CA1119607A - Alkyl phenol solutions of organo molybdenum complexes as friction reducing anitwear additives - Google Patents
Alkyl phenol solutions of organo molybdenum complexes as friction reducing anitwear additivesInfo
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- CA1119607A CA1119607A CA000336907A CA336907A CA1119607A CA 1119607 A CA1119607 A CA 1119607A CA 000336907 A CA000336907 A CA 000336907A CA 336907 A CA336907 A CA 336907A CA 1119607 A CA1119607 A CA 1119607A
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Abstract
ABSTRACT OF THE DISCLOSURE
A solution of a hydrocarbon-soluble organo molybdenum complex obtained as the solution reaction product of a hydrocarbyl substituted thio-bis-phenol, e.g. 2,21-thio-bis (4-iso-nonyl phenol), with a molybdenum compound, e.g. molybdic oxide, in the presence of an amine, e.g. ethylene diamine, in a solvent of a C8-C50 alkyl substi-tuted phenol, e.g. nonyl phenol, is a useful hydrocarbon additive, particularly when used in combination with an oil-soluble sulfur donor, e.g. a metal dialkyl dithio phosphate, which provides an additive combination for lubricants and fuels whereby the resulting lubricating composition exhibits and improved antifriction property.
A solution of a hydrocarbon-soluble organo molybdenum complex obtained as the solution reaction product of a hydrocarbyl substituted thio-bis-phenol, e.g. 2,21-thio-bis (4-iso-nonyl phenol), with a molybdenum compound, e.g. molybdic oxide, in the presence of an amine, e.g. ethylene diamine, in a solvent of a C8-C50 alkyl substi-tuted phenol, e.g. nonyl phenol, is a useful hydrocarbon additive, particularly when used in combination with an oil-soluble sulfur donor, e.g. a metal dialkyl dithio phosphate, which provides an additive combination for lubricants and fuels whereby the resulting lubricating composition exhibits and improved antifriction property.
Description
60~7
2 The present invention relates to alkyl phPnol
3 solutions of hydrocarbon-soluble molybd~num complexes of
4 thio-bis phenols, their method of preparation and their utility as an additive for hydrocarbon compositions such 6 as gasoline, fuel oil and lubricating oils including 7 ~reases, industrial oils, gear oils and lubricants for 8 engines and other equipment having moving parts operating 9 under boundary lubricating conditions.
There are many instances, as is well-known, 11 particularly under "Boundary Lubrication" conditions where 12 two rubbing surfaces must be lubricated, or otherwise pro-13 tected, so as to prevent wear and to insure continued move-14 ment. Moreover, where, as in mos~ caæes, friction between the two surfaces will increase the power required to effect 16 movement and where the movement is an integral part of an 17 energy conversion system~ it is most desirable to effect 18 the lubrication in a manner which will minimize this 19 fr~ction. As is also well-known, both wear and friction can be reduced, with various degrees of success, through 21 the addition of a suitable additive or combination thereof 9 ~:
22 to a natural or synthetic lubricant. Similarly, continued 23 movement can be insured~ again with varying degrees of 24 success, through the addition of one or more appropriate additives.
26 While there are many known additives which may 27 be classified as antiwear~ antifriction and extreme pres-28 sure agents and some may in fact satisfy more than one of 29 these functions as well as provide other useful functions, it is also known that man~ of these additives act in a ,' ~ ~ :~
.
' ~
' ~ , ' ': ' ~ : ' - : -, . , ~- ~
l diffPrent physical or chemical manner and often compete 2 with one another, e.g. 9 they may compete for the surface 3 of the moving metal parts which are subjected to lubri-4 cation. Accordingly, extreme care must be axercised in the selection of these additives to insure compa~ibility 6 and effectiveness.
7 The metal dihydrocarby;L dithiophosphates are one 8 of the additives which are known to exhibit antioxidant 9 and antiwear properties. The most commonly used additives of this class are the zinc dialkyl dithiophosphates which 11 are conventionally used in lubricant compositions. While 12 such zinc compounds afford excellent oxidation resistances 13 and exhibit superior antiwear properties, it has heretofore 14 been believed that the same increases or significantly limits the ability to decrease friction be~ween moving 16 surfaces. As a result, compositions containing 2inc di-17 alkyl dithiophosphates ware not believed to provide the 18 most desirable lubrici~y and, in turn, i~ was believed 19 that use of compositions containing the same would lead to si~nificant energy losses in overcoming friction even 21 when antifriction agents are included in the composition.
22 Known ways to solve the problem of energy losses 23 due to high friction~ e.g., in crankcase motor oils include 24 the use of synthetic ester base oils which are Pxpensive and the use of insoluble molybdenum sulfides which have 26 the disadvantage of giving the oil composition of black 27 or hazy appearance.
28 Other types of molybdenum compounds taught to 29 be useful in lubricating oils include the alkyl esters of molybdic acid as corrosion inhibitors (see UOS. 2,805,997) 31 and nitrogenous thiomolybdates as metal antiwear additives 32 which are said to function by providing a coating of re-33 duced coefficient of friction (see U.S. 2,938,869). .
34 SimiLarly, antifriction agents or oiliness or lubricity agents as the same are often referred to in the 36 prior art, function by forming a coating on the surface .:...
~, - . ~ .
,, , : , - 3 ~
1 of the moving metal parts. As in the case of antiwear 2 agents, however, the coating bonds are, ~enerally, ef-3 fected physically, rather than chemically, and7 indeed, 4 the bonding between an antifriction agent and the surface is, generally weaker than the bond formed between an anti-6 wear agent and the metal surface~
7 In light of the foregoingg the need for improved 8 lubricating compositions that will permit operation of 9 moving parts under boundary conditions with reduced fric-tion is believed to be readily apparent. Similarly, the 11 need for such a composition that can include conventional 12 base oils and other conventional additives such as ash-13 less dispersants, detergents, antioxidants (e.g., 2,6-14 ditert, butyl para-cresol9 methylene bis (4,4'-di[296-di-(tert. butyl) phenol] - see U.S. 3,591,497~ col. 2, 16 lines 49-52)7 V. I. improvers, etc., and can be used 17 without the loss of other desirable lubricant properties, 18 particularly those provided by zinc dialkyl dithiophos-19 phates, is also readily apparent.
SUMMARY OF THE INVENTION
21 In Canadian Patent Application 310,503~ there is 22 a teaching of a class of organo molybdenu~ complexes pro-23 duced by the solution reaction of a thio-bis-phenol~ a 24 source of molybdenum and an amine in a mineral oil solvent which are reported therein as useful friction-reducing 26 additives for lubrieants and fuels. It has now been dis-27 covered that said complexes containing from about 0.5 to 28 about 5~ preferably 1 to 2.5, optimally 1.4, wt. % nitrogen 29 are more readily produced in quantitative yields at lower temperatures and with a broader spectrum of amines (all with 31 respect to said teaching) when their preparative reaction 32 is carried out in an ~lkyl phenol solvent wherein said 33 phenol is a Cs to Cso, preferably C8 to Clg, optimally 34 Cg(ave ) alkyl substituted phenol.
The amine reactants include ammonia, simple 36 amines such as C6-C30 alkyl amines, alkylene polyamines 37 such as ethylene diamine (preferred) and diethylene ~: .
1 triamine, alkanolamines such as ethanolamine, ethoxylated 2 derivatives o~ al~ylene diamines such as hydroxyethyl 3 ethylene diamine, urea and ureides. When said complex is 4 introduced into the lubricating oil in combination with said phenol~ e.g., as the solution of said reaction~ the 6 modified lubricating oil exhibits a dynamic coefficient o~
7 friction comparable to if not somPwhat better than that 8 result obtained with the addition of only a common amount 9 of organo molybdenum complex.
In accordance with the present invention9 the 11 foregoing and other objects and advantages are accomplished 12 with a hydrocarbon composition comprising a ma~or propor-13 tion of a hydrocarbon, e.g., a lubricating oil, and at least 14 a friction reducing amount of a solution said organo molybdenum complex in C8-C50 alkyl phenol and preferably a lubricity 16 enhancing combination of: (a) said organo molybdenum 17 complex; (b) said C5 to C50 alkyl phenol and (c) an oil-1~ soluble sulfur donor, preferably zinc dialkyl dithiophos-19 phate, and if desire, at least a sludge-dispersing amount of an oil-soluble dispersant, e.g., an ashless dispersant9 21 and at least a rust-inhibiting amount of a rust inhibitor.
22 In practice, the lubricity enhancing combination is 23 present in an amount sufficient to provide from about 24 0.005 to 0.2, preferably 0.03 to 0.15, optimally about 0.1, wt. % molybdenum~ at least about 0.25, e~g., 0.25 to 26 1, wt. % sulfur donor and from 0.25 to 5 wt. % Cg-Cso 27 alkyl phenol, all weight percent being based on the total 28 weight o~ the hydrocarbon composition such as lubricating 29 oil or fuel.
