US2316083A

US2316083A - Lubricant

Info

Publication number: US2316083A
Application number: US384942A
Authority: US
Inventors: Clarence M Loane; James W Gaynor; Lawson W Mixon
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1941-03-24
Filing date: 1941-03-24
Publication date: 1943-04-06
Anticipated expiration: 1960-04-06

Description

Patented Apr. 6, 1943 LUBRICANT Clarence M. Loane, Hammond, Ind., James W. Gaynor, Chicago, 111., and Lawson W. Mixon. Hammond, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application March 24, 1941,

' Serial No. 384,942

8 Claims. (01. 252-48) The present invention relates to improvements inadditives for mineral oils and in particular to an improved phosphorus containing additive for mineral oils and to the method ofpreparing the same.

In copending applications, Serial No. 384,940, filed March 24, 1941, and Serial No. 384,941, filed March 24, 1941, there are respectively described as additives to mineral oils phosphorus sulfidehydrocarbon reaction products and neutralized phosphorus sulfide-hydrocarbon reaction products which are effective in inhibiting the deterioration of mineral oils and the attendant formation of sludge, carbon and varnish-like deposits and the method of preparing the additive.

While the phosphorus sulfide-hydrocarbon reaction products as described in the aforesaid copending applications are very effective in inhibiting the deterioration of mineral oils and in preventing the formation of sludge, carbon and/or varnish-like deposits in internal combustion engines during use, they possess a characteristic odor which may be considered objectionable by users of oils containing such additives.

It is an object of the present invention to provide a method of improvingthe odor ofphos phorus sulfide-hydrocarbon reaction products without decreasing the effectiveness of the reaction products. It is a further object of the invention to provide a substantially odorless phosphorus sulfide-hydrocarbon reaction product which is effective in inhibiting the deterioration of mineral oils and which is effective in, preventing the formation of sludge, carbon and/or varnish-like deposits in internal combustion engines during use; I

We have discovered that the foregoing objects can be attained by reacting the phosphorus sulfide-hydrocarbonreaction product or the neutralized reaction product with an agent having an active hydrogen atom at elevated temperatures, for example, from about 200 F'. to about 600 F., and preferably from about 300 F. to about 400 F., eitherundiluted or in solution in oil or other suitable solvents. Illustrative of the type of agents having an active hydrogen atom at elevated temperatures which are .well suited for the hereindes cribed purpose are steam, alcohols, ammonia and amines.

The phosphorus sulfide used in the'preparation of the additive can be any phosphorus sulfide, such as, for example, P2Sa, P285, P451, P433, etc. and preferably, P285.

I The hydrocarbon reactants can be paraffins, olefins, or olefin polymers, aromatics, or alkyl aromatics, cyclic aliphatics, petroleum fractions such as lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, condensation products of petroleum fractions, solvent extracts of petroleum fractions, etc.

The paraflln hydrocarbons can be those ob,-

tained from petroleum oils such as bright stock residuums, lubricating oil distillates, petrolatums, or parafiin waxes. We may also halogenate any of the foregoing parafl'ins and condense the same with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride and the like.

As examples of high molecular weight olefinic hydrocarbons which we may employ as reactants are cetene, (C16), cerotene (C26) melene (C30) and mixed high molecular weight alkenes obtained by cracking petroleum oils. I

As starting materials for the production of olefin polymers, we can employ the individual olefins themselves, mixtures of olefins, or mixtures of olefins and non-olefinic compounds. 'For example, the olefin-i0 starting material can be butylenes, amylenes, refinery gases containing normally gaseous olefins and cracked distillates or other relatively low-boiling hydrocarbon mixtures containing normally liquid olefins and mixtures of normally liquid olefins containing substantial amounts of dissolved normally gaseous olefins. We may also employ olefinsobtained by the cracking of paraflin wax or by the dehalogenation of alkyl halides, particularly long chain alkyl halides.

The polymers referred to above may be those obtained by polymerizing olefinic hydrocarbons in the presence of catalysts such as sulfuric acid. phosphoric acid, aluminum chloride, zinc chloride, boron fluoride and other catalysts of the Friedel-Crafts type. For example, we can employ the polymers resulting from the treatment of mono-olefins, preferably iso-mono-olefins such as isobutylene and isoamylene, and/or the, co-

polymers obtained by the polymerization of hydrocarbon mixtures containing low molecular weight iso-olefins and normal olefins, preferably those of less than six carbon atoms.

