US2684334A

US2684334A - Lubricating oil containing a reaction product of p2s5-terpene and 2.4.6-trialkylphenol

Info

Publication number: US2684334A
Application number: US228356A
Authority: US
Inventors: Julian G Ryan; George L Hayes
Original assignee: Shell Development Co
Current assignee: Shell Development Co
Priority date: 1951-05-25
Filing date: 1951-05-25
Publication date: 1954-07-20
Anticipated expiration: 1971-07-20
Also published as: GB717201A; FR1061981A; DE947417C

Description

Patented July 20, 1954 2,684,334

UNITED STATES PATENT OFFICE LUBRICATING OIL CONTAINING A REAC- TION PRODUCT F PzSs-TERPENE AND 2.4.6-TRIALKYLPHENOL Julian G. Ryan and George L. Hayes, Wood River, 111., assignors to Shell Development Company, Emeryville, Calif., a corporation of Delaware No Drawing. Application May 25, 1951, Serial No. 228,356

15 Claims. (01. 252-4613) 1 2 This invention relates to improved lubricating oycloalkyl hydrocarbon radicals containing if decompositions particularly for use in aviation and sired minor proportions of polar substituents, similar types of engines. e. g, N02, NHz, OH, SOsH, COOH, CN, etc, Y

The problem of engine fOul Corrosion and is a chalcogen element having an atomic number the like, is particularly acute in aviation engines, 5 of 8 to 16, namely, oxygen and sulfur (yielding in which the high temperatures developed in the the phenols and thiophenols), the radicals (Yl-l) cylinders tend to act upon lubricating oils to being attached directly to the aromatic ring, a: cause the deposition of resinous and Varnish-lik is an integer of 1 to 2 and y is an integer of at products on the pistons and elsewhere and to least 3. If a: is greater than one, then the radiproduce lacquer-like coatings and carbonaceous 10 cans YH an b th same or diff rent,

materials, which in time tend to cause ring and A preferred embodiment of additives within the valve sticking and interfere with engine operaclass as broadly defined by formula I are 2,4,6, tion. High piston temperatures in aviation entrisubstituted phenols represented by the formula:

gines promote the formation of deposits which, in turn, aggravate the situation by reducing the heat transfer. Furthermore, fuel residues from 1 R2 incomplete combustion of fuel contribute to the deposition of lacquer-like and carbonaceous materials in the engine. (11) Accordingly, it is an object of this invention to provide lubricating oil compositions which have whetaem R1 15 a ternary alkyl radlcal such as improved properties in one or more of the followg i g g igg i ua thy:- ll Y an e 1.6, pre era y (3011 all'llng up 0 ing qualities. high temperature detergency, de about 12 carbon atoms, one of R2 and R3 is a e ti n, corcreased plston rmg Stlckmg wear I due 0 3 hydrocarbon radical, preferably an alkyl radical,

rosion resistance, stability in presence of copper a n in an the either a primary, secondary or tertiary alkyl radior crankcase catalyst Oxld no Stab d cal, while the other one is the same or different like. Another purpose is to produce a superior W heavy duty lubricant particularly suitable for use i s g fgggg fifg fi 55 325 g ifi ggfi g z in aircraft and other interna1 combustion engines grtho or p y y 1 pi y g Operating at relgtlvely .hlgh cylmder temperw alkyl (ortho-hydroXy-a1kyl benzy1-) radical betures. Other ob ects will be apparent from the mg the Orthodsomm' when it is R2 d the para? ggfg g gg found that such lubricating isomer when it is Rs. When R2 or R3 is an orthob 1 co b the or para-hydroxy-alkyl phenyl-subst1tuted alkyl problems can 8 substa w W over me y radical, respectively, the alkyl substituents therein or oration in a lubricatin oil base, of minor s2", i but in critical mutually coacting of are chosen to be identical with R1 and the other one of R2 and R3; thus, the compounds are proportions, of two particular types of non-ashforming additives, the combination of which with alkylezte blsmlkylphenom' the base lubricant exerts a synergistic effect, re- Speclfic examples of compqunds represented by sultin in a composition of outstanding stability 4 formula and 4 9 particularly and lubricity useful in the practice of this invention are:

