GB2442841A

GB2442841A - Anti-oxidants from reaction of a polyacrylate, hindered phenol & amino-substituted diarylamine, & optionally an alk(en)yl amine, for use in lubrication oils

Info

Publication number: GB2442841A
Application number: GB0718303A
Authority: GB
Inventors: Naresh C Mathur
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2006-10-12
Filing date: 2007-09-19
Publication date: 2008-04-16
Anticipated expiration: 2027-09-19
Also published as: FR2907450B1; FR2907450A1; GB2442841B; DE102007045657A1; US20080090742A1; GB0718303D0

Abstract

Compounds that are the reaction product of (i) a "polyacrylate", (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an "alkyl" amine (where "alkyl" is an optionally olefinically unsaturated alkyl group), may be used as anti-oxidants in lubrication oils and formulated with a diluent as an additive for such oils. They may also be used as anti-knocking agents, for improving/maintaining viscosity, or for reducing discoloration or sludge/deposit formation in fuel compositions or plastics. A preferred product is: <EMI ID=1.1 HE=35 WI=91 LX=369 LY=349 TI=CF> <PC>where <SL> <LI>(i) H-Y-R<1>(-Y-H)-Y-H constitutes a "polyacrylate" of formula: <EMI ID=1.2 HE=11 WI=45 LX=623 LY=941 TI=CF> wherein: <DL TSIZE=7> <DT>q<DD>is 3; <DT>R<2> is<DD>H or methyl; <DT>and R1<DD>is a q-valent aliphatic (which optionally includes heteroatoms such as O) or aromatic group, </DL> <LI>(ii) <EMI ID=1.3 HE=26 WI=40 LX=620 LY=1328 TI=CF> constitutes the hindered phenol, wherein: one of R<3> and R<4> is H or C1-12 alkyl, and the other of R<3> and R<4> is a branched C3-12 alkyl; <LI>(iii) H-'R<5>-Ar-NH-Ar' constitutes the diaryldiamine, wherein: <DL TSIZE=12> <DT>'R<5><DD>is an amine-containing substituent; and <DT>Ar and Ar'<DD>are optionally substituted aryl groups; </DL> <LI>and (iv) R<6>-NH-R<7> constitutes the "alkyl" amine, wherein: <DL TSIZE=10> <DT>R<6> and R<7><DD>are optionally olefinically unsaturated alkyl groups. </DL> </SL>

Description

InteUectual DP oerty C ce::c:cJ:] Fc Cr.oiindn and iuoatn,n Application

No. GBO7 18303.1 RTM DaIc:17 January 2008 The following terms are registered trademarks and should be read as such wherever they occur in this document:

CELITE

UK Intellectual Property Office is art operating name of the Patent Office A 1)1: SERViCE

A COMPOUND AND METHOD OF MAKING THE COMPOUND

DESCRIPTION OF THE DISCLOSURE

Field of the Disclosure

1] The present application is directed to novel compounds, processes for making the compounds, and compositions that comprise the compounds.

Backaround of the Disclosure

(0002] Lubricating oils as used in the internal combustion engines and transmissions of automobiles or trucks are subjected to a demanding environment during use. This environment results in the oil suffering oxidation which is catalyzed by the presence of impurities in the oil, such as iron compounds, and is also promoted by the elevated temperatures of the oil during use.

(0003] The oxidation of lubricating oils during use is often controlled to some extent by the use of antioxidant additives. Antioxidant additives can extend the useful life of the lubricating oil by, for example, reducing or preventing unacceptable viscosity increases.

4] A combination of antioxidants are often employed in lubricants. One such combination includes both hindered phenol compounds and alkylated diphenylamines as antioxidants. These antioxidants are believed to work synergistically by converting relatively reactive alkoxy and/or aikyl radicals to less reactive phenoxy radicals.

SUMMARY OF THE DISCLOSURE

5] In accordance with the disclosure, one aspect of the present application is directed to a compound that is the reaction product of (i) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.

6] Another aspect of the present application is directed to a compound of formula V, 0HY_R1_Y_R5-Ar--A V R6 fl7 where V is a group having a formula VI, 0 R u i H2 VI -0-c--c-c -I-f R1 is an aliphatic or aromatic group, R2 is hydrogen or methyl, A3 and R4 are independently chosen from hydrogen or a linear or branched Ci to C,2 alkyl group, with the proviso that at least one of A3 and A4 is a branched C3 to C12 alkyl group, R5 is a secondary amine substituent, A8 and R7 are independently chosen from saturated or olefinically unsaturated aliphatic alkyl groups, and Ar and Ar' are groups independently chosen from substituted or unsubtituted aryl groups having from 6 to 50 carbon atoms.