We can also employ as the starting material the-polymer or synthetic lubricating oil obtained by polymerizing unsaturated hydrocarbons resulting from the vapor phase cracking of paraffin waxes in the presence of aluminum chloride. This is fully described in United States Patents 1,995,260, 1,970,002 and 2,091,398. Still another type of olefin polymer which can be employed is in a non-oxidizing atmosphere.

the polymer resulting from the treatment of vapor phase cracked gasoline and/or, gasoline fractions with sulfuric acid or solid absorbents such as fullers earth whereby unsaturated polymerized hydrocarbons are removed. We may also employ'as a starting material the polymers resulting from the voltolization of hydrocarbons as described, for example, in United States Patents 2,197,768 and 2,191,787.

Another class of compounds which maybe used as starting materials is the aromatic hydro carbons such as for example benzene, naphthalene, toluene, xylene, diphenyl and the like, or

alkylated aromatic hydrocarbons such as, for example, an alkyl substituted benzene in which the alkylradical has at least four carbon atoms and preferably at least eight carbon atoms such as a long chain paraffin wax.

The phosphorus sulfide-hydrocarbon reaction product may be obtainedby reacting a phos-' phorus sulfide, for example, P285, with any of the above described hydrocarbons at temperatures of from about 200 F. to about 500 F. and preferably from about 300 F. to about 400 F. and preferably in a non-oxidizing atmosphere, such as an atmosphere of nitrogen. From about 1.0% to product as above obtained, normally shows a titratable acidity which is neutralized when the reaction product is treated with a basic reagent.

The phosphorus sulfide-hydrocarbon reaction product when neutralized witha basic reagent having a metal constituent is characterized by the presence or retention of the metal -con stituent of the reagent. Other metal constituents, such as heavy metal constituentsjmay be introduced into the neutralization product by reacting the same with a salt of the desired heavy metal.

The term "neutralized phosphorus sulfide-hydrocarbon reaction product"v asused herein means a phosphorus sulfide-hydrocarbon reaction prodnot having at least about 1% of its titratable acidity reduced by the reaction with a basic reagent and includes the neutralized phosphorus sulfide-hydrocarbon reaction products containing a metal constituent resulting from said neutraliz ation or resulting from the reaction of a heavy metal salt'with the phosphorus sulfide-hydrocarbon reaction product treated witha basic reagent.

The phosphorus sulfide-hydrocarbon reaction product may be neutralized by treating the reaction product with a suitable basic compound such as a hydroxide, a carbonatejor an oxide of an alkaline earth metal or an alkali metal, preferably calcium oxide, potassium hydroxide, or sodium hydroxide. Other basic reagents may be-used such as, for example, ammonia or an metal constituent such as, for example, tin, titanium, aluminum, chromium, cobalt, iron and the like, may be obtained by reacting a salt of the desired heavy metal with the phosphorus sulfide-hydrocarbon reaction products which have been treated wtih a basic reagent. When the neutralization is accomplished with a polyvalent basic metal, such as lime, a product having excess basicity may be obtained.

Both the phosphorus sulfide-hydrocarbon reaction product and the neutralized reaction product, particularly ifthe latter is incompletely neutralized, possess a characteristic odor which they impart to the lubricant to which they are added. While this does not in any way impair the effectiveness of the compounds in inhibiting the formation of sludge and varnish, it may be objectionable from a sales viewpoint. These products can be substantially freedof this odor by reacting the same with a compound having an active hydrogen atom at an elevated temperature, for example, from about 100 F. to 600 F. and preferably from about 300 F. to 400 F. until a substantial portion of the sulfur is removed as hydrogen sulfide, and the product is substanti'ally odorless. While we may employ compounds such as alcohols, ammonia, and/or amines we prefer to employ steam. lhus, the aforesaid reaction products can be readily freed of the odor by blowing steam through the reaction products either in an undiluted state or in solution in oil or other suitable solvent while maintaining the mixture at the aforesaid temperatures.

Treating the phosphorus sulfide-hydrocarbon reaction products with a compound having an active hydrogen atom, such as steam, at an elevated temperature, results in the final product containing substantially smaller amounts of sulfur. This, however, has substantially no effect on the sludge and varnish inhibiting properties of the product.

The method of preparing the phosphorus sulride-hydrocarbon reaction product and the method of subsequently deodorizing the same will be illustrated by the following specific examples, which are given merely by way of illustration and not'intended 'to limit the scope of the present invention.

EXAMPLE I A mineral lubricating oil derived from a socalled Winkler crude oil, and having a gravity of 25.6 A. P. I., a Saybolt Universal viscosity at 100 F. of 285 to 300 seconds, a flash of not less than 400 F. anda pour point of 5 F. was

alkyl or aryl substituted ammonia, 'such as.

amines. The neutralization may be carried out As aforesaid when the phosphorus sulfide-hydrocarbon reaction product is neutralized with a basic compound having a metal constituent the neutralized reaction product is characterized by the presence of the metal constituent of the basic reagent. Neutralized reaction products containing a heavy mixed with 9% of phosphorus pentasulfide and the mixture heated at a temperature of from F. to 400 F. for about three hours and maintained at the maximum temperature for an additional hour. The reaction product was then diluted with 50% of an SAE 20 motor oil and blown with steam at a temperature of 340-350 F. for about three hours. The final product wa substantially freeof any odor.