One Of the additives Of the combination is a 2 t t b t 1 4 th 1 1 2,4,6 trisubstituted polar containing aromatic ZA-ditertiary butyl-fi-methylphenol compound represented by the general formula: 2,4 dimethy1 6 tertia1.y buty1phem1 2,6-di-sec-butyl-fi-tertiary butylphenol (R)yAr YHM (I) 2,4-di-n-buty1-G-tertiary-octylphenol wherein Ar is a monoor dinuclear aromatic 2,6-ditertiary-butyl-4-benzylphenol radical, R is the same or different organic radi- 2,6-ditertiary-amyl-d-methylphonol cals attached to nuclear carbon atoms, at least 2, i-ditertiary-amy16-methylphenol one of said Rs being an alkyl radical ortho in '2,4,6-tritertiary-butylphenol position to a YI-I radical and linked to the ring 2,6-ditertiary-.buty1-4-methylthiophenol carbon atom by a tertiary carbon in the alkyl 2,4-ditertiary-butyl-6-methylthiopheno1 group and the remaining Rs being the same as 2,e-dimethyl-6-tertiary-butylthiophenol the R which is ortho to YH radical or they can 2,4-dimethy1-6-tertiary-octylthiophenol be the same or different essentially alkyl, aralkyl, 2,5-ditertiary-amyl-4-methylthiophenol 2,4,6-tritertiary-amylthiophenol 2,2 methylene bis 4 methyl 6 tertiarybutylphenol) 2,2 -methylene bis (4,6-ditertiary-butylphenol 2,2-methylene bis(4,6-ditertiary-octylphenol) 2,2 methylene bis(4 methyl 6 tertiaryamylphenol) 2,2 methylene, bis(4 methyl 6 tertiaryoctylphenol) 2,2 methylene bis(4 methyl 6 tertiarybutylthiophenol) 2,2-methy1ene bis(4 octyl-6-tertiary-butylthiophenol) 2,2 methylene bis(4,6 ditertiary butylthiophenol) 2,2 methylene bis(4,6 ditertiary amylthiophenol) 2,2 methylene amylthiophenol) 2,2 methylene bis(4 methyl 6 tertiaryoctylthiophenol) (2 hydroxy 3 tertiary butyl 5 methylphenyl) -furylmethane (2 hydroxy 5 tertiary butylphenyl) furylmethane 1,1 bis(2 hydroxy 3 tertiary butyl 5- methylphenyl) isobutane Bis(2 hydroxy 3 tertiary butyl 5 methylphenyl) phenylmethane 2,2 bis(2 hydroxy 3 tertiary butyl 5- methylphenyl) propane 2,2 bis(2 hydroxy 3 tertiary butyl 5- methylphenyl) butane bis(4 methyl 6 tertiary- The trisubstituted phenolic compounds and mixtures thereof can be used in amounts varying from 0.01 to about and preferably from 0.1 to 5% by weight, with from 0.5% to 3% by weight being a still more preferred range.

The second additive used in lubricating compositions of this invention is a phosphorized terpene compound obtained as a reaction product by reacting a terpene compound with a phosphorizing agent. Terpenes suitable for producing reaction products of this invention include alphaand beta-pinene, dipentene, terpinolene, menthene, alpha-terpineol, camphene, limonene, turpentine, pine oil, camphor oil, terpenes obtained as a by-product in manufacture of synthetic camphor, carene, fenchene, terpinene, diterpenes, camphoric acid, abietic acid, etc. The phosphorizing agents which can be used to form reaction products of this invention are: P285, P483, P2S85, P2863, P, P205, POCls, PCls, PC15, PSC13, etc. Also the terpene compounds can be first reacted with a sulfurizing agent, e. g. 8012, S2C12, sodium polysulfide, 8eCl2, 8eCl4 and the like and thereafter retreated with a phosphorizing agent, e. g. P205, P285, phosphoric acid, etc., so that the final reaction product contains both sulfur and phosphorus. If desired, the reaction can be carried out in the reverse order, namely, the terpene compound can be first treated with a phosphorizing agent, e. g., P205 and thereafter treated with sulfur, metal polysulfides, sulfur chloride and the like. The reaction can be carried out in an inert diluent such as light hydrocarbons, or in a base oil to which the reaction product is intended to be added.

When the reaction products of this invention are produced in a two-step process, namely, by first sulfurizing and then phosphorizing, the sulfurization temperature can vary from 200 to 400 F. and the phosphorization step can be carried out at the reflux temperature of the reactants.

