanidine petroleum sulfonates are strongly surfaceactive, emulsion formations can be avoided in this extraction step by dissolving the oil-sulfonate mixture in an equal volume of hot alcohol, i. e., above 100 F. and as high as 150' F. or higher, as for example at its boiling point, and then slowly cooling to room temperature, e. g., to below about 100 F. followed by separation of the alcoholic phase. We have found that continuation of this batchwise extraction is desirable until the alcohol extract no longer forms guanidine picrate when treated :zwith alcoholic picric acid. For reasons not clearly understood, detergent-active guanidine petroleum sulfonates do not react with alcoholic picric acid. Ordinarily 3 to 4 extractions using one volume of alcohol per volume of oil per extraction suflices to complete the desired separation. Residual alcohol is stripped from the oil-detergent solution to give a concentrate suitable for direct addition to lubricating oils, or from which the guanidine petroleum sulfonate produced can be recovered if desired, as for example by silica-gel percolation.

The advantages of this invention are illustrated in the following examples. The reactants and their proportions and their specific ingredients are presented as being typical and should not be construed to limit the invention unduly.

EXAMPLE I Toluene was alkylated with dodecene-l in the presence of a boron trifluoride-water complex as a catalyst. The catalyst was prepared by bubbling boron trifluoride gas into water until the molecular ratio of water to boron fluoride was approximately 1:1. The catalyst and toluene 4 The dodecyltoluene obtained was sulfonated by treating it with 1.5 parts by weight of fuming sulfuric acid (20 per cent 50:). The acid was added to the hydrocarbon while stirring and holding the temperature to 15-20 C. The reaction mixture was then warmed to 50' C. for live minutes. A small amount of water was added to the reaction mixture, causin the formation of a water phase and a hydrocarbon p ase. The hydrocarbon phase was separated and dissolved in isopropyl alcohol containing 20 per cent water. An excess of solid guanidine carbonate was added causing thev water to separate and to be basic to litmus. The alcohol fraction was separated, evaporated to dryness, redissolved in anhydrous isopropyl alcohol to separate any inorganic salts and again evaporated to dryness. The rdine toluene sulfonate product was a firm glassy SOlld.

EXAMPLE II Toluene was alkylated with hexadecene-l by the procedure described in Example I. Reaction was less vigorous as heat had to be applied to maintain the reaction temperature at about 50' C. Total time of addition of olefin and heating was 5 hours. After excess toluene was removed by distillation hexadecyltoluene was recovered. The product boiled at 202-205 C. at an absolute pres sure of from 4.5 to 4.8 mm. Hg. The hexadecyltoluene was sulfonatedwith fuming sulfuric acid and converted to guanidine sulfonate by saturating the isopropyl alcohol solution of the sulfonation mixture with guanidine car! bonate. The solution was filtered and evaporated to dryness yielding the guanidine-salt of hexadecyltoluene sulfonic acid.

EXAMPLE III Toluene was alkylated with decene-l by the previously described procedure. Decyltoluene was obtained having a boiling point of l38-141 C. at an absolute pressure of from 10-11 mm. Hg. The product was sulfonated and converted to the guanidine salt.

EXAMPLE IV EXAMPLE V Diphenyl (Eastman White Label grade) was alkylated with tetradecene-l using the general procedure described in Example I. In this case it was found desirable to omit the solvent during alkylationand to raise the temperature to C. Benzene was added following the alkylation to facilitate the process of water washing. This benzene was removed by distillation and some unreacted diphenyl removed by filtration. A small amount of additional diphenyl was removed by distillation at 91--95 C. at 0.5 mm. Hg absolute. The tetradecyldiphenyl was distilled at 240-247 C. at 4 mm. Hg absolute pressure.

A portion of the above tetradecyldiphenyl was sulfonated and converted to the guanidine salt by the method described in Example I.

EXAMPLE VI Naphthalene was alkylated with decene-1 by the procedure of Example I. The crude product was distilled obtaining 45 per cent of the material boiling at 195-200 C. at 5 mm. Hg absolute pressure which repre sented the monoalkylated naphthalene. This monoalkylated product was sulfonated and converted to the guanidine salt by the method of Example I.

