US2415833A - Lubricant - Google Patents

Description

Patented Feb. 18, 1947" LUBRICANT Louis A. Mikeska and Allen R. Kittleson, Wcst- I field, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application January 1, 1942, Serial No. 425,383

.8Claims.

This invention relates to the improvement of hydrocarbon oils and more particularly to the preparation of improved lubricating'oil compositions. In the development of petroleum lubrieating oils, the trend has been to use more and more efficient refining methods in order to reduce the tendency of the oils to form carbon and deposits of solid matter or sludge. While such highly refined oils possess many advantages, their resistance to oxidation, particularly under conditions of severe service, is generally decreased and they are more prone to form soluble acidic oxidation products which are corrosive. They are generally less effective than the un-| treated oils in protecting the metal surfaces which they contact against rusting and corrosion due to oxygen and moisture; they also often deposit thick films or "vamish on hot metal surfaces, such as the pistons of internalcombustion engines. It has now been found that these defects can be greatly reduced by adding to the oils a small proportion of a new class of improving agents have the generalvformula in which T represents a negative element of group 6, such as oxygen or sulfur, selenium or tellurlum, X represents hydrogen, an organic radical, an onium base residue or a metal equivalent, Y represents hydrogen or an organic group 2 such as an alkyl radical, an aryl, alphyl or cycloalkyl radical, which radicals may contain substituent groups, Z represents an inorganic negative element or radical, such as a halogen or the radicals CNor SCN, or a radical which is linked to R by-means of a negative element of groups 5 and 6 such as oxygen, sulfur, phosphorus or nitrogen, and R represents a divalent alkyl linkage such as in which R represents either hydrogen or alkyl or aryl groups and may represent similar or different groups in the same molecule, and which molecule may contain one or more TX radicals, one or more Y radicals and one or more --RZ radicals of similar or different constitution attached to the same aryl nucleus. All such substituent radicals may be attached to the aryl nucleus in any position; when the aryl nucleus is a benzene ring, the other substituent radicals may be ortho, meta and/or para to each other and to .the OX radical. Other illustrative radicals represented by Z in the above formula are hydroxyl, mercapto, amino, nitro, nitrile, xanthogenyl, carbamyl, thiocarbamyl, sulfide, disulfide, polysulfide, phosphite, phosphate, thiophosphite, thiophosphate, and the like. The desired compounds are also characterized by sufiicient carbon atoms in aliphatic linkages to produce oil solubility and preferably have 'at least 4 carbon atoms in alkyl groups in the molecule in compounds containing no metal atoms and at least 10 or 12 carbon atoms in alkyl groups in compounds which contain a metal atom. The \preferred metals in the above-described compounds include metals of groups 2, 3 and 8. such as magnesium, barium, calcium, cobalt, cadmium, nickel, zinc, tin, aluminum, and the like. In compounds prepared with polyvalent metals, one valence bond may replace H in a phenolic hydroxyl group as described above, and other valences may replace H in other phenolic hydroxyl groups of the same molecule, or of other I slmilar'molecules (which may contain diflerent substituents) or the other valence or valences may be linked to any suitable inorganic or organic radical. The onium bases include those of sulfur, phosphorus and nitrogen.

The complex mixtures of chlormethyl alkyl phenols. prepared by condensation of phenols with formaldehyde and hydrogen chloride represent a preferred class of materials for use in this invention either directly as improving agents for lubricating oils or as intermediate products from which various derivatives are prepared which i are also eflective lubricating oil improving agents. The various components of these complex mixtures of chlormethyl alkyl phenols and of the resulting derivatives may also be separated from the complex products. or prepared in relatively pure form by any suitable methods and used similarly. The reaction between alkyl phenol. formaldehyde and hydrogen chloride is aided by passing dry hydrogen chloride con- 'tinuously through the reaction mixture when concentrated aqueous hydrochloric acid is used as an initial reagent. This reaction may also be conducted under anhydrous conditions as illustrated in the following example:

EXAMPLE 1 ClCHaOCHzCl, CICH2OCH OCH2CP and ClCHzOCHzOCI-IzOCHzCl To this mixture were added 206 grams of diisobutyl phenol (iso-octyl phenol) and the reaction temperature increased to 50 C. The react- 40 ants were stirred at this temperature for a period of 2-3 hours, a slow stream of dry HCl being passed through the mixture in the meantime. The resulting mixture was washed free of unreacted formaldehyde by washing once with concentrated aqueous HCl and the excess HCl washed from the benzene layer by cold water. After drying the washed benzene layer and removing the benzene at 70 C. under reduced pressure. a residual viscous oil (I) was obtained containing 12 to 15% chlorine.