DFTAILED DESCRIPTION OF THE INVENTION
31 OIL-SOLUBLE ORGA~O MOLYBDENUM COMPOUN~
B 32 The hydrocarbon- ~ molybdenum complexes are 33 believed to be derived from a thio-bis-phenol as shown in 34 Formula I. The R group of said Formula I as defined is substantially hydrocarbyl and thus is alkyl, aryl, aralkyl, 36 cycloalkyl, or alkaryl; however, the hydrocarbyl group may 37 contain polar substituents such as amino, aminoalkyl, .
. . ~ . .
1 hydroxy, hydro~yalkyl, halo, mercap~o, keto, phosphinyl, 2 phosphoryl, thiophosphoryl and dithiophosphoryl radicals.
3 Specific examples of the R group includes methyl, 4 ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl~ n-hexyl, heptyl, oct~l, nonyl-decyl, dodecyl, 6 tridecyl, heptadecyl, octadecyl, polyisobutyl9 and poly-7 propyl.
8 The organic molybdenum complexes are the reackion 9 product of a thio-bis-phenol, an amine and molybdenum.
The aforesaid thio-bis-phenols can be characterized by 11 Formula I.
13 OH ,OH
14 ~3 Sn R R
16 wherein R and n are each the same as previously described 17 with R preferably para to the hydroxyl substituent. These 18 thio-bis-phenols are readily produced from the reaction of 19 alkyl phanols and a source of sulfur, e. g, chemical sul-fur or sulfur halides. Ths alkyl phenols are readily p~o-21 duced ~y the reaction of an alpha-olefin or mixtures thereof~
22 e.g., a nonene-l cut which is primarily Cg but including 23 some C8 and C10 olefins as well, with phenol, in the 24 presence of an alkylation catalyst, e.g., BF3, whereby a reaction product mixture of primarily monoalkyl phenols 26 (most para to the hydroxyl group) but with a minor amount, 27 e. g., 20-35 wt. % of di-(al~yl) phenols and a small amount, 28 e.g., 2 to 5 wt. ~ of tri-(alkyl) phenols is obtained.
29 A particularly useful reactant for the preparation of the molybdenum complex can be characterized by Formula 31 II.
., l II
3 ~ S - ~
4 ~ C9Hl9 gHlg The source of molybdenum is a moly~den~m con 6 taining compound capable of rsacting with the thio-bis-7 phenol to provide a molybdenum complex containing from 8 about 0.5 to 20, preferably 2 to 10, op~imally about 9 5 wt. % molybdenum based on the total weight of said com-plex. The source~ of molybdenum include molybdic tri-11 oxide, also known as molybdic anhydride~ ammonium ~hiomolyb-12 date, ammonium bismolybdate, molybdenum halides, and 13 ammonium heptamolybdate tetrahydrate.
14 The organo moly~denum complex is substantially the product of a solution reaction between 1-2 moles thio-16 bis-phenol, 1 mole of molybdenum and 1-2 moles of an 17 amine. The reactlon is readily carried out by reaction at 18 an elevated temperature of from 135C to 225C~ preferably 19 160C to 190C, optimally 175C to accelerate said reaction and remove the water of reaction. The reaction is carried 21 out in a C8 to C50, preferably C8 to C18, alkyl substitu~ed 22 phenol, optimally Cg~a~erage) alkyl phenol. The reaction 23 is carried out over a period of from about 4 to 20, prefer-24 ably 6 to 12, hours in order to suitably stabilize the complex and for removal of the water of reaction as by 26 nitrogen qparging or distillation at abmospheric or reduc~d 27 pressure.
29 The amine reactants broadly cnntain from 1 to 5, preferably 2, nitrogens a~d from O to 60, preferably 2 to 31 20 carbons. The preferred amine~ are of the class con-32 sisting of: C6-C30 alkyl amines such as n-o tyl amine 33 and dodecyl amine; al~ylene polyamines which can be repre-34 sented by the general formula N~2(CH2)n-rNH(CH2)n]m-NH~
where n is 2 to 3 and m is a number from O to 3 including ~",;
. ., . -6 0'~
1 ethylene diamine, diethylene triamine~ te~raethylene 2 pentamine and mixtures of such polyamines formed from ~he 3 reaction of ethylene dichloride and ammonia or ethylene 4 imine and ammonia; alkanolamines such as ethanolamine and diethanolamine; ethoxylated derivatieves of alkylene poly-6 amine such as hydroxyethyl ethylene diamine and the reaction 7 product of alkylene oxides such as an ethylene oxide or 8 propylene oxide with polyamines, e.g., dinitrilo te~ra-9 ethanol; urea and ureides such as ethylurea.
Carrying out the organo molybdenum complexing 11 reaction in a C5-C50, preferably C8-C18, optimally Cg, 12 alkyl phenol solvent in an amount ranging from about 0.25 13 to 5~ preferably 1, parts by weight of phenol per part by 14 weight of organo molybdenum complex product provides a number of benefits over a reaction without solvent or in 16 a light aromatic solvent such as toluene or a light hy-17 drocarbon oil, e.g.,mineral oil including: a faster re-18 action time; completion of reaction to a stabilized molyb-19 denum complex at a lower temperature; faster and simpler filtration of the reaction product solution; and, a pro-21 duct solution which when added to lubricating oil provides 22 comparable if not enhanced friction reduction (as seen 23 from the subsequent Table I~.
The Cs to C509 preferably C8-C18, alkyl phenols 26 useful a~ solvents for the organo molybdenum complexing 27 reaction are generally the same as the alkyl phenols des-28 cribed to be reactive with a source of sulfur to provide 29 the thio-bis-phenols of FoDmula I. Rather than broadly covering Cl to Cs~ alkyl phenols, the solvent class is 31 broadly limited to Cs to C50 alkyl phenols. Their me~hod 32 of preparation is the same as earlier described and as a 33 class generally commercially available. Described herein 34 as the optimum alkyl phenol is a C8-ClO~ i e ~ C~(average~
alkyl substituted phenol commercially available as ECA
` 36 900 ~ from Exxon Chemical Company of Houston, Texas.
~ 7 _ ',;
.
(37 1 Broadly~ amyl phenol through pentacontanyl phenol are use-2 ful with octyl phenol through octadecyl phenol being pre-3 ferred.
4 The Cs-Cs~ alkyl phenols are usefully present in the hydrocarbon composition i.n an amown~ of from about 6 0.25 to 5, preferably 1, parts by weight per part by 7 weight of the organo molybdenum complex.
9 The Cg-C50 alkyl phenol solutions of the hydro-carbon-soluble organo malybdenum complexes provide en-11 hanced lubricity in lubricating oils when used in combina-12 tion with an active sulfur donor which can be defined as 13 a compound which when used in admix~ure with the organo 14 molybdenum complex reduces the coefficient of friction at least about 10% relative to that provided by the complex 16 alone. The active sulfur donor is present in an amount of 17 from a~out 0.1 to 10, preferably 0.2 to 2, parts by weight 18 per part by weight of molybdenum complex.
19 Illustrative of active sulfur donors are metal dihydrocarbyl dithiophosphates and the corresponding pre-21 cursor esters, phosphosulfurized pinenes9 sulfurized ole-22 finss and hydrocarbons, sulfurized fatty esters and sulfur-23 ized alkyl phenols.
24 Preferred are the zinc dihydrocarbyl dithio-phosphates which are salts of dihydrocarbyl esters of di-26 thiophosphoric acids and may be r~prasented by the follow-27 ing ormula:
28 _ _ 29 RO - P - S Zn OR' 31 _ _ 2 32 wherein R and Rl may be the same or different hydrocarbyl 33 radicals con~aining rom 1 to 18 and preferably 2 to 12 34 carbon atoms cmd ~ncluding radicals such as alkyl~ alkenyl9 aryl, aralkyl, alkaryl and cycloaliphatic radicals. Par-36 ticularly preferred as R and R' groups are alkyl groups ; :
9~
g 1 of 2 to 8 carbon atoms. Thus, t:he readicals may, for 2 example, be ethyl, n~propyl, i~propyl, n-butyl, i-butyl9 3 sec-butyl, tert-butyl9 amyl~ n-hexyl, i-hexyl, n-heptyl) 4 n-octyl~ decyl~ dodecyl, o~tadec:yl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylc:yclopentyl, propenyl, 6 butenyl, etc. In order to obtain oil solubility, the 7 total number of carbon atoms in the dithiophosphoric acid 8 will average abou~ 5 or greater.
