US2381127A

US2381127A - Lubricating composition

Info

Publication number: US2381127A
Application number: US477135A
Authority: US
Inventors: Jr Lebbeus C Kemp
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1943-02-25
Filing date: 1943-02-25
Publication date: 1945-08-07
Anticipated expiration: 1962-08-07

Description

Patented Aug. 7, 1945,

LUBRICATIN G COMPOSITION "Lebbeus C. Kemp; 31- Scarsdale, N. Y., assignor to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application February 25, 1943,

, Serial No. 477,135

18 Claims. (01. 252-48) The presentinvention relates to lubricating compositions possessing extreme pressure properties, and particularly to an additive composition which, when incorporated in lubricating oils and greases,- imparts extreme .pressure properties thereto.

The additive ingredients of the present inven-' tion are prepared-from the phenolic compositions present in or derived from the oils extracted from the nnacardium genus of the Anacardiaceae family. The oils included within this classification are such oils as cashew nut shell oil, marking nut shell oil, Japanese lac, etc., whose chemical composition d pends upon the particular method of extraction used. It is'the consensus of the authorities on these extracted oils that the chemical composition of the naturally-occurring oils "consists primarily of various types of aromatic derivatives such as anacardic acid (C22Ha203),

cardol (C32H52O4), cardanol (CzoHazO), anacardol (Ciel-I300) urushiol (Gaol-13002), etc. These aromatic derivatives are very unstable and .in the presence of heat form decomposition products or oil-insoluble polymerization products.

Representative of these naturally-occurring oils is cashew nut shelloil which, when obtained by solvent extraction, consists primarily of 90% The anacardic anacardic acid and cardol. acid portion of this solvent-extracted oil, which is described as a salicylic acid homolog, decomposes at slightly elevated temperatures with-the evolu- These extreme pressure additives are prepared from the oil-soluble unsaturated alkyl phenols present in or derived from the extracted oils and may take the form of mono-di-or tri-esters of phosphoricacid, with preference givento the triester. Examples or the unsaturated alkyl phe-' nols suitable for the preparation of these additives are cardanol, anacardol, urushiol, and the oil-soluble phenolic components which have not been, isolated and which may be present in admixture with other phenols in the distillate and.

distillate residues of the extracted oils. These unsaturated alkyl phenols are relatively unstable and susceptible to polymerization and condensa-' tion reactions in the presence of acids and elevated temperatures. This instability may be overcome by partially hydrogenating the unsaturated constituents prior to the preparation of the substituted derivatives forming a part of the present invention, or by a choice of substitution reaction which will avoid polymerization. The stabilization of the unsaturated alkyl phenols is not critical to the preparation of the phosphoric acid esters and as such is not intended as a lim- 'tion of carbon dioxide to yield .cardanol, which is a phenol containing an unsaturated alkyl radical (Gillian) in the meta position. This decomposition is particularly noticed .in the cashew nut shell oil obtained by a thermal extraction process which contains only about 16% anaoardic acid, I

with the balancemade up of a. major proportion of cardanoland a ,minor proportion of cardol.

It has been found than an ester of phosphoric acid in which the ester radical is derived from the unsaturated alkyl phenolsobtained from an oil extracted from the Anacardium genus of the Anacardiaceae family which have'been modified by the presence of one or more substituent groups in 0 Motor oils Aircraft engine oils s I the unsaturated alkyl radicals, is possessed of ex- I itation to the products of the present invention.

The phosphoric acid esters may be incorporated in a'hydrocarbon oil, and particularly in mineral lubricating oils and greases in amounts ranging .between 0.l-10.0% weight, depending upon the type of hydrocarbon oil base and the degree of extreme pressure properties desired. The partic ular range of proportions as applied to some of the lubricating oils and grease bases may be outlined as follows:

Per cent by weight of y L finished lubricant Gear lubricants 0.5 5.0

Gear oils a 0.5 5.0.

Cutting oils 0.5 3.0 0.25- 1.5

0.5 2.0 Diesel oils 0.5 2.0

Turbine oils 0.1 0.5

In the preparation of the substituted unsaturated alkyl phenols and the phosphoric acid esters thereof, any of the classical methods of synthesis ceptional extreme pressure properties when incorporated in-a' hydrocarbon oil. These ester radicals are preferably those obtained from the aforementioned unsaturated alkyl phenols which contain either sulfur or a halogen such as chlorine or mixtures thereof in the unsaturated alkyl radicals. Inaccordance with the present invention a high pressure lubricant is obtained by the addition of small quantities of these phosphoricacid esters to a suitable lubricating oil or grease base. As examples oi these high pressure lubricants may be mentioned gear lubricants, gear oils, cutting oils, pressure greases, lubricating oils for internal combustion engines, etc. I

may be used. The particular methodschosen depend'upon the conditions of reaction and the stability of. the phenolic compositions. When preparing the sulfur and/or halogenated derivatlves of the unsaturated alkyl phenols it is preferableto select a method of preparation which i is carried out at low temperatures and which does not yield acidic by-products or where the acidic by-products are removed from the reaction zone. These conditions of reaction, however, may be' modified if the starting material has been stabilized by partial hydrogenation.

