EP0565624A4

EP0565624A4 - Lubricant adducts and their preparation

Info

Publication number: EP0565624A4
Application number: EP92904012A
Authority: EP
Inventors: Leslie Robert Rudnich; Ross Allan Kremer; Derek A Law; C Ali Naghipur; Carleton N Rowe
Original assignee: Mobil Oil Corp
Current assignee: ExxonMobil Oil Corp
Priority date: 1991-01-04
Filing date: 1992-01-03
Publication date: 1995-12-27
Also published as: CA2098995A1; JPH06504289A; WO1992012222A1; EP0565624A1

Abstract

Alkylated diphenyl ethers, alkylated diphenyl methanes, alkylated phenoxathins and alkylated diphenyl sulfides are high-temperature stable lubricant fluids having excellent low temperature viscometrics, and excellent additive solubility. These adducts may be used as such as lubricants or may be blended with other lubricant fluids or fuel compositions.

Description

iUERicawr ADDUCES AND Ώ_EER H^ARATICI.

This invention relates to lubricant adducts and their preparation. More particularly, this invention relates to improved lubricant fluid oppositions cαtprising these adducts alone or blended with synthetic or mineral oil lubricant compositions; and to fuel c πpositions ccrπprising these adducts.

According to one aspect of the present invention, there is provided an adduct preparable by catalytically reacting :

i) at least one ccπpcund σcπprising at least one olefinic group; a hydrocarbyl substitueπt; and, optionally, at least one heteroatcm; with

ii) a substituted or υnsubstituted, fused or υnfused, polyπuclear, arαπatic compound which may contain at least one chalcogen atom.

The hydrocarbyl substitueπt of i) may be aliphatic or cyclic (including aromatic and alicyclic) and may be linear or branched. Suitably, the hydrocarbyl substitueπt comprises an adduct according to claim 1 wherein the hydrocarbyl substitueπt comprises a C. to C_50Q alkyl, alkeπyl or alkyπyl group, a C to C₅₀_ aralkyl or alkaryl group or a C_g to C_5Q0 aryl group. Preferably, the hydrocarbyl substitueπt cxxrprises from 6 to 50 carbon atoms; for example, from 8 to 18 carbon atoms. Preferably, compound i) σcπprises an alpha olefin. Where cxampound i) cxuprises a heteroatcm this may be S,N,0,P and/or F. In accordance with the invention, ccπpcund ii) preferably has the general formula :

in which :

X represents an oxygen or sulphur atom or a methylene group; and

Y represents a sulphur atom or two hydrogen atoms attached to different aromatic rings.

Die aromatic rings of compound ii) may be substituted on one ormore positions of any aromatic ring. Substitution by an alkyl group is preferred, especially with at least one a__kyl group on each ring.

It is preferred that compound ii) comprises an adduct according to claim 7 wherein ii) comprises diphenyl ether, diphenyl sulphide, dipheπyl ethane or phenσxathiin. The adducts of this invention prepared over zeolite catalysts have a higher VI at a given viscosity.

In accordance with a second aspect of this invention, there is provided a process for the preparation of an adduct, which process comprises catalytically reacting :

i) at least one compound comprising at least one olefinic group; a hydrocarbyl substituent; and, optionally, at least one heteroatcm; with ii) a substituted or unsubstituted, fused or unfused, polynuclear, aromatic compound which may contain at least one chalcogen atom

at a temperature frcm ambient to 350°C; a molar ratio of i) : ii) from 0.5:1.0 to 10.0:1.0; and a ratio of catalyst : ii) from lg : 1 mol, preferably 5g:l mol, to 100 g: 1 mol.

This invention also provides a high temperature stable lubricant fluid comprising an adduct as herein described. The invention further provides a fuel composition comprising an adduct as herein described and a liquid hydrocarbon or oxygenated fuel.

This invention, in a further aspect, provides for the use of an adduct as herein described in a high teαperatυre stable lubricant fluid or a fuel composition for its improved antiwear, high and law temperature aπtiαxidaπt, antispalling, aπtdsquawking, aπtifatigue, antistaining, additive solubility, load carrying, extreme pressure, thermal and coάdative, aπticorrosion, denulsifyiiig emulsifying, detergent or cleanliness properties.