EXAMPLE VII Toluene was alkylated with a Ca olefin fraction in the presence of anhydrous HF as a catalyst, at F. Trihexyltoluene was recovered from. the eflluents of the reaction and when sulfonated, followed by neutralization of the resulting sulfonic acid with guanidine, is converted to guanidine trihexyltoluene sulfonate.

EXAMPLE vnr tained oil of an average viscosity of about 100 SUS at 210' F. (SAE 50 base stock) and the propane extract of the second step contained oil of an average viscosity of about 220 SUS at 210' F. (SAE 250 base stock).

The raw SAE 250 base stock was recovered from the total extract'of the second extraction step and then subl5 jected to solvent extraction employing phenol as the selective solvent and to pfiane solvent dewaxing to produce a highly paraflinic r ate comprising a lubricating oil stock having the following properties:

Viscosity, SUS at 100 F 5313 Viscosity, 'SUS at 210' F 223.3 Viscosity index' 89 Gravity, API at 60 F I 24 Average molecular weight 730 A solution of 1000 grams of the lubricating oil stock described above dissolved in liquid ethylene chloride was slowly mixed with a solution of 176 grams of sulfur trioxide also dissolved in liquid ethylene chloride at a temperature maintained within the limits of 75 to 115 F. at atmospheric pressure, under which conditions reaction of sulfur trioxide with the lubricating oil began almost immediately to produce petroleum sulfonic acid. Reaction was completed shortly after admixing of the reactants was terminated.

To the resulting reaction mixture (including ethylene chloride) was added 103 grams of guanidine carbonate. The mixture was stirred vigorously at a temperature within the limits of 70 to 110 F., whereby the guanidine carbonate reacted with the acidic constituents to produce a mixture of guanidine petroleum sulfonates, guanidine sulfate, guanidine sulfite and traces of guanidine carboxylates. Ethylene chloride was then removed from the reaction mixture by vaporization.

The total reaction product, free of ethylene chloride, comprised guanidine petroleum sulfonates in oil solution and was admixed with an equal volume of anhydrous isopropyl alcohol with vigorous stirring, at a temperature near the boiling point of the alcoholat atmospheric pressure. Under these conditions the guanidine petroleum sulfonate reaction product and'oil were dissolved in the alcohol. The alcohol mixture contained some suspended solids and was filtered at its existing temperature. The filtrate was permitted to cool to room temperature, and a large portion of the solute then separated therefrom, as a gummy viscous liquid. The cooled alcohol solution, i. e., at about 70 F., containing guanidine petroleum sulfonates not readily dispersible in oil was decanted from the separated viscous liquid, the latter comprising an oil solution or dispersion of oil-soluble guanidine petroleum sulfonates. The oil solution was then washed with alcohol at room temperature and the washings were added to the previously decanted liquid. The remaining alcohol was stripped from the gummy viscous liquid, and the liquid was purified, i. e., freed of occluded salts, by dissolving it in benzene, washing the benzene solution with water, and then stripping until the product was benzenefree. The purified product consisted of 600 grams of a dark brown, viscous oil solution of guanidine petroleum sulfonate, and is referred to hereinafter in this example as the alcohol-insoluble product, i. e., insoluble at room temperature. Several properties of the alcohol-insoluble product are listed as follows:

Alcohol was stripped from the decanted alcohol solution described above. The remaining alcohol-free liquid was purified by dissolving it in toluene, water washing, and then s ing until free of toluene. Toluene was used in the pu cation of this liquid instead of benzene, in view tion purification temperature for the guanidine petroleum sulfonates. The resulting purified guanidine petroleum sulfonates, soluble in isopropyl alcohol at 70 F., as compared with the alcohol-insoluble liquid described above, are referred to hereafter in this example as alcohol-soluble guanidine petroleum sulfonate.