(0007] Another aspect of the present application is directed to a process for forming a first compound, the process comprising combining (i) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.

8] Another aspect of the present application is directed to a lubricant composition. The composition comprises a base oil; and a first compound that is the reaction product of (I) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.

9] Another aspect of the present application is directed to an additive package. The additive package comprises a diluent; and a first compound that is the reaction product of (i) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.

[00101 Another aspect of the present application is directed to a method for reducing the oxidation of a lubricating oil. The method comprising placing in the crankcase of an internal combustion engine a lubricating composition of the present application.

1] Additional aspects and advantages of the disclosure will be set forth in part in the description which follows, and can be learned by practice of the disclosure. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not

restrictive of the disclosure, as claimed.

DESCRIPTION OF THE EMBODIMENTS

LOOl 2] The present application is directed to compounds prepared by reacting (i) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine. In some aspects of the present application, the resulting compounds comprise both a hindered phenol functional group and a diaryldiamine functional group. The plurality of functional groups of the compounds of the present application may result in useful properties, such as, for example, compounds having good antioxidant function and/or other capabilities, as described In more detail below.

(0013] Representative examples of suitable polyacrylates used to form the compounds of the present application include, but are not limited to, compounds of the formula I, 0 A2 A' (OiCH2)q wherein R' is an aliphatic group or aromatic group, A2 is hydrogen or methyl and q is an integer from about 2 to about 4. Non-limiting examples of a polyacrylate suitable for use herein include trimethylolpropane triacrylate (TMPTA), hydroquinone diacrylate, hydroquinone dimethacrylate, pyrogallol diacrylate, pyrogallol dimethacrylate, pyrogallol triacrylate, resorcinol diacrylate, resorcinol dimethacrylate, glycol diacrylate, glycol dimethacrylate, glycerol diacrylate, glycerol trimethacrylate, 1,1,1 -trimethylol ethane triacrylate, glucose polyacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, propyleneglycol diacrylate and the like.

(0014] Suitable hindered phenols for use in the present application include compounds of formula II,

OH

wherein R3 and A4 can be independently chosen from, for example, hydrogen or a linear or branched C, to C12 alkyl group, with the proviso that at least one of A3 and R4 is a branched C3 to C,2 alkyl group. Non-limiting examples of suitable phenols include compounds chosen from 2-tert-butylphenol; 2,6-ditert-butylphenol; 2- isopropyiphenol; 2,6-diisopropylphenol; 2-sec-butylphenol; 2,6 di-sec-butylphenol; 2-tert-hexyiphenol; 2,6-ditert-hexyiphenol; 2-tert-butyl-o-cresol; 2-tert-dodecylphenol; 2-tert-decyl-o-cresol and 2-tert-butyl-6-isopropytphenol. In one embodiment, the hindered phenol is 2,6 di-tert-butylphenol.

(00151 Suitable diaryldiamines for use in forming the compounds of the present application include reactant compounds of the formula Ill, R-Ar-Ar Ill wherein Ar and Ar' each independently represent a substituted or unsubtituted aryl group having from about 6 to about 50 carbon atoms; and wherein A5 is an amine substituent. Non-limiting examples of suitable amines include primary amine substituents such as NH2, 4NH(CH2)n]mNH2, (CH2)NH2, and -CH2-aryl-NH2 in which n is an integer ranging from about 1 to about 20, such as from about 1 to about 10, or in another embodiment, from about 2 to about 4; and m is an integer having a value of from about 1 to about 20, such as from about 2 to about 10.. Non-limiting examples of other substituents that can also be bonded to Ar and Ar' in addition to the R5 substituent include one or more additional primary amine substituents, such as those listed above for A5; aliphatic hydrocarbon groups, such as alkyl groups having from about 1 to about 20 carbon atoms; hydroxyl; carboxyl and nitro groups. In some embodiments, both Ar and Ar' can be phenyl groups. For example, the diaryldiamine can be an N-phenylphenylenediamine (NPPDA), such as N-phenyl-1,3-phenylenediamine, N-phenyl-1, 2-phenylenediamine and N-phenyl-1,4-phenylened lam me.