The preparation of these adducts may be by means of a thermal or catalytic addition reaction. The exact mechanism of the reaction is not important to the purposes of this invention, so long as the hydrocarbyl substitueπt becomes attached to the compound (ii) described herein.

One preferred method of reaction between compound i) and compound ii) is the combination of these reactaπts in the presence of specific zeolite cataivsts; for example Oσtacar USY and MCM-22. Additional catalysts which could be used advantageously in this invention are ZSM-12 and other large-pore and/or relatively large pore zeolites. FOC Octacat USY is described in U.S. Patent No. 4,898,846. MC -22 is described in U.S. Patent No. 4,983,276. This reaction is effected at temperatures frcm ambient to 350"C, preferably frcm 100-250^βC and most preferably from 180 to 240^βC over a period required to produce the desired conversion of reactaπts to product. The reaction can be performed in a batch or semi-batch mode by cxπtinuous or partial addition of catalyst or hydrocarbyl substitueπt to the compound ii) .

The catalyst can be used at levels from 1 grany'mole of compound ii) to 100 grams/mole of compound ii) , preferably from 5 gmole of compound ii) to 50 grams/mole of ccπpound ii) and most preferably frcm 10 to 30 grams catalyst/mole of compound ii) . Generally speaking, the molar ratio of compound i) to compound ii) is frcm 0.5:1.0 to 10.0:1.0 and preferably from 1.0:1.0 to 4.0:1.0.

Optionally, the adducts of this invention can be prepared by reaction in the presence of CI. and other Lewis acids or in the presence of Brαnsted acids, as described in G. A. Olah's "I^edel-Crafts and Related Reactions", Vol. I, 1963, Iπtersciencε Publishers.

The adducts of the present invention may be used as liquid lubricants or in liquid lubricant compositions, and as solid lubricants or in solid lubricant compositions including greases, such as polyurea, lithium carbαxylate or clay-thicikened greases.

These adducts may also be used in ccmbinatiαn with known additives, for example, aπtiαxidaπts, EP/aπtiwear agents, inhibitors, detergents and diεpersants, and viscosity index improvers. Examples of aπtiαxidaπts include hindered phenols and aromatic amines. Examples of EP/aπtiwear additives include zinc phoεqphαrodithioates, sulfurized esters, sulfurized olefins, phosphonates, phosphites and phosphorothiαnates. Examples of inhibitors include TMTD and phenσthiazine. Exaπples of detergents and dispersants include sulfonates, phenates, and polymeric suσcinimides. These can be either metallic or non-metallic. Metallic detergents can be calcium or magnesium derived and can be neutral or overbased. The adducts of this invention can be used alone or in combination with other synthetic anά/ar mineral oil fluids. When used in combination with other synthetic and/or mineral oil fluids oils of lubricating viscosity may be used. In general, mineral oils, both paraffinic, naphthenic and mixtures thereof, employed as the lubricant, or grease vehicle, may be of any suitable lubricating viscosity range, as for example, frcm 45 SSU at 100'F to 6000 SSU at 100'F and preferably, frcβn 50 to 250 SSU at 210"F. These oils may preferably have viscosity indexes up to 95. The average molecular weights of these oils may be frcm 250 to 800. Where the lubricant is to be employed in the form of a grease, the lubricating oil is generally employed in an amount sufficient to balance the total grease composition, after acccuπtiiig for the desired quantity of the thickening agent, and other additive components to be included in the grease foriπulatiαn.

A wide variety of materials may be employed as thickening or gelling agents. These may include any of the conventional metal salts or soaps which are dispersed in the lubricating vehicle in grease-forming quantities in an amount to impart to the resulting grease composition the desired consistency. Other thickening agents that may be employed in the grease formulation may comprise non-soap thickeners, such as surface-modified clays and silicas, aryl ureas, calcium ccπplexes and similar materials.

In general, grease thickeners may be employed which do not melt and dissolve when used at the required temperature within a particular environment; however, in all other respects, any material which is normally employed for thickening or gelling hydrocarbon fluids for foaming grease can be used in preparing grease in accordance with the present invention.