9 The zinc dihydrocarbyl dithiophosphates which are useful as coadditive~ i.e., sulfur donor of the present 11 invention9 may be prepared in accordance with known tech-12 niques by first esterifying a dithiophosphoric acid usually 13 by reaction of an alcohol or phenol with P2S5 and then 14 neutralizing the dithiophosphoric acid ester with a suit-able zinc compound such as zinc oxide.
16 In general, ~he zinc dihydrocarbyl dithiophos-17 phate will be used in the lubricating composition at a 18 concentration within the range of about 0.01 to about 5 19 parts by weight per 100 parts of lubricating oil and preferably from abou~ 0.5 to about 1.5. This is adequate 21 ~or sulfur donation whereby the lubricity enhancement of 22 the lubrica~ing oil composition by the coadditive combina-23 tion is realized~
24 As noted earlier~ an equally suitable active sulfur donor is the dihydrocarbyl esters of dithiophos-26 phoric acid which may be represented by the formula:
27 ~ S ~
29 OR' 3~ _ _ 2 31 wherein R and R' are as previously defined. Particularly 32 useful is the dibutylphenyl dithiophosphate.
33 The phosphorosulurized terpenes as represented 34 by pinene~ dipenene, allo-ocimene, etc.~ are another i5 group of dithiophosphate di;sters which are active sulfur ,, . . ~ , 6~7 1 donors. Of the terpenes~ the bicyclic pinene is preferred.
2 The phosphosulfurized terpene is readily obtained by re-3 action of about one mole of diester of thiophosphoric acid 4 and one mole of pinene at a temperature of at least 100C, e.g., 100C.to 200C. The preflerred active sulfur donor 6 can be characterized as the bornyl ester of dihydrocarbyl 7 (C2-C20) dithiophosphoric acids (as shown in U.S. 296899258~.
8 The sulfurized olefins and hydrocarbons are 9 further esters of thiophosphoric acids which are useful sulfur donors. These esters are achieved by reaction wi~h 11 olefins such as ethylene, propylsne~ isobutylene, decene, 12 dodecene, octadecene, etc.; olef;n polymers of molecular 13 weight ranging from 100 to 507000 such as ethylene, 14 propylene, isobutylene, etc.; aromatics such as benzen~, naphthylene, toluene9 xylene, etc.; petroleum fractions 16 and condensation products of halogenated aliphatic hydro-17 carbons with aromatic compounds, e.g., wa~ naphthalene 18 (see U.S. 298047431).
19 The sulfurized fatty esters are another subclass of esters which are active sulfur donors. These products 21 are readily obtained from the reaction of P2S5 and aliphatic 22 alcohols usefully having from about 8 to 22 carbons ob-23 tained from natural sources included linoleic, palmolitic, 24 behenic, stearic, palmiticg lauric, capric, etc., as well as mixtures obtained from vegetable and animal oils such 26 as tall oil.
27 The sulfurized alkyl phenols are generally C4 28 to C20 alkyl phenol sulfides. T~ese sulfurized alkyl 29 phenols are readily produc~d by sulfurizing an alkyl phenol with a sulfur halid~ or elemental sulfur.
32 In addition to the organo molybdenum co~..plex 33 alkyl phenol and active sulfur donor, a lu~ricating oil 34 composition may contain-other well-known lubricating oil additives to provide trouble-free operation of the lubri-36 cated equipment, such as ashless dispersants, metallic , , .' . ' ' ' ~ .
' '' ' ' ' '~ ' ',~ ~' ..,, 1 detergen~s, supplemental oxidation and corrosion inhibitors, 2 extreme pressure agents, rust inhibitors, pour point de-3 pressants, viscosity index improvers, etc.
4 1. ASHLESS DISPERSANTS
As used herein, the terminology "ashless dis-6 persant" is intended to describlP the now well-known class 7 of non-metal-containing oil-soluble poly~eric additives 8 or the acyl derivatives of relatively high molecular 9 weight carboxylic acids which are capable of dispersing contaminants and the like in hydrocarbons such as lubri-11 cating oils. The carboxylic acids may be mono-or poly-12 carboxylic acids and they are generally characterized by 13 substantially hydrocarbon constituents containing an 14 average OL 50 to ?50 aliphatic carbon atoms.
A preferred class of ashless dispersants are 16 the nitrogen-containing dispersant additives which are 17 generally known in the art as sludge dispersants for 18 crankcase motor oils. These dispersants-include mineral 19 oil-soluble salts, amides, imides and esters made from high molecular weight mono-and dicarboxylic acids (and 21 where they exist the corresponding acid anhydrides) and 22 various amines of nitrogen-containing materials having 23 amino nitrogen or heterocyclic nitrogen and at least one 24 amido or hydroxy group capable of salt, amide, imide or ester formation. Usually, these dispersants are made by 26 condensing a monocarboxylic acid or a dicarboxylic acid 27 or anhydride, preferably a succinic acid producing material 28 such as alkenyl succinic anhydride, with an amine or 29 alkylene polyamine. Usually~ the molar ratio of acid or anhydride to amine is be~een 1:1 to 5:1~ e.g., 1 31 mole of C70 to C10O polyisobutenyl succinic anhydride to 32 2 moles of ~etraethylene pentamine.
33 Primarily because of its ready availability and 34 low cost, the hydrocarbon portion of the mono-, or dicar-boxylic acid or anhydride is preerably derived from a 36 polyrner of a C2 to C5 monoolefin9 said polymer generally 37 having between 50 and 250 carbon atoms. A particularly .. . .
. . ~
, ' ~
1 preferred polymer is polyisobutylene.
2 Polyalkyleneamines are usually used to make 3 the non~metal-containing dispersant. These polyalkylene-4 amines include those represented by the general form~tla:
NH2(CH2)n~[NH(CH2)n]m-NH2 6 wherein n is 2 to 3 and m is a number from O to 10.
7 Specific compounds coming within the formula include di-8 ethylene triamine, tetraethylene pentamine, dipropylene-9 triamine, octaethyleneonamine9 and tetrapropylenepentamine;
N,N-di-(2-aminoethyl) ethylenediLamine may also be used.
11 Other aliphatic polyamino compounds that may b2 used are 12 N-amino-al~ylpiperzaines, e.g.g N-(2-aminoethyl) piperazine.
13 Mixtures of alkylene polyamines approximating ~traethylene 14 pentamine are ro~mercially availa~le, e.g., Dow E-100 sold by Dow Chemical Company of Midland, Michigan.
16 Reprasentative dispersants are formed by re-17 acting about one molar amount of polyisobutenyl succinic 18 anhydride with from about one to about two molar amounts 19 of tetrae~hylene pentamine or with from about 0.5 to 1 moles of polyol9 e.g., pentaerthritol.
21 It is possible to modify the ashless dispersants 22 generally by the addition o~ metals such as boron in order 23 to enhance the dispersancy of the additive. This is 24 readily accomplished by adding boric acid to the reaction mixture after the imidation or esterification is substan-26 tially complete and heating the mixture at tempera ures of 27 100 to 150C for a few hours.
28 2. OT~ER ADDITIVES
29 Detergents useful in con~unction with dispersants, preferably the ashless type, include normal, basic or 31 overbased metal, e.g., caLcium, magnesium~ etc., salts 32 of petroleum naphthenic acids, petrnleum sulfonic acids, 33 alkyl benzene sulfonic acids, oil-soluble fatty acids, 34 alkyl salicyclic acids3 alkylene-bi~-phenols, and hydro-lyzed phosphorosulfurized polyolefins.
36 Oxidation inhibitors include hindered phenols, 37 e.g., 2,6-ditert butyl para~cresol amines, sulfurized ~.,;, :
: ~ ' - ' .
.. ~ ' . -' '7 1 phenols and alkyl phenothiazlnes.
2 Pour point depressants include wax alkylated 3 aromatic hydrocarbons, olefin pol~ners and copolymers, 4 acrylate and methacrylate polymers and copolymers.
- Viscosi~y Index Improvers include olefin poly-6 mers such as polybutene, ethylene-propylene copolymers~
7 hydrogenated pol~ners and copol~ers and terpolymers of 8 styrene with isoprene and/or bu~:adiene, polymers of alkyl 9 acrylates or alkyl methacrylate~;, copolymers of alkyl methacrylates with N-vinyl pyrollidone or dimethylamino-11 alkyl methacrylate, post-grafted pol~ners of ethylene-12 propylene with an active monomer such as maleic anhydride 13 which may be further reacted with an alcohol or an alkyl-14 ene polyamine, styrene/maleic anhydride polymers post-reacted ~ith alcohols and amines, etc.
16 The hydrocarbons in which the additive combina-17 tion of the invention is most effective are mineral oils 18 having a viscosity as measured by ASTM D-445 of ~rom about 19 2 to 40, preferably 5 to 20 centistokes at g9C.