The chlorine content of these products may be controlled by the ratio of the formaldehyde and phenol used in the initial reaction. For example, when conducting the preparation as described in Example 1 with several different ratios of formaldehyde to para-iso-octyl phenol, the chlorine contentsof the products were observed to be as follows:

- The products ofa'bout 12% to about 14% chlorine content are generally preferred, although the other products of lower and higher chlorine content may also be used in this invention.

Among the compounds present in the produc from this reaction are the following:

CHsCl Ghlormethyl diisobutyl phenol OH 10 l C lHaC CFhCl aHi'! Bis chlormethyl diisobutyl phenol on on gon -genie] UH" :Hn

2 5 Chlorinethyl bis (dlisobutyi hydroxy phenyl) methane OH OH ClHiC CH CHzOl J Bis (diiscbutyl chlormethyl hydroxy phenyl) methane Thus these compounds are considered to have the following general formula in which the substituent groups may be attached to any position of the aryl nucleus indicated diagrammatically by the hexagon, R represents a hydrocarbon group of 1 or' more carbon atoms and preferably an alkyl group of 4 or more carbon atoms, and Y epresents hydrogen or an organic radical, especially an alkyl, aryl or aralkyl radical which may in turn contain substituent groups. It is to be understood that such individual compounds may also be prepared by any other suitable method, and may be'used individually and in mixtures as lubricating oil improving agents and as intermediates in the methods described herein for the preparation of lubricating oil improving agents according to the present invention.

The individual chlorethers described above may be separated from the mixed product, or prepared by any suitable method, and then condensed with alkyl phenols to prepare lubricating oil improving agents. Other chlorethers, such as chlormethyl ethyl ether, may also be used. The 55 condensation of the alpha chlorethers and alkyl phenols may also be conducted with suitable catalysts such as stannic chloride or anhydrous zinc chloride. Also, the alkyl phenol may be dissolved in an equivalent amount of alcohol. The mixture is then saturated with HCl. Under this procedure, the reaction is easily controlled in such a way as to yield products of uniform chlorine content.

The segregation of fractions of the product of 75 Example 1, and the preparation'of other derivaa auasssh tivesof the alkyl, oxy beiizyl structure, are illus-.

trated in'the following examples.

e Exams: 2

The viscous oil product obtained as described in Example 1 was diluted with several volumes of petroleum ether. On cooling this mixture to about 0., a white solid (representing about 30% of the crude product) crystallized out. This prod uct was analyzed and found to be bis (ll-hydroxy 3-chlormethyl 5-diisobutyl phenyl) methane (II). I

on 9H cicnrgcm-gcmcl r1111 :11"

A procedure essentially the same as that used Percent I1 Analysis Found I Percent c .Q. 72.10 o. as

Exsmrm: 5

A solution or 40grams NaOHin 250 cc. of

water was added to a solution of 221 grams (0.5

mol) of diisobutyl phenol sulfide in'350 cc. of

dioxan. To thismixture were added 122 grams of formalin (37% CHaO, 1.5 mols) at 'room temperature. The reactants were'allowed to stand for four days, after which the. mixture was acidifled and'extracted as in Example 4. There were in Example 1 was followed except that 221 parts by weight of diisobutyl phenol sulfide wereused in place of the phenol. The resulting product (III) contained from 6' to 7.5% chlorine, which indicates it to consist largely of chlormethyl di- 1 isobutyl phenol sulfide.

OH OIH QsQcmm uHn aHn A method of preparing the alkyl hydroxy benzyl derivatives in relatively pure form involves reacting the alkyl phenol with formaldehyde in an aqueous alkaline vehicle. This is illustrated in the following example:

EXAMPLE 4 V m 1,236 grams (6 mols) of diisobutyl phenolw'ere added to a solution of 2,000 cc. of water and 800 cc. of methyl alcohol containing 250 grams (6.25 mols) of NaOH, 1,314 grams of aqueous formaldehyde (formalin, 37% CHeO) were added to the phenolate solution at room temperature and the mixture allowed to stand for three days.

The reaction mixture was then acidified with a small excess of dilute aqueous HCl. The dialcohol separated out in an oily layer which was taken up in a /50 mixture of U. S. P. ethyl ether and petroleum ether. The ether layer was washed twice with water, dried, and the solvent removed at 70 C., the last trace being stripped oil under reduced pressure. The residue was a light straw colored viscous oil which crystallized on standing. 1,360 grams were recovered. The analysis indicates this to be 2,6-dihydroxy methyl ii-diisobutyl Phenol (IV).

HOCHr- CHaOH then recovered 225 grams of a viscous straw colored oil which, upon analysis, was determined to be bis (hydroxy methyl) diisobutyl phenol sulflde (V).

on 0H HOCH s 031011 aHu aHu Analysis Theory Found PercentO 71.71 12125 PercentH 9.16 10.10 PercentS 6.37 6.22

Similar disulfides may be prepared by substituting the alkyl phenol disulflde in place of the mono-sulfide in the above described reaction.