__n instances where synthetic oils, or synthetic oils employed as the lubricant or vehicle for the grease, are desired in preference to mineral oils, or in combination therewith, various compounds of this type may be successfully utilized. Typical synthetic oils include polyisofcutylene, polybutenes, lydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylprcpane esters, neopeπtyl and pentaerythrάtol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl pfcthalate, fluorcσarbαns, silicate esters, silanes, esters of phosphorus-<χjπtaining acids, liquid ureas, ferrocene derivatives, hydrogenated synthetic oils, chain-type polypheπyls, siloxanes and silicones (polysilαxanes), alkvl-substituted diphenyl ethers typified by a fcutyl-substituted bis(p--phenαxy phenyl) ether, pfaenαxy pheπylethers.

When used as additives the adducts of the invention have the ability to iπpxrve both the thermal and αxidative stability as well as the additive solubilrty of the oleagenous materials, i.e. , synthetic and/or mineral oil fluids with which they have been blended.

It is to be understood, however, that the additives useful herein for their lάicwn purposes do not detract from the value of the compositions of this invention, rather these materials enhance the beneficial αiaracteristics of the disclosed adducts. Lubricant compositions in accordance with the invention may ccmprise frcm less than about 1 to about 100% of the adducts of the invention and or frcm less than about 100% to about 1% of a synthetic or mineral oil of lubricating viscosity or grease prepared therefrom and from 0.001 to 20 wt% of additive material based on the total weight of the composition.

Fuel compositions of the invention comprising the adducts herein described include both hydrocarbon fuels, including gasoline, naphtha and diesel fuels or alcoholic fuels or mixtures of alcoholic and hydrocarbon fuels. Fuel compositions can contain 10 to 1,000 pounds of additive per 1,000 barrels of fuel or, more preferably, 25 to 250 pounds per 1,000 barrels of fuel.

The following Examples illustrate the invention.

EXAMPLE 1 15 g of POC Octacat USY catalyst were added to a vigorously stirred mixture of diphenyl ether (170 g, 1.0 mole) and 1-tetradeoene (196 g, 1.0 mole) in a flask fitted with

"tftenrooouple and reflux condenser. The mixture was then heated to 200'C, with stirring, for six hours. After cooling to room temperature, the mixture was filtered to remove catalyst and vacuum distilled to 170"C at 0.5-1.5 mmHg to remove unreaσted starting materials.

EXAMPLE 2 Using the procedure of Example 1, diphenyl ether (170 g, 1.0 mole) and 1-tetradecene (196 g, 1.0 mole) were reacted using 30 grams of FCC Octacat USY catalyst.

EXAMPLE 3

Using the procedure of Example 1, diphenyl ether (120 g, 1.0 mole) and 1-dodecene (168.32 g, 1.1 moles) were reacted using 15 grams of FCC Octacat USY catalyst.

EXAMPLE 4 2.0 g of anhydrous A1C1- were added to a stirred mixture of 1-octene, 224.2 g (2 moles), and diphenyl ether, 170 g (1 mole) and heated at reflux for six hours. The mixture was then cooled; washed to remove i∞rganic materials; and dried over anhydrous MgSO.. Gas chixmatographic analysis shewed essentially complete reaction of starting material. Color of this material >5 whereas the product of Example 1 was <2.0. EXAMPLE 5 Using the procedure in Example 4, 1-decene 168 g (1 mole) and diphenyl ether (170 g, 1 mole) were reacted with Aid. (2 grams) at reflux for six hours. Vacuum distillation of the washed organic mixture to 170°C at 0.5-1.5 mrπHg resulted in the desired hydrocarbyl diphenyl ether product.

EXAMPLE 6 18.2 g of FOC Octacat USY catalyst were added to a vigorously stirred mixture of diphenyl methane (168.24 g, 1.0 mole) and 1-tetradeσene (196 g, 1.0 mole) in a flask fitted with thermocouple and reflux condenser. The mixture was then heated to 200^βC, with stirring, for six hours. After cooling to room temperature, the mixture was filtered to remove catalyst and vacuum distilled to 170'C at 0.5-1.5 mmHg to remove unreacted starting materials.

EXAMPLE 7 Using the procedure of Example 6, diphenyl methane (168.24 g, 1.0 mole) and 1-tetradecene (196 g, 1.0 mole) were reacted using 36.4 grams of FOC Octacat USY catalyst.