4 With phosphorus sulfides the reaction can be made to proceed at room temperature or higher temperatures depending upon the terpene compound being treated.

The mole ratio of the terpene compounds to the phosphorus and sulfur or phosphorizing reagent may vary over wide limits, such as from 10:1, preferably 4:1, to 3:1 moles of the abovementioned reagents, respectively.

The preparation of the reaction products can be efi'ected by heating a terpene compound to an elevated temperature of around 200 F. or higher and slowly adding the phosphorizing agent. After the addition is completed, the temperature of the reaction is increased to 250-400 F. and preferably is maintained between 300 and 350 F. until all of the phosphorizing agent such as P285 has reacted and evolution of hydrogen sulfide ceases. If desired, the reaction product can be purified or refined by solvent treatment or neutralized by treatment with a nitrogen base.

It is preferred to utilize the phosphorized and sulfurized terpene compound, as such, in the present compositions. However, they can be neutralized and/or reacted with organic nitrogen base compounds such as amines and quaternary ammonium compounds, as illustrated by triamylamine, triethanolamine, laurylamine, octadecylamine, morpholine, dibutylamine, dicyclohexylamine, trimethylhexylammonium hydroxide, dibenzylamine, methylaniline, trimethylbenzylammonium hydroxide, piperidine, and the like.

Specific examples of reaction products under discussion and their detailed method of preparation are as follows:

About 4 moles of gum spirits of terpentine was heated under agitation to around 250 F., and about 1 mole of P285 was added portionwise maintaining the temperature of the mixture around 250 F. until all of the P285 had been added. The temperature was then increased to 275-300 F. and the mixture reacted until evolution of H28 ceased. On analysis the product contained 12.8% S and 4.81% P.

Another product was prepared by heating 4 moles of alpha-pinene with 1 mole of P285 at around 240 F. until all of the P285 had been added and thereafter increasing the reaction temperature to around 300 F. and maintaining the mixture at said temperature until the reaction was completed. On analysis the product contained 12.7% 8 and 4.62% P.

The above reaction products can be modified by treating them with amines of which the long chain alkyl amines, e. g., octadecylamine and laurylamine, are preferred.

The phosphorized-terpene compound reaction product can be used in amounts varying from 0.01 to 10% and preferably between 011 and 5% by weight, with from 0.5% to 1.0% representing a still more preferred range.

The base for *additives of this invention can be any natural or synthetic material having lubricating properties. Thus, the base may be a hydrocarbon oil of wide viscosity range, e. g., SUS at 100 F. to SUS at 210 F. The hydrocarbon oils may be blended with fixed oils such as castor oil, lard oil and the like, and/or with synthetic lubricants such as polymerized olefins, copolymers of alkylene glycols and oxides; organic esters of polybasic organic and inorganic acids, e. g., di-2-ethy1hexyl sebacate, dioctyl phthalate, trioctyl phosphate; polymeric tetra-' hydrofuran; polyalkyl silicone polymers, e. g., dimethyl silicone polymer and the like. If desired, the synthetic lubricants may be used as the sole base lubricant or admixed with fixed oils and their derivatives.

Lubricating compositions of this invention are particularly useful in aviation engines operating on leaded fuels containing a halohydrocarbon scavenger such as ethylene dibromide, with or without the presence of an organic phosphate, e. g., tricresylphosphate.

Illustrative examples of final compositions of this invention in a refined mineral oil base having the properties as indicated below are set forth as Compositions A-J.

PROPERTIES OF THE BASE MINERAL OIL Gr., API 28.5 Color, NPA 4 Pour point, F Flash, F 4'70 Fire, F 560 Visc. at 100 F., SSU 1239 Visc. at 210 F., SSU 99.5 Viscosity index 96 Carbon residue, per cent wt. (Conradson) 0.32

Ash, per cent wt None Sulfur, per cent wt 0.13 Specific dispersion 109 Composition A Per cent Pass-turpentine reaction product 0.8 2,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance The properties of this composition are:

Gr., API 28.3 Color, NPA 5 Pour point, F 10 Flash, F 470 Fire, F 560 Vis. at 100 F., SSU 1150 Vis. at 210 F., SSU 95 Viscosity index 95 Carbon residue, per cent wt. (Conradson) 0.32 Ash None Sulfur 0.16 Specific dispersion 110.6