I The phosphoric acid esters of the substituted derivatives may be prepared by any of the generallyaccepted methods of preparation since the product resulting from the substitution reactions is sufliciently stable in and of itself to be-reacted under'normal conditions.

When preparing the halogenated derivatives and particularly a chlorinated derivative, of the unsaturated alkyl phenols, the phenolic compos n is p a y subjected to partial hydrogenchloride may be used in place of the chlorine or hydrogen chloride previously mentioned.

' In preparing the sulfurized or sulfur-containing derivatives the phenolic composition may either be partially hydrogenated or reacted in its full unsaturated condition, depending upon the methods of incorporating surfur.

The following example of the preparation of a tri-esi'er of phosphoric acid, in which the esterv radical was derived from partially hydrogenated sulfurized cardanol obtained from vcashew nutshell oil. is given as an illustration of one of the methods of preparing these phosphoric acid esters:

, Example 400 cos. (370-380 grams) of freshly distilled cardanol with a bromine no. of 118 was charged to an Adkins type bomb, together with 10-15 grams of- Raney nickel. Hydrogen was admitted to 2000-2200 pounds per square inch and the results obtained (indicated uni pounds of pressure required for seizure) were as follows:

Reference nil 5-10 Reference oi1+1.0% partially hydrogenated sulfurized tri-cardanyl phosphate, 34.7

( Represents average of 6 test runs) Obviously many modifications and variations of the invention as hereinbefore set'forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appendedclaims.

I claim: a 1. A lubrica'nt comprising a hydrocarbon oil containing 0.1-l0.0% b'yweightof a substituted alkyl phenyl ester of phosphoric acid, said substituted alkyl phenyl ester being derived from the unsaturated alkyl phenols present in or derived from the oils extracted from the Anacardium' genus of the Anacardiaceae family and characterized by the presence of at least one substituent group selected from the classiconsisting of sulfur and halogen in the unsaturated alkyl radicals thereof.

2. A lubricant comprising a mineral lubricating oil containing 0.1-10.0% by weight of a .substituted allryl phenyl ester of phosphoric acid, said substituted alkyl phenyl ester being derived from the unsaturated alkyl phenols present in 'or derivedfrom oils extracted from the Anacardium bomb rocked at 250-300 1'. until the pressure dropped to 1000-1100 pounds per square inch.

The process was repeated until a quantity of hy-- drogen had been added sufncient to give a calculated bromine np. of 85-05. In this particular case the resulting bromine no. was 95; After hydrogenation'the product was illteredfree of Raneyrnickel. 400 grams of the partially hydrogenated cardanol were then sulfurized with 28 grams of sulfur at 330-350* 1!, which was calculated to give a sulfur content in the product of from etc 7%. The resulting par ially hydrogenated sulfuriaed cardanol was then dissolved in toluene and 115 grams of pyridine were added.

To this solution was then added 80 grams of POCh at room temperature. The reaction mixture was allowed-to stand for 16 hours and was thereafter stirred .at 85-75 C. for an additional four hours. The phosphate ester was then flltered free of pyridine hydrochloride and; the '01- vent removed by stripping. The analysis of the trl-phoephate ester of partially hydrogenated sulfurisedc'ardanol was as follows; 2 I

Found Theory,

' The efl'ectivenees of the phosphoric deters of the present invention as extreme pressure agents when incorporated in lubricating oils has been demonstrated by tests conducted on analmen testing machine. I'br these the product obtainedbythefomoingexamplewaeincorpo rated in a solvent-refined. dewaxed. lfld-Conti 'nentlubricating'oilofan8..d.l80grade.'1h'

genus of the Anacardiaceae family which have been modified by the addition of substituent groups selected from the class consistingof sulfur and halogen in the unsaturated alkyl radicals thereof. I v v 3. A lubricant comprising a major proportion of a hydrocarboi'i oil and a minor proportion, suiilcient to impart,extreme pressure propertiesto said hydrocarbon oil, of a substituted alkyi phenyl ester of phosphoric acid, said substituted alkyl phenyl ester-being derived from the unsaturated alkyl phenols present in or derived from the oils extracted from the Anacardium genus,

of the A'nacardiaceae family which have been modified by the addition of substitutent groups in the unsaturated alkyl radicals thereof. said substituent groups being selected from the consisting of sulfur and a halogen.