The hydroxy benzyl alcohols may be readily converted to the corresponding chlorides as illustrated in the following example:

ExsMPLr: 6

200 grams of (IV) were diluted with cc. of naphtha. Dry HCl gas was bubbled through the solution at room temperature for 8 hours. The aqueous layer formed was removed and the naphtha layer washed twice with ice and water, dried with calcium chloride and a portion of the solvent allowed to evaporate off. 164 grams of a crystalline'product separated out. This product melted between 70 and 75 C. and was determined by analysis to be largely bis chlormethyl diisobutyl phenol (VI).

Various derivatives of the types of products described in the above examples may be prepared and used as improving agents in lubricating oils according to this invention. The hydrogen of one or more of the phenolic hydroxy] groups in the molecule may be replaced by organic or inorganic radicals, as by esterlflcation or etherification. or

= by a metal equivalent of a monovalent or polyvalent metal.

EXAMPLE '7 4.6 grams (0.2 mol) of metallic sodium were reacted with 100 cc. of absolute ethyl alcohol in a flask equipped with stirrer and reflux condenser. 71.5 grams (0.2 mol) of dioctyl dithiophosphoric acid were added to the sodium aicoholate solution.

To the alcoholic solution of sodium dioctyl dithiophosphate were added 27.9 grams of his chlormethyl diisobutyl phenol (VI). The reaction mixture was then refluxed for 1% hours, after which it was poured into water, acidified, and extracted with ether. The ether layer was washed several times with water, dried over sodium sulfate and the ether stripped off.

The phenolic derivative thus obtained was converted to the sodium salt by adding 43.? grams of the former to 1.15 grams of sodium in 40 cc. of absolute ethyl alcohol. The sodium phenolate thus formed was treated with a solution of 2.5 grams of anhydrous Ca(NOa) 2 in 40 cc. of acetone to obtain the calcium salt. The NaNOs was fil- H I] (CaIElnOhP-SCH CH1SP(OC2H11): Ca

aHi'l Analysis Theory Found Per cent Ca Per cent S EXAMPLE 8 18.4 grams of metallic sodium (0.8 mol) were reacted with 400 cc. of absolute ethyl alcohol. To this sodium ethylate solution were added 83.2 grams (0.8 mol) of amyl mercaptan. The resultant alcoholic solution of sodium amyl mercaptide was cooled to about 10 C., after which a solution of 104 grams of (II) in 200 cc. of dioxan were added. The reaction mixture was refluxed for 1 hours, after which it was allowed to stand at room temperature overnight. The product was then neutralized by pouring over cracked ice in dilute HCl. The oily layer which separated was extracted with ether andthe ether layer washed several times with water. The ether solution was dried over CaClz and the solvent and excess mercaptan removed at 100 C. under reduced pressure.

126 grams of a straw colored viscous oil were thus obtained.

To prepare the barium salt, grams of the above product in about 600 cc. of toluene were added to 57 grams of Ba(OH)28HzO dissolved in 150 cc. of methyl alcohol. The reaction mixture was refluxed, the methyl alcohol and waterof reaction being removed from the mixture by means of a-trap. After all the water had been removed, the toluene solution was filtered to remove BaCOa and unreacted Ba(0H)-2. The filtrate was stripped free of solvent at 100 C., reduced pressure being used to remove the last traces.

111 grams of a straw colored pulverizable solid (VIII) were thus obtained. This product was indicated by analysis to have the following structure:

K Ba\ CaHnSGHz- CHa- CHzSCa-Hu aHn uHn Analysis Theory Found Per cents s. 10 1.35 Per cent Ba 17. 30 14.71

EXAMPLE 9 133 grams (0.5 mol) of (IV), 150 grams (1.5 mols) of amyl mercaptan and 300 cc. of xylene were charged to a flask equipped with heater, stirrer, reflux condenser and water trap, The mixture was refluxed, trapping oil the water of reaction. After 3 hours a total of 17 cc. of H20 were recovered and the reaction discontinued. The xylene and excess amyl mercaptan were removed at C. under reduced pressure. 223 grams of a straw colored oil (IX) were recovered. This was indicated by analysis to be his (amyl thlomethyl) diisobutyl phenol.

this sodium alcoholate solution were added 146 grams A; mol) of (IX). To the alcoholic substituted phenolate solution were then added 53 grams of BaBrz dissolved in 200 cc. of methyl alcohol. The reaction mixture was refluxed for two hours, after which the alcohols were distilled oil. The residue was diluted with petroleum ether and filtered to remove the NaBr. The filtrate was stripped free of solvent, leaving a very viscous oil residue (X), which was indicated by analysis to be the barium salt bis (amyl thiomethyl) diisobutyl phenol.