If the additive combination of oil-soluble organo 21 molybdenum comple~ C5-C50 alkyl phenol ~nd active sulfur 22 donor are used as an additive concentrate, the concentrate 23 may consist essentially of from about 5 to 95/O of the ad-24 ditive combination, the remainder being an additional hydro-carbon solvent, such as kerosene, mineral oil, a naphtha 26 and the like, or a C5-C50 alkanol.
27 The preferred concentrate contains about 40 to 28 90% of the additive combination in a second solvent of 29 mineral oil.
Whether the organo moly~denum complex-alkyl 31 phenol solution is used alone or in combination with an 32 active sulf~r donor, its concentration may vary appreciably 33 with the part:icular hydrocarbon. For example, when said 34 molybdenum complex-alkyl phenol solution is used alone in a fuel such as gasoline, the concentration of the complex 36 ranges from lV to 1~000, preferably 20 to 50 weight parts 37 per million b~lsed on the total weight of the fuel composition, ~ 3Lg~;07 whereas in a lubricant, it is used in combination with the active sulfur donor, which three-component combination then ranges from about 0.5 to 5, prefera~ly l to 3 wt. ~ based on the total weight of the l~bricating oil.
The invention will be further understood by reference to the following examples which illustrate a preferred form of the invention and compares the same with different~ though similar compositions.
The following examples illustrate more clearly the compo-sitions of the present invention. However, these illustrations are not to be interpreted as specific limitations on this invention.
*
Nonyl phenol sulfide (183 g) as ECA 9001 , Solvent Neutral 150 mineral oil (183 g) and molybdic trioxide (28.1 g) as an undensified grade obtained from Climax Molybdenum Company, Fort Madison, Wisconsin were stirred together and then raised in temperature to 94C at which time ethylene diamine (23.4 g) was thereafter slowly added over a 20-minute period. The temperature was raised with stirring to 121C over 0.6 hour. While stirring at this temperature, the volatiles including water and ammonia were removed by gentle nitrogen sparging for 18 hours. After filtration, the resulting product solution, useful as a lubricat-ing oil additive, had a viscosity of 177 S.U.S. @ 100C and was black in color and contained about 4.3 wt. % molybednum and 1.9 wt. % nitrogen. ECA 9001 , a 70 wt. % active mineral solution of di-(Cg average) nonyl phenol sulfide is commercially available from Exxon Chemical Company, EIouston, Texas.
This is an organo metallic complex prepared according to the teachings of said copending Canadian Application Serial No.
310,503, using a mineral oil solvent for the reaction medium.
Filtration through a steam-heated Buchner funnel holding a ~" pre-coat of Celite 535 took in excess of one hour. Exposure of the product solution to about 150C for 3 hours reduced its nitrogen content to 1.43 wt.
* Trade Mark -- 1~ --~, , 1 and appeared to ~volve ammonia during said three hours.
3 The procedure of Example 1 was followed except 4 that the mineral oil was replaced by: 183 g of nonyl
There are many instances, as is well-known, 11 particularly under "Boundary Lubrication" conditions where 12 two rubbing surfaces must be lubricated, or otherwise pro-13 tected, so as to prevent wear and to insure continued move-14 ment. Moreover, where, as in mos~ caæes, friction between the two surfaces will increase the power required to effect 16 movement and where the movement is an integral part of an 17 energy conversion system~ it is most desirable to effect 18 the lubrication in a manner which will minimize this 19 fr~ction. As is also well-known, both wear and friction can be reduced, with various degrees of success, through 21 the addition of a suitable additive or combination thereof 9 ~:
22 to a natural or synthetic lubricant. Similarly, continued 23 movement can be insured~ again with varying degrees of 24 success, through the addition of one or more appropriate additives.
26 While there are many known additives which may 27 be classified as antiwear~ antifriction and extreme pres-28 sure agents and some may in fact satisfy more than one of 29 these functions as well as provide other useful functions, it is also known that man~ of these additives act in a ,' ~ ~ :~
.
' ~
' ~ , ' ': ' ~ : ' - : -, . , ~- ~
l diffPrent physical or chemical manner and often compete 2 with one another, e.g. 9 they may compete for the surface 3 of the moving metal parts which are subjected to lubri-4 cation. Accordingly, extreme care must be axercised in the selection of these additives to insure compa~ibility 6 and effectiveness.
7 The metal dihydrocarby;L dithiophosphates are one 8 of the additives which are known to exhibit antioxidant 9 and antiwear properties. The most commonly used additives of this class are the zinc dialkyl dithiophosphates which 11 are conventionally used in lubricant compositions. While 12 such zinc compounds afford excellent oxidation resistances 13 and exhibit superior antiwear properties, it has heretofore 14 been believed that the same increases or significantly limits the ability to decrease friction be~ween moving 16 surfaces. As a result, compositions containing 2inc di-17 alkyl dithiophosphates ware not believed to provide the 18 most desirable lubrici~y and, in turn, i~ was believed 19 that use of compositions containing the same would lead to si~nificant energy losses in overcoming friction even 21 when antifriction agents are included in the composition.
22 Known ways to solve the problem of energy losses 23 due to high friction~ e.g., in crankcase motor oils include 24 the use of synthetic ester base oils which are Pxpensive and the use of insoluble molybdenum sulfides which have 26 the disadvantage of giving the oil composition of black 27 or hazy appearance.
28 Other types of molybdenum compounds taught to 29 be useful in lubricating oils include the alkyl esters of molybdic acid as corrosion inhibitors (see UOS. 2,805,997) 31 and nitrogenous thiomolybdates as metal antiwear additives 32 which are said to function by providing a coating of re-33 duced coefficient of friction (see U.S. 2,938,869). .
34 SimiLarly, antifriction agents or oiliness or lubricity agents as the same are often referred to in the 36 prior art, function by forming a coating on the surface .:...
~, - . ~ .
,, , : , - 3 ~
1 of the moving metal parts. As in the case of antiwear 2 agents, however, the coating bonds are, ~enerally, ef-3 fected physically, rather than chemically, and7 indeed, 4 the bonding between an antifriction agent and the surface is, generally weaker than the bond formed between an anti-6 wear agent and the metal surface~
7 In light of the foregoingg the need for improved 8 lubricating compositions that will permit operation of 9 moving parts under boundary conditions with reduced fric-tion is believed to be readily apparent. Similarly, the 11 need for such a composition that can include conventional 12 base oils and other conventional additives such as ash-13 less dispersants, detergents, antioxidants (e.g., 2,6-14 ditert, butyl para-cresol9 methylene bis (4,4'-di[296-di-(tert. butyl) phenol] - see U.S. 3,591,497~ col. 2, 16 lines 49-52)7 V. I. improvers, etc., and can be used 17 without the loss of other desirable lubricant properties, 18 particularly those provided by zinc dialkyl dithiophos-19 phates, is also readily apparent.
SUMMARY OF THE INVENTION
21 In Canadian Patent Application 310,503~ there is 22 a teaching of a class of organo molybdenu~ complexes pro-23 duced by the solution reaction of a thio-bis-phenol~ a 24 source of molybdenum and an amine in a mineral oil solvent which are reported therein as useful friction-reducing 26 additives for lubrieants and fuels. It has now been dis-27 covered that said complexes containing from about 0.5 to 28 about 5~ preferably 1 to 2.5, optimally 1.4, wt. % nitrogen 29 are more readily produced in quantitative yields at lower temperatures and with a broader spectrum of amines (all with 31 respect to said teaching) when their preparative reaction 32 is carried out in an ~lkyl phenol solvent wherein said 33 phenol is a Cs to Cso, preferably C8 to Clg, optimally 34 Cg(ave ) alkyl substituted phenol.
The amine reactants include ammonia, simple 36 amines such as C6-C30 alkyl amines, alkylene polyamines 37 such as ethylene diamine (preferred) and diethylene ~: .
1 triamine, alkanolamines such as ethanolamine, ethoxylated 2 derivatives o~ al~ylene diamines such as hydroxyethyl 3 ethylene diamine, urea and ureides. When said complex is 4 introduced into the lubricating oil in combination with said phenol~ e.g., as the solution of said reaction~ the 6 modified lubricating oil exhibits a dynamic coefficient o~
7 friction comparable to if not somPwhat better than that 8 result obtained with the addition of only a common amount 9 of organo molybdenum complex.