The alcohol-soluble and alcohol-insoluble guanidine petroleum sulfonates were each incorporated with separate portions of a lube oil base, and each resulting blend was tested in accordance with the NBS stability test (McKee and Fritz, Analytical Chemistry" 21, 568, 1949). In carrying out this test, thermal stability of an oil, in this case a lubricating oil containing a guanidine petroleum sulfonate as an additive, is determined by passing it as a thin film over a steel strip under controlled temperature conditions, over a specified period, and the amount of any resulting deposition of degradation product on the strip is measured. Flat steel strips are employed. The tests conducted were modified in two particulars: (1) the steel strips were curved slightly upward at the edges to prevent the test oil from running off the sides, and (2) a single 12 hour period was used instead of the two 6 hour periods. Each product, i. e., the alcohol-soluble and the alcohol insoluble guanidine petroleum sulfonate, was added to the base oil 1 in a concentration which yielded an oiladditive solution containing the same number of milli equivalents of additive as does a 2 per cent solution of a commercially available detergent sold under the trade name of Paranox 64" and comprising an alkaline earth metal salt of an alkylphenol sulfide. A blend of the same base oil with 4 volume per cent of Paranox 64 was tested in the same manner'for comparison. The results of these thermal stability tests are summarized in the following tabulation:

Appearance Deposit,

mg. of Strip Material Tested Very poor.

1 A solvent refined SAE 30 lubricating oil containing 0.75 volume pergent of a commercially available oxidation inhibitor, Pass-reacted erpenes.

1 The alcohol soluble guanidine petroleum sulfonate did not dissolve completely in the base oil.

The alcohol-insoluble guanidine petroleum sulfonate was evaluated as a lubricating oil additive by dissolving it in the base oil already described and then testing the resulting blend in a mounted single cylinder H2 Lauson test engine operated under conditions simulating the (IRC L-4 test conditions. The test performed consists of placing 900 grams of the lubricating oil in the crankcase of the single cylinder engine, and operating the engine under a 1.2 H. P. load at 1600120 R. P. M., while maintaining a cooling jacket temperature of 210 F., and oil temperature of 310 F., and an air to fuel ratio of 13.5: 1. At the end of 60 hours operation under these conditions, the engine is stopped, disassembled, and the piston, crankcase, and bearings are examined. The piston varnish, crankcase, base sludge, overall varnish and carbon, and overall sludge are rated on an arbitrary scale of l to 10, the value 10 representing as nearly perfect as ascertainable, number 1' being very poor and numbers 2 to 9 each representing intermediate ratings. As a standard for further evaluation of the blend of lubricating oil and alcohol-insoluble guanidine petroleum sulfonate, the same base oil, but without added guanidine petroleum sulfonate, was tested in exactly the same manner. The base oil blend tested contained the same per cent by weight of the alcohol-insoluble guanidine petroleum sulfonate as used in the strip test described in the foregoing paragraph. For a further comparison, a blend of the same base oil with 4.4 volume per cent of a commercially available oil detergent sold as Lubrizol 67 and comprising a barium petroleum sulfonate was tested in the Lauson engine, in the same manner. This latter blend of base oil with Lubrizol 67 contained the same number of equivalents of of its higher boiling point, thus permitting a higher solusulfonate groups as the tested blend containing guanidine petroleum sulfonate. The following is a tabulation of the results of the Lsuson type engine test described:

I Solvent refined BA! 30 lubricating oil, containing 0.75 volume per cont a commercially available oxidation inhibitor comprising i;S;rc-

I This lend contains an amount of Lubrizol 67 in a concentration equivalent to the number of active detergent groups in an oil containing 2 volume per cent Psranox.

This blend contains an amount of alcohol-insoluble guanldlnc petroleum sullounta in a concentration equivalent to the number of active dete nt cups in an oil containing 4 volume per cent Paranox 64.

i '1 is b nd contains an amount 0! alcohol-insoluble guanidine petroleum sultonato in a concentration equivalent to the number of active detergent groups in an oil containing holume per cent Paranox 64.

established commercial metal-containing detergents.

EXAMPLE 1X A water solution containing guanidine carbonate in slight excess of that required to react with sodium petroleum sulfonate was added with agitation to an aqueous dispersion of a commercially available sodium petroleum sulfonate maintained at 70 F. Under these conditions the sodium petroleum sulfonate reacted with the guanidine carbonate to form a firm plastic mass which separated from the resulting reaction mixture, and which upon cooling formed a gel that while suitable as a grease was not suitable for use as an oil detergent. This reaction demonstrates that a guanidine petroleum sulfonate detergent material of our invention cannot be prepared merely by reacting a commercially available petroleum sulfonic acid or a salt thereof, with'a guanidine salt such as guanidine carbonate. Further, it demonstrates the commercially available sodium petroleum sulfonate to be sufiiciently water-soluble to be reactive in aqueous medium with guanidine carbonate.