30 grams of (VI) were added to an alcoholic solution of NaSH and stirred for about one hour. The mixture was acidified, diluted with water and extracted with a 50/50 mixture of U. S. P. ethyl ether and petroleum ether. The ether layer was washed several times with water, dried; and the solvent stripped oil. The residue was taken up in petroleum ether andcooled to about 0, C. About 8 grams of a crystalline precipitate formed (XI-A) which was filtered oil. The filtrate was stripped free of solvent, leaving a semi-solid resinous product (XI).

' Analysis XI XI-A Per cent 8 16.1 18. 3

The crystalline compound ICE-A is considered to be the mercaptan HSCH CHaSH slit"! and the resinous substance X1 is considered to be a polymeric form oi disulfide oxidation product containing the structure EXAMPLE 12 125 grams of (V) 40 grams oi. amyl mercaptan,

' 400 cc. of toluene and 1.0 gram of p-toluene sulionic acid were reacted as in Example 9. There were thus recovered 133 grams of a dark viscous oil (XII), which is considered, in view of the analysis, to have the structure C HnSCH B CHzSCsH 65H" aH|1 Analysis Theory Found Per cent 8 14. 2 12.4

ExAMrLa I 13 150 grams of (IV), 72 grams or reflnerymercaptans (boiling range '26-80 0., 'derived from petroleum oils and consisting mostly of methyl, ethyl and propyl mercaptans) and 1.0 gram of p-toluene sulfonic acid werecharged to a stainless steel bomb. The bomb was heated to 120 C. for a period of 2 hours, after which the reaction product was isolated by diluting with a,

solvent such as petroleum ether, followed by water washing to remove the p-toluene sulfonic acid, drying and finally stripping off the solvent. 182 grams of a straw colored oil (XIII) were recovered, having the following analysis:

Analysis of product Per cent C 69.46 Per cent H 10.00 r cent S EXAMPLE 14 The Ba salt of (x111) was prepared by the process described in Example 8, adding 60 grams of Ba(0H)28HzO dissolved in 200 cc. of methyl alcohol to 115 grams of (XIII) dissolved in 400 cc. of toluene. There were recovered 117 grams of a light straw colored pulverizable solid (XIV having the analysis:

Analysis of product Per cent Ba Per cent EXAMPLE 15 50.8 grams of the mixture of chlormethyl diisobutyl phenols (I) obtained as the product in Example I were dissolved in 50 cc. of absolute ethyl alcohol and added slowly from a dropping funnel to a stirred solution of 22.0 grams of KzS in ethyl alcohol. After all of the hloride was added, the solution was'refiuxed for 2 hours. The alcoholic solution was then poured into ice and water and extracted with ether. The ether layer was washed once with dilute HCl, then water, then dried over NazSOe and the ether stripped 01f under reduced pressure to remove the last traces. There were recovered 42 grams of astraw colored oil containing 8.4% sulfur.

The barium derivative was prepared as in Example 8, using 36 grams of the above sulfide; 200

cc. xylene, 23 grams Ba(OH)z8HzO, and 200 cc. methyl alcohol. There were recovered 46 grams of a yellowish pulverizable solid (XV) containing 17.1% barium.

EXAMPLE 16 50.8 grams of the mixture of chlormethyl diisobutyl phenols (I) in 100cc. of dioxan were added dropwise to a stirred solution of 60 grams of potassium ethyl xanthate in 250 cc. of dioxan. Aiter all of the chloride was added, the mixture was stirred for several hours at room temperature.

The dioxan solution was poured into water and extracted with ethe I The ether layer was washed once with dilute acid followed by several water washes,'then dried over NazSOe and the ether stripped off.

There were recovered'5-9 grams of a reddish oil (XVI) containing 18.2% sulfur which was a complex mixture of xanthates of chlormethyl diiso- 75 butyl phenols. The reaction with respect to the l1 simpler components may be indicated by the following general formulae:

100.8 grams of KOH were dissolved in 900 cc. of absolute ethyl alcohol and H28 added until 61.2 grams were absorbed. To thissolution of KSH were added slowly with stirring 152.4 grams of the mixture of chlormethyl diisobutyl phenols (I) dissolved in 300 cc. of absolute ethyl alcohol. The mixture was stirred at room temperature for 2 hours and then at 80 C. for 3 hours. The solution was then poured into ice and water; acidified with HCl, extracted with ether and the extract washed with Water, dried over NazSOr, and the ether finally removed at 100 C. There were recovered 132 grams of a light colored soft resin.

The barium salt was prepared by the procedure followed in Example 8, using 50.4 grams of the above resinous product, 300 cc. of xylene, 200 cc. of methyl alcohol and 63 grams of Ba(OH) 28H2O. There were recovered 64 grams of a yellow powder (XVII) containing 17.4% barium.