Composition B Per cent Past-turpentine reaction product 0.5 2,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance Composition C Per cent Past-turpentine reaction product 0,25 2,6-ditert-butyll-methylphenol 1 Mineral lubricating oil Balance Composition D Per cent Pass-turpentine reaction product 0.8 2,S-ditert-butyl-4-methylphenol '8 Mineral lubricating oil Balance Composition E Per cent Pzss-pinene reaction product 0.8

2,6-ditert-butyl-4-methylphenol l 1 Mineral lubricating oil Balance Composition F Per cent PzS5-pinene reaction product; 0.5

2,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance 6 Composition G Per cent PzSs-pinene reaction product 0.25 2,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance Composition H Per cent PZSE-pinene reactionv product 0.8 2,S-ditert-butyl-4-methylphenol 3 Mineral lubricating oil Balance Composition I Per cent Pass-turpentine reaction product 0.8 2,2'-methylene bis(4-methyl-6-tert-butylphenol) 1 Mineral lubricating oil Balance Composition J Per cent P2S'5pinene reaction product 0.8 2,2-methylene bis(4-methyl-6-tert-butylphenol) 1 Mineral lubricating oil Balance To illustrate the pronounced improvement obtained using lubricating. compositions of this invention in aircraft engines the following tests were made and the data are presented in the table.

I. Compositions of this invention were tested in a Pratt and Whitney 3-4360 single-cylinder engine in accordance with the procedure outlined by the Pratt and Whitney Aircraft Corporation for evaluating coking tendency of piston engine lubricating oils by noting the resistance of the oil to high temperature oxidation by temperature stressing the test oil in the exhaust rocker box of an R-4360 cylinder.

11,. Compositions of this invention were also tested in a COT engine, developing 8 horsepower at 2400 R. P. M. for hours at the end of which time the condition of the engine was examined and rated.

111. Compositions of this invention were also subjected to the Dornte oxidation test as described in the Industrial and Engineering Chemistry 28, page 26 (1936).

TABLE.--TEST RESULTS Dornte oxidation test [1800 cc., time-minutes, Cu and Fe catalyst] Composition Cu Cat. Fe Cat.

Mineral oil Mineral oil 1% 2.6-ditert-butyl-4-methylphenol 400 340 Mineral oil 25% PiSi-terpene reaction product 480 l, 480 Composition A 680 2, 480 Composition E 680 2,480

Cooperative oil test, CRC project number CLEO-40-46 [Engine (80 hours general performance test) D Total Bearing Composition Engine wt. loss Rating (Mg.)

Mineral oil .L "12 l, 758 Mineral oil 1% 2,G-ditert-butyI-i-inethylphenol 60 1, 555 Mineral oil 25% PzS -terpene reaction produ 1,502 Composition B 87 38 Composition F 89 24 Composition H 76 33 '100=perfect; 50=fair; 0=very poor. {Operation stopped before the 80-hour test because of excess engine fouling.

*Composition Y=Commcrcial compounded aviation oil containing Zn salt of alkyl salicylic acid.

{*Composition XX Mineral oil 1% 2,6-ditert-butyl-4-methylp cm e 10 perfect; very poor.

' Thus, the present invention provides outstanding non-ash-forming lubricating oils for use in aviation engines, which lubricating oils consist essentially of a lubricating oil containing a minor amount each of certain alkylphenols and of a phosphorized-, sulfurized-terpene, to the essen tial exclusion or" other materials. Although the preferred compositions consist essentially of the three components specified, the addition of minor amounts of other additives is advantageous in some applications, additives such as blooming agents, pour point depressants or viscosity improvers, extreme pressure agents, anti-foaming agents and the like. Among the specific additives which can be'used are oil-soluble non-ashforming salts of various nitrogen bases with detergent-forming acids. Organic bases include various nitrogen bases as primary, secondary, tertiary amines and quaternary ammonium bases.

Examples of detergent-forming acids are the various fatty acids of say to 30 carbon atoms, wool fat acids, paraffin wax acids (produced by oxidation of paraifin Wax), chlorinated fatty acids, rosin acids, aromatic carboxylic acids including aromatic fatty acids, aromatic hydrcxy fatty acids, parafiin wax benzoic acids, various alkyl salicylic acids, phthalic acid mono-esters, aromatic keto acids, aromatic ether acids, and the like.