EXAMPLE 8 Using the procedure of Example 6, diphenyl methane (168.24 g, 1.0 mole) and 1-hexadeoene (224.43 g, 1.0 moles) were reacted using 19.6 grams of P0C Octacat USY catalyst.

EXAMPLE 9

2.0 g of anhydrous A1C1. were added to a stirred mixture of 1-octene, 224.2 g (2 moles), and diphenyl methane, 168.24 g (1 mole) and heated at reflux for six hours. The mixture was -then cooled; washed to remove inorganic materials; and dried over anhydrous MgSO.. Gas dι_xmatographic analysis shewed essentially complete reaction of starting material. Color of this material was >5 whereas the product of Example 1 was <2.0. EXAMPLE 10 19.5 g of FCC Octacat USY catalyst were added to a vigorously stirred mixture of phenoxathin (202 g, 1.0 mole) and 1-tetradecene (196 g, 1.0 mole) in a flask fitted with thermocouple and reflux condenser. The mixture was then heated to 200'C, with stirring, for six hours. After cooling to room temperature, the mixture was filtered to remove catalyst and vacuum distilled to 170'C at 0.5-1.5 mmBg to remove unreaσted starting materials. EXSMPLE 11

Using the procedure of Example 11, phenoxathin (202 g, 1.0 mole) and 1-tøtradeαene (196 g, 1.0 mole) were reacted using 39 grams of P0C Octacat USY catalyst.

EXAMPLE 12 Using the procedure of Example 11, phenoxathin (202 g, 1.0 mole) and 1-hexadecene (224.43 g, 1.0 moles) were reacted using 42.4 grams of FOC Octacat USY catalyst.

EXAMPLE 13 2.0 g of anhydrous A1C1₃ were added to a stirred mixture of 1-octene, 224.2 g (2 moles), and phenoxathin (202 g, 1 mole) and heated at reflux for six hours. The mixture was then cooled; washed to remove inorganic materials; and dried over anhydrous MgSO.. Gas chrcmatographic analysis showed essentially complete reaction of starting material. Color of this material was >5 whereas the product of Example 1 was <2.0.

EXAMPLE 14 19.1 g of FOC Octacat USY catalyst were added to a vigorously stirred mixture of diphenyl sulfide (186.2 g, 1.0 mole) and 1-tetradecene (196.4 g, 1.0 mole) in a flask fitted with thermocouple and reflux condenser. The mixture was then heated to 200"C, with stirring, for six hours. After cooling to room temperature, the mixture was filtered to remove catalyst and vacuum distilled to 170'C at 0.5-1.5 mmHg to remove unreacted starting materials.

EXAMPLE 15 Using the procedure of Example 14, diphenyl sulfide

(186.2 g, 1.0 mole) and 1-tetradeoene (196.4 g, 1.0 mole) were reacted using 38.2 grams of FCC Octacat USY catalyst.

EXAMPLE 16 Using the procedure of Example 14, diphenyl sulfide (186.2 g, 1.0 mole) and 1-hexadecene (224.4 g, 1.0 moles) were reacted using 19.1 grams of FCC Octacat USY catalyst.

EXAMPLE 17 2.0 g of anydrous Aid. were added to a stirred mixture of 1-octene, 224.2 g (2 moles), and diphenyl sulfide (186.2 g, 1 mole) and heated at reflux for six hours. The mixture was then cooled, washed to remove inorganic materials; and dried over anhydrous MgSO.. Gas chrcmatographic analysis showed essentially complete reaction of starting material. Color of this material was >5 whereas the product of Example 1 was <2.0. Typical properties of exemplified hydrocarbyl diphenyl ethers are shown in TABLE 1.

TABLE l

Typical properties of exemplified diphenyl methanes are shown in TABLE 2.

Flash Point ('F) 446 457 478

Typical properties of exemplary hydrocarbyl phenoxathins are shown in TABLE 3.

Typical properties of exemplified hydrocarbyl diphenyl sulfides are shown in TABLE 4.

Tetradecene alkylated diphenyl ether hexadecene alkylated phenoxathin and both tetradecene and hexadecene alkylated diphenyl sulfide were compared with polyolefin base stock in a Four-Ball Wear test. The results show that at hi er load, both the alkyl diphenyl ether and sulfides and alkyl phenoxathin produced less wear than the other base stock, without any adverse effect on coefficient of friction (f) .