EXAMPLE 18 stirred during addition of the chlormethyl deriva-- tive. The mixture was stirred for an additional hour at refluxing temperature after which'the reactants were poured on ice, acidified with HCl extracted with ether and the extract washed with water, dried and the solvent and excess mercaptan removed at 100 C. under reduced pressure. There were recovered 239 grams of a straw colored oil containing 10.9% of sulfur. This product was converted to the barium salt (XVIII) by the same process used in Example 8. The reactions involved are illustrated with respect to one of the chlormethyl diisobutyl phenols as follows:

:-Ol1 i 011.01 NsCl Ct nSNa CHaSCtHu \JHHH sHn i Hamil):

Ba salt EXAMPLE 19 The mixed xanthates (XVI) described in Example 16 were treated in absoluteethyl alcohol solution with sodium ethylate to prepare the corresponding sodium salts. To the solution ofthe resulting sodium phenolate derivatives was added an abolute ethyl alcohol solution containing about 14% of calcium chloride. The reaction mixture was then diluted with naphtha, the sodium chloride precipitate filtered off and the filtrate evaporated to dryness under reduced pressure to obtain the calcium salt (XIX) which is indicated with respect to one of the simpler components of the mixture as having the formula ll CIHIO CSCH 2 din EXAMPLE 20 A solution of the sodium salt of cardanol was prepared by adding 30 grams NaOH in 500 cc. water to 576 grams of cardanol in 300 cc. of dioxan. 486 grams of formalin (37%CH20) were added to the phenolate solution at room temperature and the mixture allowed to stand for 4 days. The hydroxy-methyl derivative was recovered by the method described in Example 4. 116 grams of this hydroxymethyl cardanol product, grams of refinery mercaptans and 1 gram of p-toluene sulfonic acid were charged to a stainless steel bomb. The bomb was heated to 100110 C. for 5 hours, after which the product was removed, diluted with naphtha, washed several times with water, dried, and the solvent stripped off. 120 grams of a dark viscous oil (H) were recovered which contained 12.1% sulfur. The reaction may be indicated by the following general formulae:

on on 031011). crass). CuH21 CHE" in which R represents the organic radical of the refinery mercaptans (described in Example 13) and n is 1 or 2.

EXAMPLE 21 420 grams of a mixture of phenols extracted from a petroleum oil distillate and having an average molecular weight of 141 were dissolved in 300 cc. of dioxan and mixed with a solution of 120 grams of sodium hydroxy in 600 cc. of water. 608 grams of formalin solution (37% CHzO) were then added and the mixture allowed to stand at room temperature for 4 days. The reaction mixture was then treated by the method described in Example 4 to recover the hydroxymethyl derivatives. This product was converted to the alkyl thiomethyl derivative by the process described in Example 20, using 120 grams of the hydroxymethyl petroleum phenols," 100 grams of the same refinery mercaptans and 1 gram of p-toluene sulfonic acid. The resulting product was a. reddish mobile oil (XXI) containing 14% sulfur.

The effectiveness of these products as improving agents for hydrocarbon oils is illustrated by the following examples:

EXAMPLE 22.--QxIoA'rIoN Rm;

Blank oil+additive 13 oil maintained at 392 F. The results of this test were as follows:

Oxidation rate. cc.

Oil

Blank oll 29, 38. 37, 31 Blank oll+ndditive (XV) 9, 13,13 16 Blank oil+additlve (XVI). l9, 3], 24, 21 Blank oil+additive (XVII)--. 18, 1 12, la

XIX) 6, 3, 44, 20

Thus the tendency of oils to become oxidized is greatly reduced by the addition of the improving agents of this invention, as indicated by the 01/15 min. intervals Diesel engines and in automobile engines which operate with high crankcase temperatures. The ability of the improving agents of this invention to reduce varnish formation, as shown in the above example, isthus of special importance in preparing lubricants for such uses.

EXAMPBE 24.ALLOY BEARING CORROSION TESTS The corrosiveness of lubricating oil blends was evaluated in the following manner: 500 cc. of the reduced rate of oxidation of the blend, as comoil were Plac in a glass oxidation tube fitted paredwith the unblended oil, in the above test.

' This represents a substantial improvement, especially in regard to highly refined petroleum oils; for the oxidation of such oils results in acidic at the bottom with an air inlet tube perforated to facilitate air distribution. The tube was then immersed in a heating bath so that the oil temperature was maintained at 325 F. during the oxidation products which remain largely distest. Two quarter sections of automotive bearsolved in the oil and thereby cause it to become corrosive, less resistant to emulsification and to become impaired in quality in regard to color, odor, taste and stability.