In accordance with the present invention9 the 11 foregoing and other objects and advantages are accomplished 12 with a hydrocarbon composition comprising a ma~or propor-13 tion of a hydrocarbon, e.g., a lubricating oil, and at least 14 a friction reducing amount of a solution said organo molybdenum complex in C8-C50 alkyl phenol and preferably a lubricity 16 enhancing combination of: (a) said organo molybdenum 17 complex; (b) said C5 to C50 alkyl phenol and (c) an oil-1~ soluble sulfur donor, preferably zinc dialkyl dithiophos-19 phate, and if desire, at least a sludge-dispersing amount of an oil-soluble dispersant, e.g., an ashless dispersant9 21 and at least a rust-inhibiting amount of a rust inhibitor.
22 In practice, the lubricity enhancing combination is 23 present in an amount sufficient to provide from about 24 0.005 to 0.2, preferably 0.03 to 0.15, optimally about 0.1, wt. % molybdenum~ at least about 0.25, e~g., 0.25 to 26 1, wt. % sulfur donor and from 0.25 to 5 wt. % Cg-Cso 27 alkyl phenol, all weight percent being based on the total 28 weight o~ the hydrocarbon composition such as lubricating 29 oil or fuel.
DFTAILED DESCRIPTION OF THE INVENTION
31 OIL-SOLUBLE ORGA~O MOLYBDENUM COMPOUN~
B 32 The hydrocarbon- ~ molybdenum complexes are 33 believed to be derived from a thio-bis-phenol as shown in 34 Formula I. The R group of said Formula I as defined is substantially hydrocarbyl and thus is alkyl, aryl, aralkyl, 36 cycloalkyl, or alkaryl; however, the hydrocarbyl group may 37 contain polar substituents such as amino, aminoalkyl, .
. . ~ . .
1 hydroxy, hydro~yalkyl, halo, mercap~o, keto, phosphinyl, 2 phosphoryl, thiophosphoryl and dithiophosphoryl radicals.
3 Specific examples of the R group includes methyl, 4 ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl~ n-hexyl, heptyl, oct~l, nonyl-decyl, dodecyl, 6 tridecyl, heptadecyl, octadecyl, polyisobutyl9 and poly-7 propyl.
8 The organic molybdenum complexes are the reackion 9 product of a thio-bis-phenol, an amine and molybdenum.
The aforesaid thio-bis-phenols can be characterized by 11 Formula I.
13 OH ,OH
14 ~3 Sn R R
16 wherein R and n are each the same as previously described 17 with R preferably para to the hydroxyl substituent. These 18 thio-bis-phenols are readily produced from the reaction of 19 alkyl phanols and a source of sulfur, e. g, chemical sul-fur or sulfur halides. Ths alkyl phenols are readily p~o-21 duced ~y the reaction of an alpha-olefin or mixtures thereof~
22 e.g., a nonene-l cut which is primarily Cg but including 23 some C8 and C10 olefins as well, with phenol, in the 24 presence of an alkylation catalyst, e.g., BF3, whereby a reaction product mixture of primarily monoalkyl phenols 26 (most para to the hydroxyl group) but with a minor amount, 27 e. g., 20-35 wt. % of di-(al~yl) phenols and a small amount, 28 e.g., 2 to 5 wt. ~ of tri-(alkyl) phenols is obtained.
29 A particularly useful reactant for the preparation of the molybdenum complex can be characterized by Formula 31 II.
., l II
3 ~ S - ~
4 ~ C9Hl9 gHlg The source of molybdenum is a moly~den~m con 6 taining compound capable of rsacting with the thio-bis-7 phenol to provide a molybdenum complex containing from 8 about 0.5 to 20, preferably 2 to 10, op~imally about 9 5 wt. % molybdenum based on the total weight of said com-plex. The source~ of molybdenum include molybdic tri-11 oxide, also known as molybdic anhydride~ ammonium ~hiomolyb-12 date, ammonium bismolybdate, molybdenum halides, and 13 ammonium heptamolybdate tetrahydrate.
14 The organo moly~denum complex is substantially the product of a solution reaction between 1-2 moles thio-16 bis-phenol, 1 mole of molybdenum and 1-2 moles of an 17 amine. The reactlon is readily carried out by reaction at 18 an elevated temperature of from 135C to 225C~ preferably 19 160C to 190C, optimally 175C to accelerate said reaction and remove the water of reaction. The reaction is carried 21 out in a C8 to C50, preferably C8 to C18, alkyl substitu~ed 22 phenol, optimally Cg~a~erage) alkyl phenol. The reaction 23 is carried out over a period of from about 4 to 20, prefer-24 ably 6 to 12, hours in order to suitably stabilize the complex and for removal of the water of reaction as by 26 nitrogen qparging or distillation at abmospheric or reduc~d 27 pressure.
29 The amine reactants broadly cnntain from 1 to 5, preferably 2, nitrogens a~d from O to 60, preferably 2 to 31 20 carbons. The preferred amine~ are of the class con-32 sisting of: C6-C30 alkyl amines such as n-o tyl amine 33 and dodecyl amine; al~ylene polyamines which can be repre-34 sented by the general formula N~2(CH2)n-rNH(CH2)n]m-NH~
where n is 2 to 3 and m is a number from O to 3 including ~",;
. ., . -6 0'~
1 ethylene diamine, diethylene triamine~ te~raethylene 2 pentamine and mixtures of such polyamines formed from ~he 3 reaction of ethylene dichloride and ammonia or ethylene 4 imine and ammonia; alkanolamines such as ethanolamine and diethanolamine; ethoxylated derivatieves of alkylene poly-6 amine such as hydroxyethyl ethylene diamine and the reaction 7 product of alkylene oxides such as an ethylene oxide or 8 propylene oxide with polyamines, e.g., dinitrilo te~ra-9 ethanol; urea and ureides such as ethylurea.
Carrying out the organo molybdenum complexing 11 reaction in a C5-C50, preferably C8-C18, optimally Cg, 12 alkyl phenol solvent in an amount ranging from about 0.25 13 to 5~ preferably 1, parts by weight of phenol per part by 14 weight of organo molybdenum complex product provides a number of benefits over a reaction without solvent or in 16 a light aromatic solvent such as toluene or a light hy-17 drocarbon oil, e.g.,mineral oil including: a faster re-18 action time; completion of reaction to a stabilized molyb-19 denum complex at a lower temperature; faster and simpler filtration of the reaction product solution; and, a pro-21 duct solution which when added to lubricating oil provides 22 comparable if not enhanced friction reduction (as seen 23 from the subsequent Table I~.
The Cs to C509 preferably C8-C18, alkyl phenols 26 useful a~ solvents for the organo molybdenum complexing 27 reaction are generally the same as the alkyl phenols des-28 cribed to be reactive with a source of sulfur to provide 29 the thio-bis-phenols of FoDmula I. Rather than broadly covering Cl to Cs~ alkyl phenols, the solvent class is 31 broadly limited to Cs to C50 alkyl phenols. Their me~hod 32 of preparation is the same as earlier described and as a 33 class generally commercially available. Described herein 34 as the optimum alkyl phenol is a C8-ClO~ i e ~ C~(average~
alkyl substituted phenol commercially available as ECA
` 36 900 ~ from Exxon Chemical Company of Houston, Texas.
~ 7 _ ',;
.
(37 1 Broadly~ amyl phenol through pentacontanyl phenol are use-2 ful with octyl phenol through octadecyl phenol being pre-3 ferred.
4 The Cs-Cs~ alkyl phenols are usefully present in the hydrocarbon composition i.n an amown~ of from about 6 0.25 to 5, preferably 1, parts by weight per part by 7 weight of the organo molybdenum complex.
9 The Cg-C50 alkyl phenol solutions of the hydro-carbon-soluble organo malybdenum complexes provide en-11 hanced lubricity in lubricating oils when used in combina-12 tion with an active sulfur donor which can be defined as 13 a compound which when used in admix~ure with the organo 14 molybdenum complex reduces the coefficient of friction at least about 10% relative to that provided by the complex 16 alone. The active sulfur donor is present in an amount of 17 from a~out 0.1 to 10, preferably 0.2 to 2, parts by weight 18 per part by weight of molybdenum complex.
19 Illustrative of active sulfur donors are metal dihydrocarbyl dithiophosphates and the corresponding pre-21 cursor esters, phosphosulfurized pinenes9 sulfurized ole-22 finss and hydrocarbons, sulfurized fatty esters and sulfur-23 ized alkyl phenols.