EXAMPLE X VIII. The petroleum sulfonic acid product was then converted to a sodium salt by neutralization with sodium hydroxide, and the total resulting neutralization product was subjected to solvent extraction with isopropyl alcohol at room temperature. A portion of a resulting alcoholinsoluble sodium salt thus formed, was treated with aqueous guanidine carbonate in accordance 'with the procedure of Example IX. No reaction appeared to take place and the sodium sulfonate layer was separated from the aqueous guanidine carbonate layer and then contacted with a fresh aqueous guanidine carbonate solution. The sulfonate layer was again separated and water washing was attempted but resulted in formation of a stable emulsion. A sample of the sulfonate layer upon analysis for nitrogen was found to contain 0.55 per cent nitrogen. The sulfated ash content of the sulfonate product was determined and was found to be 4.68 per cent, indicating a high sodium content. These two analytical resultsindicate that the sodium petroleum sulfonate of this example was substantially unreacted with the guanidine carbonate. In this regard the sodium petroleum sulfonate prepared from the SAE 250 oil, as already described in this example, differs markedly from the commercially available petroleum sodium sulfonate of Example IX, inasmuch as in the present example the sodium petroleum sulfonate is too insoluble in water to be reacted with the aqueous guanidine carbonate, whereas the commercially available sodium petroleum sulfonate was sufliciently soluble in water so as to be reacted with guanidine carbonate.

8 axmmzm fonate prepared as described in Example X was treated in the sarne manner as in Example X except that barium chloride was substituted for guanidine carbonate; The resulting reaction product lined hereinbefore.

was analyzed for sulfated ash. The sulfated ash formed was leached with water to remove water-soluble ash. The total suifated ash content was 18.2 per cent and the watermsoluble sulfated ash content was only 1.6, thus indicating that the alcohol-insoluble sodium petioleum sulfonate was substantially unreactive to form the salt. These data further distinguish the commercially available sodium petroleum sulfonates from the sodium petroleum sulfonates of Example X inasmuch as that material can be converted to the barium salt by the method of this example.

EXAMPLE xn Listed as oil com itions l-V in the follow tabulation are several lu roil blends and also a base riil free of any additive material, each of which was evaluated in a series of Lauson engine tests of the type described in Exgnlilple VIII. These evaluation tests are summarized as o ows:

Composition I a n m iv v Lubricatl on volume percent.. 100.0 90.25 Oxidation nhibitor, volume per-' 99 o M 5 cen 0.0 0.75 a Gpanigine pcltiztsdocyltoluene auio 5 o 1 w rma weg percen 0.0 0.0 0.5 U.B.Bl"ayDctergent,weightperv. 00

cent 0.0 0.0 0.0 4.5 as

1 Commercially available (Pass-reacted terpenes) oxidation inhibitor.

The oil employed as the base oil in these compositrons was a solvent refined Mid-Continent oil of lubrieating grade having the following characteristics:

Gravity API 30.3 V scos ty at 210 F 61.8 SUS Viscosity index 98 Neutralization No 0.01

Rating of Composition (Evaluation Scale, 1-10) I II III IV V Piston Varnish Rating- 9. 2 7. 9 8. 4 9. 8 9. 5 crankcase and base sludge rating.... 9. 0 8. 6 8. 2 8. 0 9. 3 Overall varnish and carbon rating. 8. 4 Overall sludge rating 8. 7 Bearing weight loss, mg 1, 005, 6. 5 l. 2 201 lm The d ata of Example XII illustrate the base oil alone' to exhibit desirable piston varnish ratings and crankcase and base sludge ratings. However use of the base oil alone results in high bearing weight loss. Accordingly an oxidation inhibitor is employed as illustrated in column II for the purpose of reducing bearing weight loss. The use of such an inhibitor eifectively reduces piston varmshratmg, and crankcase and base sludge rating. Guanldme octadecyltoluene sulfonate, althoughitcontams only 26 carbon atoms in the molecule and is forthat' reason less desirable than are other oil detergents havmg a largennumber of carbon atoms in the molecule, provides an improvement in the bearing weight loss and in the varnish rating of the base oil tested.