EXAMPLE 23.VARNISH TEST ings of copper-lead alloy of known weight were attached on opposite sides of a stainless steel rod which was then immersed in the test oil and rotated at 600 R. P. M., thus providing eflicient agitation of the sample during the test. -Air was blown through the oil at the rate of 2 cu. ft. per hour. The hearings were removed at intervals, washed with naphtha and weighed to determine the loss in weight.

The results of tests with highly refined petroleum lubricating oils and with blends of the same oils containing small amounts of the products described in the above examples were as follows:

Bearing corrosion loss, mgs. Oil

1 hour 4 hours 8 hours 12 hours 16 hours 20 hours 24 hours Blank SJA. E. 20 oil A 5 169 Blank S. A. E.+0.257 (VII) 3 20 63 Blank s. A. E.+o.25i (IX) 1 a 1 e17 169 Blank S. A. E.+0.25% (X) 0 1 17 52 Blank S. A. E.+0.257 (XI) 0 0 2 4 18 Blank s. A. E.+o.2s ?Z, (XII) 7 14 74 Blank S. A. E.+0.25% (XIII)- 0 0 0 0 7 Blank S. A. E.+0.25% (XIV) 2 7 37 Blank S. A. E.+0.25% (XXL- 0 3 97 Blank S. A. E.-|-0.25% (XX 0 4 147 Blank S. A. E. 20 01 3 61 279 Blank S. A. E.+1.0% (VIII) 3 11 16 30 39 59 was placed. At the end of the 48-hour period the glass plate was removed, washed with naph- Similar tests at 325 F. with both copper-lead and cadmium-silver alloy hearings were as foltha, air dried and weighed to determine the lows:

Bearing corrosion loss, mgs.

Oil Cu-Pb Cd-Ag 4hours 12 hours l6hours 4hours 12 hours 16 hours Blank S. A. E. 20 oil B 18 12 Blank S. A. E.+l% (XVII) 0 0 Blank S. A. E. 200i] 0 4 42 0 Blank S. A. E.+0.1% (XIX)--- 1 0 0 0 weight of varnish deposit. The results were as follows:

Varnish formed in 48 hours, mg.

This formation of varnish-likedepo sits is characteristic of many highly refined petroleum with the blank or unblended oils. in the above test.

Exmrn 25.Enom 'I'rsrs Engine tests to demonstrate the efiectiveness' of the test oil under the severe conditions encountered in lubricating Diesel engines were conducted by using the test oil as crankcase lubri- V cant during 60 hours operation of a single cylinder Caterpillar Diesel engine operated under full load conditions at 850 R. P. M. with an air temperature of 140 F. and a crankcase oil temperature of 195 C. Atthe end of each sixty-hour test the engine was dismantled and carefully inspected, the condition of the parts being reported on a demerit basis in which zero indicates a condition equal to the start of the test. The results of tests on a highly refined petroleum lubricating oil having a Saybolt viscosity at 210 F. at 52 seconds and on blends of the same oil with 1% of compounds described in the above examples, are given in the following table:

The lower demerit ratings observed in each instance with the blended oils demonstrate the eifectiveness, in improving engine conditions, of the oil improving agents of this invention.

- In addition to the compounds, the preparation of which is described in the above examples, many other derivatives of the chlormethyl alkyl phenols may be prepared and used as improving agents in accordance with this invention. Examples of some of these derivatives are given below in a brief outline of suitable methods for their preparation.

While these preparations are generally applicable to the complex mixtures of the chlormethyl alkyl phenol products obtained by reaction of the phenols, aldehydes and HCl as described above, the preparations may also be carried out with the individual chlormethyl derivatives of phenols however prepared. Such derivatives may contain one or more chlormethyl groups attached to a single aryl nucleus and P eferably contain an alkyl group, R, attached to the aryl nucleus. This alkyl group contains preferably 4 to 8 or more carbon atoms. The preparations are illustrated with respect to one of the chlormethyl alkyl phenols as follows:

Heavy metal atoms or H may besubstituted for one or both of the sodium atoms.

on on NaSH O zmon RO-cmcn a omen +NaCl ONa ' 16 Other metal atoms or H may be substituted for one or both of the sodium atoms.

on OK NaSH PO13 n cmcl 12 cmsa A metal atom may be substituted for the hydroxyl hydrogen atom. Alkylated phenols can be readily converted into alkylated dimethylol phenols by condensing alkaline salts of the former with formaldehyde.

On condensation of these dimethylol phenols, with such products as P285; P283; PCla; POCla; PSCla; HsPo-r; HaPOa, etc., total or partial esters are obtained:

CHaOH +NaCl Metal atoms may be substituted for one or both of the hydroxyl hydrogen atoms.