24 Preferred are the zinc dihydrocarbyl dithio-phosphates which are salts of dihydrocarbyl esters of di-26 thiophosphoric acids and may be r~prasented by the follow-27 ing ormula:
28 _ _ 29 RO - P - S Zn OR' 31 _ _ 2 32 wherein R and Rl may be the same or different hydrocarbyl 33 radicals con~aining rom 1 to 18 and preferably 2 to 12 34 carbon atoms cmd ~ncluding radicals such as alkyl~ alkenyl9 aryl, aralkyl, alkaryl and cycloaliphatic radicals. Par-36 ticularly preferred as R and R' groups are alkyl groups ; :
9~
g 1 of 2 to 8 carbon atoms. Thus, t:he readicals may, for 2 example, be ethyl, n~propyl, i~propyl, n-butyl, i-butyl9 3 sec-butyl, tert-butyl9 amyl~ n-hexyl, i-hexyl, n-heptyl) 4 n-octyl~ decyl~ dodecyl, o~tadec:yl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylc:yclopentyl, propenyl, 6 butenyl, etc. In order to obtain oil solubility, the 7 total number of carbon atoms in the dithiophosphoric acid 8 will average abou~ 5 or greater.
9 The zinc dihydrocarbyl dithiophosphates which are useful as coadditive~ i.e., sulfur donor of the present 11 invention9 may be prepared in accordance with known tech-12 niques by first esterifying a dithiophosphoric acid usually 13 by reaction of an alcohol or phenol with P2S5 and then 14 neutralizing the dithiophosphoric acid ester with a suit-able zinc compound such as zinc oxide.
16 In general, ~he zinc dihydrocarbyl dithiophos-17 phate will be used in the lubricating composition at a 18 concentration within the range of about 0.01 to about 5 19 parts by weight per 100 parts of lubricating oil and preferably from abou~ 0.5 to about 1.5. This is adequate 21 ~or sulfur donation whereby the lubricity enhancement of 22 the lubrica~ing oil composition by the coadditive combina-23 tion is realized~
24 As noted earlier~ an equally suitable active sulfur donor is the dihydrocarbyl esters of dithiophos-26 phoric acid which may be represented by the formula:
27 ~ S ~
29 OR' 3~ _ _ 2 31 wherein R and R' are as previously defined. Particularly 32 useful is the dibutylphenyl dithiophosphate.
33 The phosphorosulurized terpenes as represented 34 by pinene~ dipenene, allo-ocimene, etc.~ are another i5 group of dithiophosphate di;sters which are active sulfur ,, . . ~ , 6~7 1 donors. Of the terpenes~ the bicyclic pinene is preferred.
2 The phosphosulfurized terpene is readily obtained by re-3 action of about one mole of diester of thiophosphoric acid 4 and one mole of pinene at a temperature of at least 100C, e.g., 100C.to 200C. The preflerred active sulfur donor 6 can be characterized as the bornyl ester of dihydrocarbyl 7 (C2-C20) dithiophosphoric acids (as shown in U.S. 296899258~.
8 The sulfurized olefins and hydrocarbons are 9 further esters of thiophosphoric acids which are useful sulfur donors. These esters are achieved by reaction wi~h 11 olefins such as ethylene, propylsne~ isobutylene, decene, 12 dodecene, octadecene, etc.; olef;n polymers of molecular 13 weight ranging from 100 to 507000 such as ethylene, 14 propylene, isobutylene, etc.; aromatics such as benzen~, naphthylene, toluene9 xylene, etc.; petroleum fractions 16 and condensation products of halogenated aliphatic hydro-17 carbons with aromatic compounds, e.g., wa~ naphthalene 18 (see U.S. 298047431).
19 The sulfurized fatty esters are another subclass of esters which are active sulfur donors. These products 21 are readily obtained from the reaction of P2S5 and aliphatic 22 alcohols usefully having from about 8 to 22 carbons ob-23 tained from natural sources included linoleic, palmolitic, 24 behenic, stearic, palmiticg lauric, capric, etc., as well as mixtures obtained from vegetable and animal oils such 26 as tall oil.
27 The sulfurized alkyl phenols are generally C4 28 to C20 alkyl phenol sulfides. T~ese sulfurized alkyl 29 phenols are readily produc~d by sulfurizing an alkyl phenol with a sulfur halid~ or elemental sulfur.
32 In addition to the organo molybdenum co~..plex 33 alkyl phenol and active sulfur donor, a lu~ricating oil 34 composition may contain-other well-known lubricating oil additives to provide trouble-free operation of the lubri-36 cated equipment, such as ashless dispersants, metallic , , .' . ' ' ' ~ .
' '' ' ' ' '~ ' ',~ ~' ..,, 1 detergen~s, supplemental oxidation and corrosion inhibitors, 2 extreme pressure agents, rust inhibitors, pour point de-3 pressants, viscosity index improvers, etc.
4 1. ASHLESS DISPERSANTS
As used herein, the terminology "ashless dis-6 persant" is intended to describlP the now well-known class 7 of non-metal-containing oil-soluble poly~eric additives 8 or the acyl derivatives of relatively high molecular 9 weight carboxylic acids which are capable of dispersing contaminants and the like in hydrocarbons such as lubri-11 cating oils. The carboxylic acids may be mono-or poly-12 carboxylic acids and they are generally characterized by 13 substantially hydrocarbon constituents containing an 14 average OL 50 to ?50 aliphatic carbon atoms.
A preferred class of ashless dispersants are 16 the nitrogen-containing dispersant additives which are 17 generally known in the art as sludge dispersants for 18 crankcase motor oils. These dispersants-include mineral 19 oil-soluble salts, amides, imides and esters made from high molecular weight mono-and dicarboxylic acids (and 21 where they exist the corresponding acid anhydrides) and 22 various amines of nitrogen-containing materials having 23 amino nitrogen or heterocyclic nitrogen and at least one 24 amido or hydroxy group capable of salt, amide, imide or ester formation. Usually, these dispersants are made by 26 condensing a monocarboxylic acid or a dicarboxylic acid 27 or anhydride, preferably a succinic acid producing material 28 such as alkenyl succinic anhydride, with an amine or 29 alkylene polyamine. Usually~ the molar ratio of acid or anhydride to amine is be~een 1:1 to 5:1~ e.g., 1 31 mole of C70 to C10O polyisobutenyl succinic anhydride to 32 2 moles of ~etraethylene pentamine.
33 Primarily because of its ready availability and 34 low cost, the hydrocarbon portion of the mono-, or dicar-boxylic acid or anhydride is preerably derived from a 36 polyrner of a C2 to C5 monoolefin9 said polymer generally 37 having between 50 and 250 carbon atoms. A particularly .. . .
. . ~
, ' ~
1 preferred polymer is polyisobutylene.
2 Polyalkyleneamines are usually used to make 3 the non~metal-containing dispersant. These polyalkylene-4 amines include those represented by the general form~tla:
NH2(CH2)n~[NH(CH2)n]m-NH2 6 wherein n is 2 to 3 and m is a number from O to 10.
7 Specific compounds coming within the formula include di-8 ethylene triamine, tetraethylene pentamine, dipropylene-9 triamine, octaethyleneonamine9 and tetrapropylenepentamine;
N,N-di-(2-aminoethyl) ethylenediLamine may also be used.
11 Other aliphatic polyamino compounds that may b2 used are 12 N-amino-al~ylpiperzaines, e.g.g N-(2-aminoethyl) piperazine.
13 Mixtures of alkylene polyamines approximating ~traethylene 14 pentamine are ro~mercially availa~le, e.g., Dow E-100 sold by Dow Chemical Company of Midland, Michigan.
16 Reprasentative dispersants are formed by re-17 acting about one molar amount of polyisobutenyl succinic 18 anhydride with from about one to about two molar amounts 19 of tetrae~hylene pentamine or with from about 0.5 to 1 moles of polyol9 e.g., pentaerthritol.
21 It is possible to modify the ashless dispersants 22 generally by the addition o~ metals such as boron in order 23 to enhance the dispersancy of the additive. This is 24 readily accomplished by adding boric acid to the reaction mixture after the imidation or esterification is substan-26 tially complete and heating the mixture at tempera ures of 27 100 to 150C for a few hours.
28 2. OT~ER ADDITIVES
29 Detergents useful in con~unction with dispersants, preferably the ashless type, include normal, basic or 31 overbased metal, e.g., caLcium, magnesium~ etc., salts 32 of petroleum naphthenic acids, petrnleum sulfonic acids, 33 alkyl benzene sulfonic acids, oil-soluble fatty acids, 34 alkyl salicyclic acids3 alkylene-bi~-phenols, and hydro-lyzed phosphorosulfurized polyolefins.
36 Oxidation inhibitors include hindered phenols, 37 e.g., 2,6-ditert butyl para~cresol amines, sulfurized ~.,;, :
: ~ ' - ' .
.. ~ ' . -' '7 1 phenols and alkyl phenothiazlnes.
2 Pour point depressants include wax alkylated 3 aromatic hydrocarbons, olefin pol~ners and copolymers, 4 acrylate and methacrylate polymers and copolymers.