The data of Example XII further illustrate the huprovement of guanidine-octadecyltoluene sulfonate over a commercial additive marketed by the U. B. Bray Company particularly in regard to hearing weight loss.

EXAMPLE XIII A guanidine petroleum sulfonate detergent was prepared substantially in accordance with the procedure out- The petroleum sulfonation stock was the same as described in Example VIII. Batch sulfonation was carried out in a stainless steel vessel by slowly addingwith agitation 450 grams of S03, stabilized 10 agains t l rization, and dissolved in 2000 s of The above results are especially significant inasmuch as ethylene ghli i ri de, to 4000 grams of oil dissolv in 3000 Paranox 64 is a qualified diesel oil detergent capable of grams of ethylene chloride. The sulfonation temperature was maintained at 70' .F. throughout the reaction. The

passing the stringent between L-l test. The only unfavorable comparison the two additives is that of ring reaction mixture was immediately neutralized by stirsticking where the actual difference was not as proring in 700 grams of commercial guanidine carbonated nounced as the rating would indicate. in the form of an aqueous slurry. The neutralized reaction mixture was washed fourltimes with water using one v EXAMPLE XIV volume of wash water per vo ume o tota reaction mix- Y ture per wash. The ethylene chloride solvent was evap Table l g1ves the physical properties of the white orated from the water-washed product and separation of mineral oil used in the preparation and attempted prepundesirable guanidine sulfonates was efiected by multiple aratlon of g eases as shown in Table 2. v batch extraction with isopropyl alcohol. Four batch ex- Table 2 shows clearly ho the alkyl a ryl sulfonates of tractions were carried out using 2 volumes of the alcohol t e etals ordinarily used n greaseniaking did not form per volume of hydrocarbon phase in the first extraction the proper gels under similarconditionsas did the cornnd 36 volume of alcohol in the subsequent extractions. respo Sulfenales 0f guahldme- Lls'ted a oss the After-evaporation of isopropyl alcohol from the final extop of the table are the various aromatics an d olefins traction residue the yield'of guanidine petroleum sulwith which they were alkylated. After alkylation, each fonates plus unreacted oil amounted to 2500 grams. The alkyl aromatic was sulfonated and then neutralized to total nitrogen content of this concentrate was 0.96 per fo m t e s lt of the element or compound in the leftcent by weight which indicates a guanidine petroleum h Vertleal h; each column beneath the P sulfonate content of about 20 per cent by weight. ticularalkyl aromatic indicated are the results of attempt- For purposes of engine evaluation 21.4 weight per cent g o rm a g ease With the mineral oil described in of the above concentrate was added to a base oil, the same Table as that of Example VIII, which contains the oxidation Table 3 lhdleates the mlel'epehetl'atlon 0 two of the inhibitor primarily to provide bearing protection for the better greases, these e Wlth guahldllle y [est i gxprcssed as h b of i i weight toluene-sulfonate and guanidine hexadecyltoluene sulequivalents the preceding blend provides a concentrafonatershewh In Table P llldleflted t s of a tion of guanidine and sulfonate groups exactly equal to g e Worker- The est method used for determining that of the barium and phenate groups contained in a 4 the mwrppenetratwn the g e IS e} of the Amenvolume per cent concentration of the commercial detercan Society for lng Materials and is d as gent Paranox 64 in the same base oil, also containing D 17- 71 as modified according to Indus- 0.75 volumeper cent of the oxidation inhibitor. The and Ehglheel'lhg chemlstl'y, halytleal qm q, 0 two test oils, therefore, were exactly equivalent insofar PP- 103-110 9 The P et 'a l0n is the as concentration of surface active groups are concerned; dlstanee, measured In temh Of a mllhmetel, W qh the i. e., two sulfonate molecules per one Paranox 64 molep penetrates the grease 1n 5 onds. According to cule since the latter contains 2 active phenolic groups thlS method, M P e Ometer is used with a modiper l k, fied cone weighing 20 grams. The grease of which the Parallel engine tests were completed on both of the pehetratlonjs to be measured P the grease 601!- above oils using a modified H2Lauson engine operating 40 tamer holdlhg about 3 f and the P Surface under severe conditions simulating the CRC L-l diesel leveled The eol'ltalnel' 15 Placed on the P engine test for lube oil detergents. The essential test tremeiel base and t s ed. The grease worker referred to difference between these tests and those of Example VIII above is ls n d 1n the indicated ASTM test methare: oil temperature 225 F. and jacket temperature, 300 It bflehy eempl'lses a P with a P 61051112 F. On completion of the tests, the engines were rated through Wh1eh extends a P r- Attached o the as described in Example VIII to give the following re- P a Perfqrated Plate Whleh, When the grease n worker 18 in operation, passes back and forth forcing the grease in the cup to pass through the perforations.