The antiwear properties of the examples were evaluated using the Four Ball Wear Test as shown in TABLE 5 below. The results clearly exhibit the excellent antiwear properties inherent in these compositions.

In the Four Ball Test three -stationary balls are placed in a lubricant cup; a lubricant containing the σcmpcund to be tested is added thereto; and a fourth ball is placed in a chuck mounted on a device which can be used to spin the ball at known speeds and loads. The examples were tested using half inch stainless steel balls of 5200 steel for thirty minutes under 40 kg load at 600 and 1800 rpm and 200'F. If additional infoπation is desired consult test method ASIM D2266 an3 or U.S. Patent 4,761,482. K, as reported in the Table, is the wear coefficient calculated frcm the wear volume, V, of the stationary ball. The wear volume is calculated frcm the wear scar diameter D in mm as follows:

V - [15,5 D3 - 0.001033L] D x 103 mm3 where L is the machine load in kg. This equation considers the elastic deformation of the steel balls.

Wear Coefficient K

Dimsnsionless K is defined as K = VH dN where V = wear volume, mm3

H = hardness 9725 kg mm2 for 52100 steel d = (23.3 mm rev) (RHϊ x Time)

N = (0.408) (Load in kg) The Four-Ball Wear Test results demonstrate the excellent antiwear properties of these compositions when used in synthetic oils.

4.0 wt% of sulfurized isobutylene (as generally described by A. G. Hαrodysky in U.S. 3,703,504) and 0.5 wt% of a hindered phenolic inhibitor obtained from Ethyl Corp. as Ethyl 702 were added to a synthetic lubricant base stock. The mixture of additives was insoluble in the base stock and the sample was cloudy. In separate runs, 20 wt% C. - alkylated diphenyl methane; 21 wt% C, _Λ a__kylated diphenyl sulfide; and 21 wt% C, _Λ alkylated diphenyl ether were added to this mixture. The sample was mixed; in each case the additives completely dissolved and the mixture became clear.

Improved τ*v=>n _ and Light Stability over Other lubricant Classes Thermal Stability Test

Sample % Viscosity Change After

72 hrs at 288°C 72 hrs at 310°C

-2.2

-5 -5 -15 -8.2 (Commercial Synthetic Lubricant -14.8 Ccmmerσial Synthetic Lubricant -19.4 CcBmercial Synthetic Lubricant -38.8 Ocminercial Synthetic Lubricant -60.9 Ccmmerσial Synthetic Lubricant -67.9 Lube Ester -34.2

(* -DEE, -DEM and -DPS are abbreviations for alkylated diphenyl ether, alkylated diphenyl methane and alkylated sulfide, respectively.)

Over St ra 0° 5 da s

Commercial Synthetic lubricant 1 ^"1.5 (Sample 1)

200-Second Solvent Paraffinic

Neutral Lubricating oil 2 >5.5

Light stability was good as no color change or precipitate !0 was observed over two months.

Iπprobed Qxidative Stability Of Hydrocarbyl Dipheπyl Methane Over Commercial Synthetic Lubricant

Rating

Ccmmercial Synthetic Lubricant 9-10

!5 C_χ6 DEM 3.5

¹ Hot Tube Oxidation Test (315'C/16 hrs) Rating (0 = clean; 10 = black, plumed)

Tested as base stock components in synthetic diesel engine oil formulation Performance As A T_.hr-ir_.nt With T proved Load Carrying Properties

Load-carrying properties were measured using ASTM D2596 at both room temperature and 100^βC.

23'C 100'C DjS Dtt Weld INS IWI Weld

Polyolefin base stock 50 22.7 126 32 14.6 126

C₁₆ Ehenαxathin 50 23.7 160 40 20.6 160

C₁₄ DEB 40 22.5 160 32 17.9 126

C₁₆ DES 40 21.4 160 50 22.9 126

The use of adducts of this invention as a suitable replacement for components of current lubricant formulations is highly desirable. For example, synthetic and or mineral based lubricant composition containing esters for improved additive solubility would be significantly improved by replacement with adducts of this invention due to their excellent thermal stability, additive solubility and or EP/antiwear properties. Adducts prepared as described herein provide excellent base stock properties and could -themselves serve as the base stock in fαmulations for various applications, for example, applications where high temperatures and EP are maintained.