- Viscosi~y Index Improvers include olefin poly-6 mers such as polybutene, ethylene-propylene copolymers~
7 hydrogenated pol~ners and copol~ers and terpolymers of 8 styrene with isoprene and/or bu~:adiene, polymers of alkyl 9 acrylates or alkyl methacrylate~;, copolymers of alkyl methacrylates with N-vinyl pyrollidone or dimethylamino-11 alkyl methacrylate, post-grafted pol~ners of ethylene-12 propylene with an active monomer such as maleic anhydride 13 which may be further reacted with an alcohol or an alkyl-14 ene polyamine, styrene/maleic anhydride polymers post-reacted ~ith alcohols and amines, etc.
16 The hydrocarbons in which the additive combina-17 tion of the invention is most effective are mineral oils 18 having a viscosity as measured by ASTM D-445 of ~rom about 19 2 to 40, preferably 5 to 20 centistokes at g9C.
If the additive combination of oil-soluble organo 21 molybdenum comple~ C5-C50 alkyl phenol ~nd active sulfur 22 donor are used as an additive concentrate, the concentrate 23 may consist essentially of from about 5 to 95/O of the ad-24 ditive combination, the remainder being an additional hydro-carbon solvent, such as kerosene, mineral oil, a naphtha 26 and the like, or a C5-C50 alkanol.
27 The preferred concentrate contains about 40 to 28 90% of the additive combination in a second solvent of 29 mineral oil.
Whether the organo moly~denum complex-alkyl 31 phenol solution is used alone or in combination with an 32 active sulf~r donor, its concentration may vary appreciably 33 with the part:icular hydrocarbon. For example, when said 34 molybdenum complex-alkyl phenol solution is used alone in a fuel such as gasoline, the concentration of the complex 36 ranges from lV to 1~000, preferably 20 to 50 weight parts 37 per million b~lsed on the total weight of the fuel composition, ~ 3Lg~;07 whereas in a lubricant, it is used in combination with the active sulfur donor, which three-component combination then ranges from about 0.5 to 5, prefera~ly l to 3 wt. ~ based on the total weight of the l~bricating oil.
The invention will be further understood by reference to the following examples which illustrate a preferred form of the invention and compares the same with different~ though similar compositions.
The following examples illustrate more clearly the compo-sitions of the present invention. However, these illustrations are not to be interpreted as specific limitations on this invention.
*
Nonyl phenol sulfide (183 g) as ECA 9001 , Solvent Neutral 150 mineral oil (183 g) and molybdic trioxide (28.1 g) as an undensified grade obtained from Climax Molybdenum Company, Fort Madison, Wisconsin were stirred together and then raised in temperature to 94C at which time ethylene diamine (23.4 g) was thereafter slowly added over a 20-minute period. The temperature was raised with stirring to 121C over 0.6 hour. While stirring at this temperature, the volatiles including water and ammonia were removed by gentle nitrogen sparging for 18 hours. After filtration, the resulting product solution, useful as a lubricat-ing oil additive, had a viscosity of 177 S.U.S. @ 100C and was black in color and contained about 4.3 wt. % molybednum and 1.9 wt. % nitrogen. ECA 9001 , a 70 wt. % active mineral solution of di-(Cg average) nonyl phenol sulfide is commercially available from Exxon Chemical Company, EIouston, Texas.
This is an organo metallic complex prepared according to the teachings of said copending Canadian Application Serial No.
310,503, using a mineral oil solvent for the reaction medium.
Filtration through a steam-heated Buchner funnel holding a ~" pre-coat of Celite 535 took in excess of one hour. Exposure of the product solution to about 150C for 3 hours reduced its nitrogen content to 1.43 wt.
* Trade Mark -- 1~ --~, , 1 and appeared to ~volve ammonia during said three hours.
3 The procedure of Example 1 was followed except 4 that the mineral oil was replaced by: 183 g of nonyl
5 phenol (as ECA 9003, a Cg avera~e) nonyl phenol containing
6 about 62 wt. /O monoalkyl and 33 wt. % dialkyl phenol;
7 use of densified MoO3; going to 177C over a 2-hour p~riod
8 while adding the theylene diamine; and reacting at 177C
9 for 4 hours prior to filtration. The resul~ing filtered
10 product solution (the filtration of which took less than
11 10 seconds to fully filter) analyzed for 4.5 wt.
12 molybdenum.
13 EXAMPLE 3
14 As earlier noted before, a preferred process pro-
15 vides ~r from 6 to 12 hours e~posure of the reaction medium
16 to a temperature of about 175C, usefully 160C to 190C.
17 This is shown in a procedure in which 183 weight parts of A 18 nonyl phenol sulfide (e.g.9 ECA 9001~ are admixed with 183 19 weight parts of nonyl phenol (e.g" ECA 900 ~ and heated 20 toward 105C dur~ng which time 28.1 weight parts of molybdic 21 trioxide are added. When 105C is reached, 23.4 weight 22 parts of ethylene diamine is slowly added over a 30-minute 23 period. Thereafter ra;se the temperature to about 150C
24 and initiate inert gas (e.g., nitrogen~ sparge. Raise 25 to about 175C during the next 2-hour period and heat soak 26 at 175C for about 4 to 6 hours after which it can be 27 readily filtered as shown in Example 2.
28 EXAMPT~ 4 29 A lubricating oil composltion was prepared for 30 comparative testing of additives by blending together the 31 individual components, noted below, usually at a slightly 32 elevated temperature~ i.e., ~rom about 45C to above 65C
33 to insure complete mixing. The final composition of Blend 34 4 formulated into a lOW/30SE quality automotive engine 35 oil was as follows:
1 Blend 4 2 Wt. % Active In~redient 3 Mineral Oil 94.9 4 Ashless Dispersant 2.9 Magnesium Sulfonate 0.2 6 zDDp(l) O 9 7 Rust-Inhibitor 0.1 8 Viscosit~ Index Improvers 1.0 9 Silicone Defoamer 0.01 Ashless Antioxidant ----11 Métal Detergent-Inhibitor ----13 (l)Zinc dihydrocarbyl dithiophosphate such 14 as zinc dinonyl phenol dithiophosphate This formulated blend was itself and in modified 16 forms according to tha teaching of this i~vention subjected 17 to testing as hereinafter set forth:
24 and initiate inert gas (e.g., nitrogen~ sparge. Raise 25 to about 175C during the next 2-hour period and heat soak 26 at 175C for about 4 to 6 hours after which it can be 27 readily filtered as shown in Example 2.
28 EXAMPT~ 4 29 A lubricating oil composltion was prepared for 30 comparative testing of additives by blending together the 31 individual components, noted below, usually at a slightly 32 elevated temperature~ i.e., ~rom about 45C to above 65C
33 to insure complete mixing. The final composition of Blend 34 4 formulated into a lOW/30SE quality automotive engine 35 oil was as follows:
1 Blend 4 2 Wt. % Active In~redient 3 Mineral Oil 94.9 4 Ashless Dispersant 2.9 Magnesium Sulfonate 0.2 6 zDDp(l) O 9 7 Rust-Inhibitor 0.1 8 Viscosit~ Index Improvers 1.0 9 Silicone Defoamer 0.01 Ashless Antioxidant ----11 Métal Detergent-Inhibitor ----13 (l)Zinc dihydrocarbyl dithiophosphate such 14 as zinc dinonyl phenol dithiophosphate This formulated blend was itself and in modified 16 forms according to tha teaching of this i~vention subjected 17 to testing as hereinafter set forth:
18 1. Testing Procedure A
19 The ~oxana Four-ball wear tester with the Brown/&E modification from Roxana Machine Works, St. Louis, 21 MO was used to measure friction properties by the follow-22 ing procedure. The tester was assembled in the normal 23 wear procedure as described in ASTM D2266-67 using four 24 ~" bearing-steel balls. The tester was brought to 110C
and run at 1200 rpm and 15 kg for a minimum of 45 minutes.
26 If the frictional force as seen on the strip chart recorder 27 s constant for the last 10 minutes, the speed is reduced 28 to 25 rpm. Otherwise, the test is carried on until 29 frictional force has stabilized. The test at 25 rpm is carried out at 110C and 15 kg for 15 minutes or until 31 frictional force has stabilized.
32 ~ The compounds of the invention were then :
- - . ~
:; ~ : ..
1 evaluated by subjecting the products to a study of their 2 utility as a lubricity enhancing and/or antiwear additive 3 for lubricating oils by using the Testing Procedure A.
4 ~he weight percentage of amount~; of molybdenum complex added is given in amount of complex added.
6 The results of tes~s ~mder Procedure A are set 7 forth in Table I.
8 From Table I, it is shLown that the additive 9 combination of the invention provides improved lubricity enhancement to lubricating oils wken an active sulfur 11 donor is present and that these combinations have utility 12 as additives for lubricating oils.