4. A lubricant comprising a. hydrocarbon containing (Ll-10.0% by mm 0! a substituted aikyl phenyl ester of.phoephoric acid, said sub- 'stituted 'alkyi phenyl ester being derived mm the unsaturated alkyl phenols present in or derived fromcashew nutshell oil which have been I halogen in the unsaturated alkyl radicals thereof.

a. a lubricantoomprising a mineral lubricating oil containing 0.1-10.0% by weight of a submodiiled by'the additiomofeubstituent groups selectedfrom'theclasecomisting ofsulfurand halogenintheunsaturated alkylradicalstheretherein 0.1-10-0 weisht of a alkylph nrleeterofpboephoric stiuted alkyl.phenyluterbeing derl theuneaturatedelblphenohpseeentinin' Poundsrived from the oils extracted-from the Anacardium genus of the Ana'cardiaceae family, and char,- acteriaed by the addition of at least one substituent group selected'from the class consisting of sulfur and halogen in the unsaturated alkyl radicals thereof. 7. A lubricant comprising a mineral lubricatin oil containing (Ll-10.0% by weight of a substituted tri-alky lphenyl ester of phosphoric acid, said substituted tri-alkylphenvl ester being derived from the unsaturated alkyl phenols present in or derived from oils extracted from the Anacardium genus of the AnacardiaceaeIfamiIy which have been modified by the addition ofsubstituent groups selected from the class consisting of sulfur and halogen in the unsaturated alkyl radicals thereof.

a. Alubricant comprising a mineral lubricat 13. A lubricant comprising a hydrocarbon oil and 0.l- 10.0% byweight of partially hydrogenated sulfurized tri-cardanyl phosphate.

14. A high pressure lubricant comprising lubrieating oils and greases having incorporated therein (Ll-10.0% byiweight of partially hydrogenated suli'urized tri-cardanyl phosphate.

15. A lubricant comprising a hydrocarbon 'oil containing a small quantity, sumcient to impart saturated alkyl phenols present in or derived from cashew nut shell oil. and characterized by the addition of at least one substituent group selected from the class consisting of sulfur and halogen in the \msaturated alkyl radicals thereof.

10. A lubricant comprising a hydrocarbon oil containing (ll-10.0% by weight of a substituted alkyl phenyl esterof phosphoric acid said substituted alkyl phenyl ester being derived from the partially hydrogenatedunsaturated alkyl p s present in or derived from cashew nut shell oil and characterised by the addition of ,at least one substituent r up selected from the class consistin: of sulfur and halogen in the unsaturated alkyl radicals thereof.

11. A lubricant comprising a hydrocarbon oil and 0.140.095 by weight of sulfurised til-cardanyl phosphate.

12. A lubricant comprising a mineral lubricating oil and 0.140. by weight of sulfurized tricardanyl mm.

extreme pressure properties to said hydrocarbon oil, of a substituted alkyl phenyl ester of phosphoric acid, said substituted alkyl phenyl ester being derived from the unsaturated alkyl phenols present in or derived from cashew nut shell oil which have been partially hydrogenated and modified by the addition of sulfur to the remaining unsaturated linkages of the alkyl radical thereof.

16. A lubricant comprising a hydrocarbon oil containing a small quantity. suillcient to impart extreme pressure properties to said hydrocarbon oil. of a substituted alkyl phenyl ester of phos-v phoric acid, said substituted 'alkyl phenyl ester being derived from the unsaturated alkyl phenols present in or derived from cashew nut shell oil which have been partially hydrogenated and modified by the addition of chlorine to the remaining unsaturated linkages of the alkyl radical thereof.

17. A lubricant comprising a hydrocarbon oil containing a small quantity. suiiieient to impart extreme pressure properties to said hydrocarbon oil, of said substituted alkyl phenyl ester of phosphoric acid, said substituted alkyl phenyl ester being derived from the unsaturated alkyl phenols present in or derived from cashew nut shell oil which have been modified by the addition of sulfur to the unsaturated linkages of the alkyl radical thereof. b b

18. A lubricant comprising a hydrocarbon oil containing a small quantit suillcient to impart extreme pressure properti to said hydrocarbon oil. of a substituted alkyl phenyl ester of phosphoric acid, said substituted alkyl phenyl ester being derived from the unsaturated alkyl phenols present inor derived from cashew nut shell oil which have been modified by the addition of chlorine to the unsaturated linkages of the alkyl radical thereof.

LEBBEUB C. KEMP, Jr.