Claims

CLAPS

1. An adduct preparable by catalytically reacting :

i) at least one compound comprising at least one olefinic group; a hydrocarbyl substitueπt; and, optionally, at least one heteroatcm; with

ii) a substituted or unsubstituted, fused or unfused, polyπuclear, aromatic compound which may contain at least one chalcogen atom.

2. An adduct according to claim 1 wherein the hydrocarbyl substitueπt comprises ac. to C__QQ alkyl, alke yl or alkyπyl group, a C to C_5Q0 aralkyl or alkaryl group or a C. to C₅₀₀ aryl group.

3. An adduct according to claim 1 or 2 wherein the hydrocarbyl substitueπt comprises frcm 8 to 18 carbon atoms.

4. An adduct according to any preceding claim wherein the hydrocarbyl εubstituent is a linear substitueπt.

5. An adduct according to any preceding claim wherein ^■ i) cxuprises an alpha olefin.

6. An adduct according to any preceding claim wherein the or each heteroatcm comprises S.N.O.P.F or a mixture thereof. 7. An adduct according to any preceding claim wherein ii) has the general formula :

in which :

X represents an oxygen or sulphur atom or a methylene group; and

8. An adduct according to claim 7 wherein ii) comprises diphenyl ether, diphenyl sulphide, dipherψlmethane or phenoxathiin.

9. An adduct according to any preceding claim preparable in the presence of a Lewis acid or zeolite catalyst.

10. A process for the preparation of an adduct, which process comprises catalytically reacting :

i) at least one compound comprising at least one olefinic group; a hydrocarbyl substitueπt; and, optionally, at least one heteroatcm; with ii) a substituted or unsubstituted, fused or unfused, polynuclear, aromatic ccmpound which may contain at least one chalcogen atcm

at a temperature from ambient to 350°C; a molar ratio of i) : ii) from 0.5:1.0 to 10.0:1.0; and a ratio of catalyst : ii) frcm lg : 1 mol to 100 g: 1 mol.

11. A process according to claim 10 wherein i) and or ii) are defined in any of claims 2 to 8.

12. A process according to claim 10 or 11 wherein the catalyst comprises a Lewis acid or a zeolite.

13. A process according to claim 12 wherein the catalyst comprises A1C1,, Octacat USY orMCM-22.

14. A process according to any of claims 10 to 13 wherein i) cxuprises octene-1, decene-1, dodecene-1 or tetradeαene-l.

15. A high temperature stable lubricant fluid comprising an adduct according to any of claims 1 to 9.

16. A lubricant according to claim 15 also comprising an oil of liibricating viscosity, or grease prepared therefrcm, in an amount frcm less than 1%^"to 99% by weight of the total composition. 17. A lubricant according to claim 15 or 16 wherein the oil of lubricating viscosity comprises a mineral oil, a synthetic oil, a mixture of mineral and synthetic oils, or a grease prepared therefrom.

18. A lubricant according to any of claims 15, 16 or 17 wherein the adduct comprises a relatively minor proportion of the lubricant and the oil of lubricating viscosity comprises a relatively major proportion of the lubricant.

19. A lubricant according to claim 18 wherein the adduct comprises frcm 0.01 to 10% by weight of the total opposition.

20. A fuel composition comprising an adduct and a liquid hydrocarbon or alcoholic fuel or a mixture thereof.

21. A fuel composition according to claim 20 wherein the fuel comprises gasoline, naphtha, diesel or an oxygenated fuel.

22. A fuel composition according to claim 22 or 22 wherein the adduct comprises a relatively minor proportion of the fuel and the fuel comprises a relatively major proportion of the composition.

23. Use of an adduct according to any of claims 1 to 9 in a high temperature stable lubricant fluid or a fuel composition for its improved antiwear, high and low temperature aπtiαxidaπt, aπtispalling, aπtisquawking, aπtifatique, antistaining, additive solubility, load carrying, extreme pressure, thermal and αxidative, aπticorτosiαn, denulsifying/emulsifying, detergent or cleanliness properties.