13 Another advantage of said alkyl phenol as a 14 solvent for the reaction of the hydrocarbyl phenol sul-fide and molybdenum compownd, preferably molybdic 16 oxide ~MoO3~, resides in the enhanced rea~tivity of the 17 components9 i.e., shorter reaction times and/or more heat 18 stable complexes when such a solvent is used as compared 19 with mineral oil solvent.
.
;- , - ;
:
~C~7 ~, a~
S~ ~ I ~ a~
o ,. ~ ~
u~
E t . I.
c~ c~ r~
.
t) ? ~ 6 r1 0 0 , ~ ~ ,0 0 ,0'' ~_1 ' O ..
~ ~ Ul . ' .
_ ' ';t o~
4~ C~ O O' O
a~
O ~ O O O
V
. ~ C'J 'C'~
I o ' ~ t ~ ~1 C`~
'. ~ .. . .
~ S
O .
:
`
n ~1 C~
:: :
.:
.~ :: :
: :
and run at 1200 rpm and 15 kg for a minimum of 45 minutes.
26 If the frictional force as seen on the strip chart recorder 27 s constant for the last 10 minutes, the speed is reduced 28 to 25 rpm. Otherwise, the test is carried on until 29 frictional force has stabilized. The test at 25 rpm is carried out at 110C and 15 kg for 15 minutes or until 31 frictional force has stabilized.
32 ~ The compounds of the invention were then :
- - . ~
:; ~ : ..
1 evaluated by subjecting the products to a study of their 2 utility as a lubricity enhancing and/or antiwear additive 3 for lubricating oils by using the Testing Procedure A.
4 ~he weight percentage of amount~; of molybdenum complex added is given in amount of complex added.
6 The results of tes~s ~mder Procedure A are set 7 forth in Table I.
8 From Table I, it is shLown that the additive 9 combination of the invention provides improved lubricity enhancement to lubricating oils wken an active sulfur 11 donor is present and that these combinations have utility 12 as additives for lubricating oils.
13 Another advantage of said alkyl phenol as a 14 solvent for the reaction of the hydrocarbyl phenol sul-fide and molybdenum compownd, preferably molybdic 16 oxide ~MoO3~, resides in the enhanced rea~tivity of the 17 components9 i.e., shorter reaction times and/or more heat 18 stable complexes when such a solvent is used as compared 19 with mineral oil solvent.
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Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a concentrate consisting essentially of one part by weight of an organo molybdenum complex ob-tained from a solution reaction of 1-2 moles of a C1 to C50 hydrocarbyl-substituted thio-bis-phenol, 1-2 moles of an amine containing from 1 to 5 nitrogens and from 2 to 20 carbons and 1 molar equivalent of a source of molyb-denum of the class consisting of molybdic trioxide, ammonium thiomolybdate, ammonium bismolybdate, molybdenum halides and ammonium heptamolybdate tetrahydrate, the improvement of using from 0.25 to 5 parts by weight of an alkyl-substituted phenol wherein said alkyl group contains from 5 to 50 carbons for said reaction solvent which is carried out at a temperature of from 135°C to 225°C whereby a more readily filterable reaction product is obtained.
2. A concentrate according to claim 17 wherein said complex is obtained as the product of a hydrocarbyl-substituted thio-bis-phenol reacted with about 0.5 molar equivalent of molybdic trioxide and one mole of an amine selected from the class of C6-C30 alkylamine, alkylene polyamines and their ethoxylated derivatives, alkanolamine, urea and ureides and dissolved in from 0.25 to 5 parts by weight of a C5-C50 alkyl-substituted phenol solvent per part by weight of said product.
3. A concentrate according to claim 1, wherein said alkyl substituent contains from 8 to 18 carbons, said temperature is from 160°C to 190°C and the reaction is carried out over a period of from 4 to 20 hours.
4. A concentrate according to claims 1-3 wherein said thio-bis-phenol is nonyl phenol sulfide, said molybdenum source is molybdic trioxide, said amine is ethylene-diamine and said phenol solvent is nonyl phenol present in an amount of about 1 part by weight.
5. A concentrate according to claims 1-3 diluted with mineral oil in an amount of up to about the weight of said phenol solvent.
6. A hydrocarbon composition comprising a major portion of a hydrocarbon and at least a friction reducing amount of the combination of: (a) an organo molybdenum complex obtained from an alkanol solution reaction of 1-2 moles of a C4 to C50 hydrocarbyl substituted thio-bis-phenol, 1-2 moles of an amine reactant containing from 1 to 5 nitrogens and from 2 to 20 carbons and 1 molar equiva-lent of a source of molybdenum of the class consisting of molybdic trioxide, ammonium thiomolybdate, ammonium bis-molybdate, molybdenum halides and ammonium heptamolybdate tetrahydrate;
(b) an oil-soluble active sulfur donor; and from 0.25 to 5 parts by weight of a C5-C50 alkyl substituted phenol per part by weight of said complex, said combination providing from about 0.005 to 0.2 weight percent molybdenum and said sulfur donor being present in at least 0.25 weight percent, all of said weight percent being based on the total weight of said composition.
(b) an oil-soluble active sulfur donor; and from 0.25 to 5 parts by weight of a C5-C50 alkyl substituted phenol per part by weight of said complex, said combination providing from about 0.005 to 0.2 weight percent molybdenum and said sulfur donor being present in at least 0.25 weight percent, all of said weight percent being based on the total weight of said composition.
7. A hydrocarbon composition according to claim 6 wherein said hydrocarbon is mineral oil, said organo complex is an oil-soluble reaction product of a hydrocarbyl substituted thio-bis-phenol with about 0.5 molar equivalent of said molybdenum source and one mole of ethylene diamine, said sulfur donor is an oil-soluble dihydrocarbyl ester of dithiophosphoric acid and the alkyl group of said phenol contains 8 to 18 carbons.
8. A hydrocarbon composition according to claims 6 or 7 wherein said mineral oil has a viscosity as measured by ASTM D-445 of about from 2-40 centistokes at 99°C, said thio-bis-phenol is nonyl phenol sulfide, said molybdenum source is molybdic trioxide, said active sulfur donor is zinc dihydrocarbyl dithiophosphate present in an amount of from 0.2-2 parts by weight per part by weight of molybdenum complex and said phenol is nonyl phenol.
9. A gasoline composition comprising gasoline containing from 10 to 1,000 parts per million based on the total weight of the gasoline composition of a molybdenum complex-phenol solution obtained from an alkyl phenol solution reaction of a C1 to C50 hydrocarbyl substituted thio-bis-phenol with about 0.5 molar equivalent of a molyb-denum source of the class consisting of molybdic trioxide, ammonium thiomolybdate, ammonium bismolybdate, molybdenum halides, and ammonium heptamolybdate tetrahydrate and one mole of an amine containing from 1 to 5 nitrogens and from 2 to 20 carbons while dissolved in from 0.25 to 5 parts by weight of a C5-C50 alkyl substituted phenol solvent per part by weight of said complex.
10. A method of preparing an organo molybdenum complex containing from about 0.5 to 5 wt. % nitrogen com-prising the steps of reacting a C1 to C50 hydrocarbyl substituted thio-bis-phenol with about 0.5 molar equivalent of a molybdenum source of the class consisting of molybdic trioxide, ammonium thiomolybdate, ammonium bismolybdate, molybdenum halides and ammonium heptamolybdate tetrahydrate and one mole of an amine containing from 1 to 5 nitrogens and from 2 to 20 carbons, while dissolved in from 0 to 5 parts by-weight of an C5-C50 alkyl substituted phenol solvent per part by weight of said product at a temperature of from about 145°C to 225°C for about 4 to 20 hours.
11. The method of claim 10 wherein said time of reaction is from 6 to 12 hours and at a temperature of about 160°C to 190°C.
12. The method of claim 10 wherein said thio-bis-phenol is nonyl phenol sulfide, said alkyl phenol is nonyl phenol and said amine is ethylene diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000336907A CA1119607A (en) | 1979-10-03 | 1979-10-03 | Alkyl phenol solutions of organo molybdenum complexes as friction reducing anitwear additives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000336907A CA1119607A (en) | 1979-10-03 | 1979-10-03 | Alkyl phenol solutions of organo molybdenum complexes as friction reducing anitwear additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1119607A true CA1119607A (en) | 1982-03-09 |
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ID=4115275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336907A Expired CA1119607A (en) | 1979-10-03 | 1979-10-03 | Alkyl phenol solutions of organo molybdenum complexes as friction reducing anitwear additives |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1119607A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960660A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Gasoline engine lubricating oil composition and preparation method thereof |
-
1979
- 1979-10-03 CA CA000336907A patent/CA1119607A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960660A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Gasoline engine lubricating oil composition and preparation method thereof |
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