' OH OH NaSH $60: R CHaCl R CHzSH r HO OH l S CICHI R on no i n cmoc-s-om-O-nflnm 17 Metal atoms may be substituted for one or both of the hydroxyl hydrogen atoms.

vOH

Metal atoms may be substituted for one or both of thehydroxyl hydrogen atoms.

RGO HaCH-NaO R --t A metal atom may be substituted for the hydroxyl hydrogen atom.

a cr'ncHHczcn no ROCHz-CECH RO-CJm-oO- m A metal atom may be substituted for the hydroxyl hydrogen atom.

on rzOornc1+cmcocnmcooa 0E s ROCHz-CH-COOR $OCH5 +NaCl erri RC-CH2C-COOR+H5 u on oo-ont R-O-CHzCH-NaCEKCOOR) Mg. RGCHMEKCOORM e0 +NaCl 0-MK RGCH2C(COOR)2+HQ O-Ga 18 Wherever the group SH occurs in the products of the above reactions, the products may be converted by oxidation or by treatment with SCI: or 82C]: into compounds containing the following groups -S--S-, SS S, and

respectively.

Although very satisfactory procedures for preparing the oil improving agents of this invention have been described with reference to the use of chlormethyl alkyl phenols prepared by condensing an alkyl phenol, an aldehyde and hydrogen chloride, it is to be understood that other procedures may be employed for preparing similar hydroxy aryl-alkyl halides for'use as intermediates in the above-described processes. In the alternate procedures the order of the reaction steps may be changed and other similar reactants may be used. For example, it may be desired to alkylate the base or the basederivatives of the phenol condensation product, e. g., with an alkylating agent such as di-ethyl sulfate, an alkyl halide, an alcohol, ketone, or olefin, by known alkylating methods, and reduction by hydrogen, if needed or desired.

The phenols used in any of the above-described in vegetable oils, for example, cardanol, obtained from cashew nuts, may be used. As indicated above, it is preferred that the phenols contain an alkyl group of at least 1 carbon atom attached to the nucleus. This may be accomplished by alkylating any of the above-described phenols which do not already contain suitable alkyl groups. The alkyl phenols may be prepared by alkylation of phenols with olefins, including mixtures of olefins such as obtained in cracked petroleum fractions, and by alkylation of phenols vwith alkyl halides, including chlorinated parafiin wax and chlorinated petrolatums derived from petroleum. Such chlorinated waxes may contain dichlorides and polychlorides and may be used in aikylating phenols by the customary Friedel-Crafts type of synthesis to give complex alkylated phenols of high molecular weight in which several phenol radicals are linked by allryl radicals in a single molecule. These high molecular weight complex alkyl phenolic products, whenused in the reactions described herein, give products which are effective in reducing the pour point of waxy oils and in raising the viscosity index of lubricating oils as well as in improving their lubricating properties, such as film strength, and their stability and resistance to oxidation.

A further advantage of the improving agents of this invention is that many are soluble in highly parafi'inic lubricating oils and may be used to pre-] pare improved lubricants with highly refined base oils and greases having a viscosity index of to 103 and even higher. Such oils may be obtained directly as distillate and residual fractions of paramn base lubricants or by suitable refining,

- such as solvent extraction, hydrogenation and the like of lower quality lubricating oil fractions, such ent invention should thus be selected in regard to the particular service for which the blended lubricant is intended. Thus, these oils may be obtained from various types of crudes such as paraflinic, naphthenic, asphaltic or mixed crudes and they may be either plain distillates or fractions obtained by treating or refining of distillate or residual fractions by the various methods known to the art such as acid treating, clay treating, solvent extraction, dewaxing, etc. or they may be synthetic hydrocarbon oils resulting from various types of chemical reactions such as cracking, polymerization, condensation and the like. The present invention thus applies to the preparation of improved crankcase engine lubricants, turbine oils, highly refined light colored and white oils, as well as steam cylinder oils, gear oils, extreme pressure lubricants and greases, upper cylinder lubricants, slushing oils and the like. 1

While the products described herein are especially useful for improving mineral lubricating oils, these materials may also be used as improving agents in other hydrocarbon oils and products such as waxes, fuel oils, Diesel fuels, naphthas, gasoline, burning oil and the like. These materials may also be used as oxidation inhibitor improving agents in other products derived from petroleum oils and in difierent types of products such as fatty oils, soaps, aldehydes, resins, rubber, synthetic rubber, paper and in the various synthetic products which tend to deteriorate by oxihaving a molecular weight above 1,000, also pour depressants, other types of corrosion inhibitors,

antioxidants, detergents, etc., such as the 011-.

soluble metal soaps especially of the alkaline earth metals, etc.

Other assisting agents which are particularly desirable are the higher alcohols having 8 or more 4 carbon atoms and preferably 12 to 20 carbon dation either alone or in accompaniment with other chemical phenomena.