Table 4 shows the decrease in the micropenetration for Base 011 Base guanidine dodecyltoluene sulfonate grease, for which the gg' gggg 4v01ume micropenetrations per indicated strokes in the grease petroleum p r c worker are shown in Table 3, after sitting undisturbed sulionate 64 for the times indicated.

Piston varnish 7 4 .7 Table 1.Characteristics of white mineral il d crankcase and base sludge"-.. 8 5 9.2 833211 seam-ass:- 3? 3;? i i y at 100 F. sUs 183.2 011 ring plugging 9 a 9.0 Viscosity at 210 F. SUS 44.92 nmlisticnng 6 7 -2 Viscosity index Bearma s fl e s- 6 3 6 Refractive index, N 1.474s Specific gravity, D4 0,3590 1 The same as employed in Example VIII. Specific dispersion 102 Table 2- Hydrocarbon Group Radical With Which Salt Is Formed Methylbntene Octene-l Deoene-l Dodeeene-l Hexadeeene-l +Benzene +Toluene +Tolnene +Toluene +Toluene Lithium Soft Plastic Mass, SolulblelnOlLNo SQluIblelnOILNo E 9 e Sodium Insolnbl ln Oil"... SIi ght gel -f Solu1blelnOll,No solilblelin Oil, Potassium Insoluble in 011, SolubleinOlLNo fi l.

Waxy Solid. Gel. Calcium Insoluble in on, SolubleinOll,No .....do Do.

Waxy So gel. Strontium do SOIIIIbIGIHOlLNO Slight gel. arlnm Veryweakgel Weak el Waik l Weakgel. Gnanldlne InsollubletnolhNo lnzszoljuglle in Oil, Fair rease Good tease Good Grease.

trometer, after only 10,000 strokes in the grease worker.

11 1 I2 Table 3.Work stability EXAMPLE XVII exlmple Mieropenetration at Indicated Working Strokes f our new 5 & the lar character as tested by the conventional grease testing 1 I so I 1,000 I 5,000 10,000 I 20,000 [100,000 method CRC designation L-24-745 in a wheel bearing 7 tester, b uilt by Freeman Scientific Company and as de- Gumdmo Dodo, scribed in the above reference.

toluene Sulionnto Table 6 Grease 40 50 70 75 so 141 Guanidine Honda- 10 eyltoluene Salto- G nate Grease 45 4s 02 I 82 01 115 171 tr s-All e Comm Greaseworked 322:3323 Table 4.'-Rev'ersion of guanidine dodecyltoluene sulfog gg g gggf 100,000 Strokes nate worked 100,000 times mg PrlorwTeltins aggg ggg fig' g Mlcropenetmtion g5: very 3118mm None.

(0) Spindle None D0. I n 147 (0) wt. in grams... .0 0.9.

71' o G g 2 55 Conhitlonfififiafi: Gm Gm and to 49 (0) Structure change None Slightly more it- ZLO 43 brous. 48.0 40 (0) Micro netrationchauge 144N064 to 61.

Condition 0! ing:

( Deposits None None. EXAMPLE xv (0) Film oi'lubricant ordry Lubricated Lubricated. This example shows another great advantage of our invention, that of utilizilgg tahllarlrixture of olefinfs for alkyli XAMPLE XVIII ating the aromatic instance, a raction o In i example a white mineral o ve similar cracked naph bollmg 111 the 8? 246 properties to that used in the previous two e r amples, w: and containing only 40 per cent olefins was used to t This oil was admixed with the sodium barium y T1135 Product was sulfonated and and guanfdine salts of trihexyltoluene sulfonic acid under neu ral with s a carbonate. The olefins, 9 conditions described in this specification hereinabove. It of which were branched, had the double bondun various i clearly shown by the data'in Table 7 below that the P05010118 addlllol'l t0 -p l Thus, 13 guanidine salt was the only one which made a satisfactory that our utv n l n m y be prqctlced Y 1 8 grease. It is also shown that a satisfactory grease may easily obtained refinery cuts without extensive -pur1fica be made by using between 5 and 32 wcight cem f 0 the guanidine salt. The sodium and barium salts used in The ar P made y {113116131118 20 Pm by 8 amounts in about the middle of this range were unsatis- Of thfl fi fi sulfonatc i' g g of 33 factory. Although a gel was formed in the case of minera o' y eating to a empera e 0 con b and 240 C. and then cooling. The resulting gel was 23;? on slums for sacral. days lt comes liqmd then milled to a smooth grease. Tab, 7

Table 1 gives the physrcalproperties of the mineral oil used to form the grease with the guamdme alkyl aryl ulfonate, Radical with which gag Malta In Table 5 the micropenetration of the grease prepared salt 18 Fmmd as descrifid above is compared 1:vithdthat at three commereial -purpose greases purc ase on e open mar- 60 ket. Grease A was a barium base grease made from lube ifih'fiIIIIIIIIII 13 iiii s'it'si fliss, u uones alter oil in which the gelation agent was derived from fatty G several days. acids. Grease B was a lithium base grease having the g: gfia ffi w m m to gelation agent made by treating fatty acids. Commercial ud grease C is a sodium base of which the gelation agent was made by sapomfymg nonedible tallow with sodium hydroxide. As may be observed, our grease is EXAMPLEXIX equal to or better than the comparative greases. Note that commercial grease B exceeded a penetration of 420, example shows m Table 8 the lack of utility of which is about the maximum measuring limit of the pene- 'y g to make a suitable 8" y p g to disperse a guanidine salt, of the fatty acids used in grease making Table 5 .Work stability Micropenetration at Indicated Working Strokes Change in Micro- Peroent Change in penetration between 1.000 and betweenlmonnd 1 00 1,000 5,000 10,000 50,000 100,000 100,000 strokes 100,000 strokes Glanidlne Alkyl Aryl Sullonate 27 52 so 94 122 07 as.

male. Commercial Grease A 125 124 115 192 244 200 124. 00. Commercial Grease B 10a 103 215 380 420 above 14:50:10,000.-- above a: at 10,000. Commercial Grease C 53 73 107 137 151 237 127 119.

75 as their metal salts, in a mineral oil. A mineral oil simi- XA X lar to those used in the previous examples was used here.

Table 8 I A soft grease was made by using the 'guanidine salt of an alkyl aryl sulfonic acid in which the olefins used in 80 a Salt, SoluhllityinOll producing the alkyl aromatic boiled in the range of 190 to 200 C., and the aromatic was toluene. Only a small Guanidine laurate Insoluble, strstiiled on cooling. portion of the thus formed soa or gelation agent dl3- g ts Hardwuycako, workedtopoor grease. persed in the mineral oil used; however, the portion a enylbmm m"" PM which did, produced a satisfactory soft grease.

oil and the disulfonate are given in the following table along with formulas calculated from these analyses.

mg Dlguanzldlne Dlsnltonate 0t], Found Calculated 0 85. 60 65. 6 66. 4 H 12. 84 9. 7 10. 5 a 6. 2 6. 3 N 8. 2 8. 3 O Q 10. 3 9. 6 M01 Wt 730 I, 050 *6 Form nHu CnHnSrNmOaa IUHII l IOO I By dlflerenoe. 5 Based on formula of charge oil.

The diguanidine disulfonate thus produced was dissolved in hot oil; the resulting oil-diguanidine disulfonatedmixture became a grease upon cooling.

As will be evident to those skilled in the art, various modifications can be made or followed, in the light-of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the claims.

We claim:

1. As a new class of compositions, synthetic guanidine alkyl hydrocarbonaryl sulfonates containing a total number of at least carbon atoms in the alkyl groups.

2. As a new class of chemical compounds, the guanidine salts of alkyl hydrocarbonaryl sulfonic acids having a total number of carbon atoms in the alkyl groups in the range of 10 to 20.