EXAMPLE II temperature range for three more hours, and the product was blown with steam within this same as the product in Example IV.

2,316,083 v temperature i 'ange for t hree more hours. The

fi'nafp'mduct containing phosphorus and potassium, was substantially odor-free.-

EXAMPLE III A cracked cycle stock,"recovered as bottoms from a bubble tower, andhaving a Saybolt Universal viscosity at 100. E. of 53 seconds, a gravity of 23.2 A. P. 1., an initial boiling point of 408 F., and a 90% distillation point of 734 F., was mixed with 9% or phosphorus pentasuifide and the mixture heated at a'temperature of from about 300-400 I". The mixture was then dissolved in hexane, filtered, and the filtrate distilled to remove the hexane.- The product was then diluted with 50% of an SAE 20 motor oil and blown with steam at a temperature of 340- 380" F. untilsubstantially no hydrocarbon sulilde was evolved. This product was substantially odor-free.

An. isobutyi'ene 'polymer havingafiaybolt Universal'viscosity at 210 F. of about 3000 seconds was'heated with 10% of phosphorus pentasulfide at a temperature or about 380 F. for eight hours. The, "reaction product so obtained was cooled, 3% of KOH 'was'added, and the mixture was heated at 180 F. for two hours. end of the two hour period the temperature was raised to about 340-350 F. and'maintained within this temperature range for three hours. This product had a characteristic odor and showed the "following analysis:v

I Percent j; Phosphorus 3.0? Sulfur 3.97 Potassium 2.1

The aboveproduct was diluted with an equal volume or an SAE 20'motor oil and steam blown for" three andone-hali hours at temperatures of from about (MO-350 F. At the end of this period the product wassubstantially free of any characteristic odor, end showed approximately the same phosphorus and potassium content but showed substantially no sulfur.

- EXAMPLE V The olefin polymer-used in Example IV was treated with 1.0% phosphorus pentasulilde at a temperature oi 380. F. for eight hours. The phosphoruspentasulflde-olefln polymer reaction product was then. diluted with an equal volume of an SAE20 motor oil and treated with 3% oipo-. tassium hydroxide at a temperature of 180 -F. for two hours. At the end of thetwo hours heating period the temperature was raised to 340-381) F. and the product was steam blown within this temperature range for three hours. The final product was substantially free. of sulfur and the characteristic odor, andcontained substantially thessm'e amount of phosphorus and potassium At the not substantially free of the characteristic odor was obtained.

The effectiveness of the deodorized phosphorus sulfide-hydrocarbon reaction products in improving the stability of lubricating oils maybe demonstrated by a test described as follows: Two hundred and fifty cc. of the oil to be tested is heated at 330 F. to 332 F. in a 500 cc. glass beaker in the presence of five square inches of copper and ten square inches of iron. Four glass rods of six millimeter diameter are suspended in the oil which is stirred at about 1300 R. P. M. with a glass stirrer having a 40 blade pitch. At stated intervals oil samples are taken and the sludge, acidity and viscosity values determined. The glass rods are also inspected for evidence of varnish formation thereon. Varnish values are based on a visual rating in which glass rods free of any varnishare given a rating of 10, heavily coated rods are given a rating of 1, and rods having coatings between these extremes are given intermediate values between 1 and 10.

The following oils were subjected to the above test:

Oil A-Control (high grade SAE 20 motor oil).

Oil BOil A+1% of the deodorized product of Example IV. l

Oil C-+Oil A+1% of the deodorized product of Example V.

i Saybolt Universal viscosity at F.

l 10=no deposit; 1 =very heavy deposit.

The above data show the marked improvement obtained by the addition of small amounts of the deodorized phosphorus sulfide-hydrocarbon reaction product to a high grade SAE 20 motor oil.

The effectiveness of the deodorized phosphorus sulfide-hydrocarbon reaction products in inhibiting the formation of carbon, sludge and/or varnish in internal combustion engines is demonstrated by the following data obtained in an engine 'test conducted in a standard six cylinder spark-ignition engine operating for sixty hours at 35 B H. P. and 3000 R. P. M. and an oil sump temperature of about 285 F. At the end of each test period the engine was dismantled-and given a visual engine rating in which a rating of 10 means that the engine parts had substantially the same appearance at the end of the test as at the start of the test, while an engine rating or 1 means that the engine parts are very badly coated. An engine rating of intermediate value between 1 and 10 means that the appearance of the engine parts after the test is between these extremes. In the tabulation below the visual ratings are given on the following oils.