The metal derivatives of the compounds described herein are also useful as wetting and spreading agents in oil vehicles, and may be used inrust-proofing oils and for improving the adhesiveness of asphaltic and resinous compositions.-

As indicated above, the improving agents of this invention are added to hydrocarbon oils, especially lubricating oils, in concentrations sufficient to be effective for the particular purpose desired, whether it be oxidation inhibiting, corrosion inhibiting, color stabilization, or other purpose, and the concentrations vary somewhat for best results. Generally, concentrations as low as 0.001% are 'eifective for stabilizing color, although larger amounts are not excluded, and concentrations ranging from about 0.01% to 1% and even up to 5% or 10% or more are useful in inhibiting corrosion and for other purposes.

If desired other known addition agents or lubricant improving agents may be incorporated in the lubricants prepared according to the present invention to assist or make more effective the action of the above-described improving agents, and to improve the oil in other respects. These include the fatty acid and naphthenic acid soaps, which may be used in small amounts in the preparation of liquid oil compositions or in larger amounts in the preparation of greases, including both the anhydrous types and those containing water. Other addition agents that may also be included are the fatty oils, synthetic esters, sulfur and halogen compounds and other agents for increasing oiliness and film strength, and various thickeners such as polyisobutylene atoms per molecule. The alcohols may be saturated straight and branched chain aliphatic al cohols such as octyl alcohol, CaHnOI-I, lauryl alcohol, C12H25OH, cetyl alcohol, CmHaaOH, stearyl alcohol, sometimes referred to as octadecyl alcohol, C18H3'IOH, and the like; the corresponding olefinic alcohols such as oleyl alcohol; cyclic alcohols, such as naphthenic alcohols; and aryl substituted alkyl alcohols, for instance, phenyl octyl alcohol, octadecyl benzyl alcohol, and mixtures of any of these various alcohols, which may be pure or substantially pure synthetic alcohols. One may also use mixed naturally occurring alcohols such as those found in wool fat .(which is known to contain a substantial percentage of alcohols having about 16 to 18 carbon atoms) and in sperm oil (which contains a high percentage of cetyl alcohol); and although it is preferable to isolate the alcohols from those materials, for some purposes, the wool fat,'sperm oil or other natural products rich in alcohols may be used per se. Products prepared synthetically by chemical processes may also be used such as alcohols prepared by the oxidation of petroleum hydrotaining at least one substituent linked to an aromatic nucleus selected from the group consisting of hydroxyl and sulfhydryl radicals salts thereof.

2. An improved lubricating 011 comprising a mineral lubricating oil having incorporated therein 0.1% to 5.0% by weight of an aromatic methylene thioether containing at least one substituent linked to an aromatic nucleus selected from the group consisting of hydroxyl and sulthydryl radicals and metal salts thereof.

3. An improved lubricating oil comprising a mineral lubricating oil having incorporated therein 0.25% to 2.0% by weight of an aromatic methylene thioether containing at least one substituent linked to an aromatic nucleus selected from the group consisting of hydroxyl and sulfhydryl radicals and metal salts thereof.

4. An improved lubricating oil according to claim 1 in which the metal of the metal salts is barium. I

5. A petroleum hydrocarbon oil having incorporated therein a small proportion, sumcient to stabilize said oil, of an aromatic methylene amyl thioether containing at least one substituent linked to an aromatic nucleus selected from the group consisting of hydroxyl and sulfhydryl radicals and metal salts thereof.

6. An improved lubricating oil comprising a mineral lubricating oil having incorporated therein a small proportion, sufficient to stabilize said oil, of an aromatic methylene amyl thicether containing at least one substituent linked and metal mineral lubricating to an aromatic nucleus selected from the group consisting of hydroxyl and sulfhydryl radicals and metal salts thereof.

7. An improved lubricating oil according to claim 6 in which the metal-of the metal salts is barium.

8. An improved lubricating oil comprising a oil having incorporated therein a small proportion, sufiicient to stabilize said oil, of a barium salt of an aromatic methylene amyl thioether containing a hydroxyl group linked to an aromatic nucleus. 1

LOUIS A. MIKESKA. ALLEN R. KI'I'ILESON.

REFERENCES CITED The following references are of record in the file of this patent:

Number UNITED STATES PATENTS Name Date Mikeska Sept. 26, 1939 Cook July 15, 1941 Cook Jan. 13, 1942 Prutton July 16, 1940 Prutton July 16, 1940 Farrington Nov. 5, 1935 Fuller June 6, 1939 Prutton June 18, 1940 Lieber Sept. 28, 1943 Gardiner Aug. 20, 1940 McCleary et a1 June 22, 1943 Prutton Sept, 29, 1942