Extreme pressure agents which may be used comprise: neutral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, diaryl disulfides, alkyl aryl disulfides, e. g., diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand tri-sulfides, and the like: sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g., sperm oil, jojaba oil, etc.; in which the sulfur is strongly bonded, sulfurized long-chain olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized-phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphorus or phosphoric acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons, such as chlorinated parafiin, aromatic hydrocarbons and chlorinated esters of fatty acids containing the chlorine in other than the alpha position.

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g., urethanes, allophanates, carbazides, carbazones, etc., poiyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with the two primary additives of this invention.

Compositions of this invention may also be used with motor oils, turbine oils, steam cylinder oils, marine engine oils, refrigeration oils, and used for various lubricating purposes other than engine lubrication, such as slushing and flushing oils, rust inhibiting oils, quenching and drawing oils, greases, wax compositions, and the like.

We claim as our invention:

1. A non-ash aviation engine lubricating oil composition having the following formulation:

2,6 ditertiarylbutyl-4-methylphenol 1 Reaction product of PzSs-turpentina 0.8 Mineral lubricating oil Balance 2. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.5 to 1% of a reaction product of Pzss-turpentine and from about 0.5 to 3% of 2,2-'nethylene bis(i-methyl-S-tertiarybutylphenol).

8. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.5 to 1 of a reaction product of Pzss-pinene and from about 0.5 to 3% of 2,2- methylene bis(4 methyl-o -tertiarybutylphenol).

4. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.5 to 1% of a reaction prod net of PzSa-pinene and from about 0.5 to 3% of 2,6-ditertiarybutyll-methylphenol.

5. A non-ash containing lubricating oil composition for aviation engines consisting essen tially of a mineral lubricating oil having incorporated therein from about 0.5 to 1% of a reaction product of Pass-turpentine and from about 0.5 to 3% of 2,6-ditertiarybutyl-4methylphenol.

6. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of Pzss-pinene and of 2,6-ditertiarybutyll-methylphenol.

7. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of Pass-turpentine and of 2,6- ditertiarybutyl-4-methylphenol.

8.A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of PzSs-pinene and of 2,4,6- trialkylphenol, at least one of the alkyl radicals ortho to the hydroxyl group being a tertiary alkyl radical.

9. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a a reaction product of Pass-turpentine and of 2,4,6-trialkylphenol, at least one of the alkyl radicals ortho to the hydroxyl group being a tertiary alkyl radical.

10. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of Pzss-terpene and of 2,4,6- trialkylphenol, at least one of the alkyl radicals ortho to the hydroxyl group being a tertiary alkyl radical.

11. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of PzSs-turpentine and of 2,2- methylene bis( e-alkyl-6-tertiaryalkvlpheno1) 12. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorpoporated therein from about 0.1 to 5% each of a reaction product of Pass-turpentine and of 2,2- alkylidene bis(4-alkyl-G-tertiaryalkylphenol) 13. A non-ash containing lubricating oil composition for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a reaction product of PzSs-terpene and or" 2,2-alky1- idene bis(4-alkyl-6-tertiaryalkylphenol) 14. A non-ash containing lubricating oil com- Iii position for aviation engines consisting essentially of a mineral lubricating oil having incorporated therein from about 0.1 to 5% each of a phoshporus sulfide-terpene reaction product and of a trisubstituted phenol selected from the group consisting of 2,4,6-trialkylphenol, at least one of the alkyl radicals thereof ortho to the hydroxyl group being a tertiary alkyl radical and 2,2-alkylidene bis( i-alkyl-G-tertiaryalkylphenol) 15. A non-ash containing lubricating oil composition for aviation engines comprising a mineral lubricating oil having incorporated therein 0.8% of a reaction product of pinene with P235 and 1% of 2,6-ditertiary-butyl-4-methyl phenol.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,257,872 Trautman Oct. '7, 1941 2,486,188 May Oct. 25, 1949 2,489,249 Adelson Nov. 29, 1949 2,493,217 Berger Jan. 3, 1950

Claims

10. A NON-ASH CONTAINING LUBRICATING OIL COMPOSITION FOR AVIATION ENGINES CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL HAVING INCORPORATED THEREIN FROM ABOUT 0.1 TO 5% EACH OF A REACTION PRODUCT OF P2S5-TERPENE AND OF 2,4,6TRIALKYLPHENOL, AT LEAST ONE OF THE ALKYL RADICALS ORTHO TO THE HYDROXY GROUP BEING A TERTIARY ALKYL RADICAL.