3. As a new class of chemical compounds, the guanidine salts of alkyl hydrocarbonaryl sulfonic acids having a total number of carbon atoms in the alkyl groups in the range of 10 to 20, having at least one alkyl group containing at least .10 carbon atoms, and having the pifroperty of forming lubricants when dispersed in mineral o 4. A new class of chemical compounds according to claim 3 wherein the aryl nucleus 18 selected from the group consisting of benzene, naphthalene, diphenyl, anthracene, and their lower alkyl homologues.

5. As a new class of chemical compounds, the uanidine salts of alkyl hydrocarbonaryl sulfonic acids aving a total number of carbon atoms in the alkyl groups of not more than 20, having at least two alkyl groups of at least 8 carbon atoms each, and having the property of forming a lubricant when rsed in mineral oil, wherein the aryl nucleus is select from the group consisting of benzene, naphthalene, diphenyl, anthracene, and their lower alkyl homologues.

6. As a new chemical compound, guanidine dode-- cyltoluene sulfonate.

7. As a new chemical compound, guanidine hexadecyltoluene sulfonate.

8. A guanidine alkyl hydrocarbonaryl sulfonate contaimng at least 10 alkyl carbon atoms and not more than carbon atoms in the molecule.

9. A process for the manufacture of a guanidine alkyl aryl sulfonate suitable as a lubricant component, comprising sulfonating a synthetic alkyl aromatic hydrocarbon containing at least 10 alkyl group carbon atoms in the molecule, neutralizing sulfonic acid thus produced with a guanidine compound selected from the group consisting of guanidine and a basic guanidine salt, result ing neutralization product containing a guanidine alkyl aryl sulfonate of at least one of the group consisting of oil-soluble and oil-insoluble guanidine alkyl aryl sulfonates, separating one of said oil-soluble and oilinsoluble guanidine alkyl sulfonates from any of the other in said neutralization product, and recovering at least one of said oil-soluble and oil-insoluble sulfonates thus separated, as product of the process.

10. The process of claim 9 wherein an oil-soluble guanidine alkyl aryl sulfonate is recovered as said product.

11. The process,of claim 9 wherein an oil-insoluble guanidine alkyl aryl sulfonate is recovered as said product.

12. The process of claim 10 wherein said oil-soluble guanidine sulfonate contains from -70 carbon atoms in the molecule.

13. The process of claim 10 wherein said oil-soluble guanidine sulfonate contains from 24-34 carbon atoms in the molecule.

14. The process of claim 11 wherein said oil-insoluble sulfonate contains from 17-35 carbon atoms in the molecule.

15. The process of claim 9 wherein oil-soluble and 011- insoluble sulfonates are separated by alcohol extraction.

16. The process of claim 11 wherein said alkyl aromatic hydrocarbon to be sulfonated, is a product of alkylation of an aromatic hydrocarbon with an olefin fraction boiling in the range of 190-350 F.

17. As a new class of chemical compounds, the guanidine salts of alkyl aryl sulfonic acids wherem the aryl nucleus is selected from the group consisting of benzene, naphthalene, diphenyl, anthracene, and their lower alkyl homologues, having a total number of carbon atoms in the alkyl groups of not more than 20, having at least three alkyl groups of at least 6 carbon atoms each, and having the property of forming a lubricant when d1spersed in mineral oil.

18. As a new chemical compound, guanidine trihexyltoluene sulfonate.

19. A guanidine alkyl hydrocarbonaryl sulfonate containing from 40 to carbon atoms in the molecule.

20. As a new chemical compound, guanidine decylnaphthalene sulfonate.

21. As a new chemical compound, guanidine tetradecyldiphenyl sulfonate.

ReferencesCltellintheflleofthlspatent UNITED STATES PATENTS 2,061,601 Steik Nov. 24, 1936 2,076,623 De' Groote r. 13, 1937 2,223,935 Daniels et al. 1940 2,473,112 Sh June 14, 1949

Claims (1)

1. AS A NEW CLASS OF COMPOSITIONS, SYNTHETIC GUANIDINE ALKYL HYDROCARBONARYL SULFONATES CONTAINING A TOTAL NUMBER OF AT LEAST 10 CARBON ATOMS IN THE ALKYL GROUPS.