Oil A-Control (high grade SAE 20 motor oil). Oil B-Oil A+%% deodorized reaction product of Example VI. Oil C-Oii A+%% deodorized reaction product of Example VI. v Oil D-Oil A+1% deodorized reaction product oi Example V.

TABLE II Aconnmwrnp Enema Tns'r Visual engine ratings at end of 60 hours Oil samples A B O 1) Piston varnish 5 6 10 i Sludge deposits-... 6 8 9 10 Ring belt carbon 0 l0 l0 Under crown carbon 5 10 Overall rating--- 5. 3 7. 2 9. l5 10 'While we may use the deodorized phosphorus.

sulfide hydrocarbon reaction products in lubrieating oils, which may be used in such oils in amounts of from about 0.001% to 10.0% and preferably from about 0.01% to about 3.0%, our invention is not limited to such use, since these products may be used in other petroleum products, such as insulating oils, white oils, greases,

' waxes, etc. to inhibit the oxidation, sludging and deterioration thereof.

Although we have described preferred embodiments of our invention, other modifications may be made without departing from the scope and spirit of the invention, and we do not wish to limit our invention to the specific examples set forth herein, except insofar as the same is defined by the following claims.

We claim:

1. A lubricant comprising a mineral lubricating oil'anda small amount of theproduct obtained by reacting a phosphorus sulfide with a hydrocarbon, neutralizing the reaction productlresult ing therefrom with abasic reagent whereby a neutralized phosphorus "and sulfur-containing reaction product is obtained, and subsequently blowing the neutralized phosphorus sulfide-hy- -drocarbon reaction product with steam at a temperature of from about 200 F, to about 600 F. to obtain a substantially sulfur-free product.

2. A lubricant as described in claim 1 in which the hydrocarbon is a petroleum oil fraction.

3. The method of inhibiting the formation of sludge, carbon and varnish in an internal combustion engine lubricated with a mineral lubricating oil comprising lubricating the internal combustion engine with a lubricant comprising a mineral lubricating oil normally susceptible to form sludge; carbon and varnish during use in an internal combustion engine, and a small amount of the product obtained by reacting a, phosphorus sulfide with a hydrocarbon, neutralizing the resulting reaction product with a basic reagent whereby a neutralized phosphorus and sulfurcontaining product is obtained and subsequently treating the neutralized reaction product with a compound having an active hydrogen atom at an elevated temperature above about F. to obtain a final product having a substantially lower sulfur content than the initial neutralized reaction product.

4. The method of inhibiting the formation of sludge, carbon and varnish=in an internal combustion engine lubricated with a mineral lubri eating oil, comprising lubricating the internal combustion engine with a, lubricant comprising a mineral lubricating oil normally susceptible to form sludge, carbon and varnish during use in an internal combustion engine, and a small amount of the product obtained by reacting a. phosphorus sulfid with a hydrocarbon, neutralizing the resulting reaction product with a basic reagent whereby a neutralized product containing phosphorus and sulfur is obtained and subsequently blowing the neutralized reaction product with steam at an elevated temperature above about 200 F. to obtain a substantially sulfur-free product.

5. A lubricant comprisinga hydrocarbon lubricating oil and a small amount of the product obtained by reacting'a phosphorus sulfide with a hydrocarbon, neutralizing with a'b'asic reagent whereby a neutralized product containing phosphorus and sulfur is obtained, and subsequently treating said reaction product"at'a temperature above about 100 F. witha compound having an active hydrogen atom to obtain a; product having a substantially lower sulfur'content' than the initial reaction product.

- 6. A new composition comprising a hydrocarbon oil and the product obtained by the process comprising reacting a phosphorus sulfide with a hydrocarbon, whereby a product containing phosphorus and sulfur is obtained, neutralizing with a basic reagent and treating the reaction product at a temperature above about 100 F. with a compound having an active hydrogen atomto'obtain a final product having a substantially lower sulfur content than the initial reaction product. f-

7. A new composition comprising a hydrocarbon oiland the product obtained by reacting a phosphorus sulfide with a hydrocarbon, neutralizing the reaction productresulting therefrom' with a basic reagent having a metal constituent whereby a phosphorus and sulfur-containing product having a, metal constituent is obtained and subsequently blowing the neutralized reaction product with steam ata temperature above about 200 F. to obtain a substantially sulfur-free product. g

8. A new composition comprising a. hydrocarbon oil and the product obtained by the process comprising reacting a phosphorus sulfide with a hydrocarbon whereby a phosphorus and sulfurcontaining product is obtained-neutralizing with a basic reagent having a metal constituent, and treating the reaction product at a temperature above about 100. F. with a compound having an active hydrogen atom to obtain a substantially sulfur-free product.

CLARENCE M. LOANE. JAMES W. GAYNOR. LAWSON W. MIXON.