(0016] Any suitable alkyl amines can optionally be included as reactants in the present application. When included, the alkyl amines can provide increased solubility of the resulting compounds. In some embodiments, suitable alkyl amines can include secondary amines of formula IV, Re_I A7 IV where R6 and A7 are independently chosen, saturated or olefinically unsaturated aliphatic alkyl groups. For example, A and A7 can be C1 -C alkyl groups. Representative examples of such secondary amines include, but are not limited to, di-iso-amylam me, di-n-octylamine, di-(2ethylhexyl)amine, di-(tert-octyl)amine, di-n-nonylamine, dilauryl amine, di-hexadecylamine, di-octadecylam me, and di-oleylamine. In some embodiments, primary amines can be employed, such as n-octyf amine, 2-ethyihexylammne, tert-octylamine, n-decylamine, n-undecylamine, lau ryl amine, hexadecylamine, heptadecylam me, octadecylamine, decenylam me, dodecenylam me, palmitoleylamine, oleylamine, linoleylamine, and eicosenylam me.

(0017] The above described reactant compounds can be employed to produce the product compounds of the present application. The product compounds of the present application can be compounds of general formula V. OHYR-Y-'R-Ar--A V R8 A7 where Y is the acrylate or methacrylate group of the polyacrylate of formula I above, the V group having a formula VI, o R2 ii H VI -0-c-c-c -

H

and where A5 is an amine formed by bonding the R5 amine with a V group of the polyacrylate of formula I, and R', A2, A3, A4, A6, A7, Ar and Ar' are defined as set forth above. Suitable examples of A5 amine substituents include -NH-, -[NH(CH2)- ]mNH, -(CH2)-NH-, and -CH2-aryl-NH-in which n and m are as defined above.

(0018] In one embodiment, the product compound can have the formula VII, H3C CH3 C2H5 HO*rcYN H3C...C

VII

H3C CH3 where Y, A6 and A7 are defined as above.

9] The process of reacting the reactant compounds described above can be performed in any suitable manner which will produce the desired product compounds of the present application. During the reaction, the vinyl group double bonds of the polyacrylate can react with the hindered phenol, diaryldiamine and the alkyl amine reactant compounds to form the desired product compounds.

(0020] Any suitable concentrations of the above reactant compounds can be mixed together and reacted under suitable conditions that will result in the compounds of the present application. For example, reactants can be combined in ratios ranging from about a 1:x:y:z molar ratio of polyacrylate, hindered phenol, diaryldiamine and alkyl amine, where x and y can range from about 1 to about 4; and z can range from 0 to about 2. Suitable reaction temperatures and concentrations of reactants employed in forming the compounds of the present application can be determined by one of ordinary skill in the art.

[0021) In one embodiment, the process can include mixing suitable amounts of all the ingredients, including the polyacrylate, hindered phenol, diaryldiamine and the alkyl amine reactant compounds under conditions which result in a reaction to form the desired product compounds. in other embodiments, the reactant compounds can be reacted in a stepwise manner.

2] In stepwise reaction processes, the diaryldiamine, hindered phenol, and alkyl amine can be combined with the polyacrylate in any order to form the product of Formula V, as illustrated below. For example, the polyacrylate can be reacted with the diaryldiamine to form a first intermediate product; followed by providing and reacting the hindered phenol with the first intermediate product to form a second intermediate product; and then combining and reacting the alkyl amine with the second intermediate product to form the final product of formula V above. In another example, the polyacrylate can be reacted with the alkyl amine to form a first intermediate product; followed by combining and reacting the hindered phenol with the first intermediate product to form a second intermediate product; and then combining and reacting the diaryldiamine with the second intermediate product to form the final product of formula V above.

(00233 The compounds of the present application may have many uses. For example, the compounds may be useful as antioxidants, anti-knocking agents, and/or as performance enhanced additives useful for improving or maintaining viscosity, or reducing discoloration and/or sludge or deposit formation in a variety of formulations, such as lubricant compositions, fuel compositions, or plastics. Other related applications may also be readily apparent to one of ordinary skill in the art.

(0024] The lubricating compositions disclosed herein can comprise a base oil.

Base oils suitable for use in formulating the disclosed compositions can be selected from, for example, synthetic or mineral oils, or mixtures thereof.

5]The base oil can be present in a major amount, wherein "major amount" is understood to mean greater than or equal to 50% by weight of the lubricant composition, such as from about 80% to about 98% by weight of the lubricant composition. The base oil typically has a viscosity of, for example, from about 2 to about 15 cSt and, as a further example, from about 2 to about 10 cSt at 100 C.

6] Non-limiting examples of mineral oils suitable as base oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as other mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinlc-naphthentc types. Oils derived from coal or shale are also suitable. Further, oils derived from a gas-to-liquid process are

also suitable.

7] Non-limiting examples of synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olef ins (e.g., polybutytenes, polypropylenes, propylene isobutylene copolymers, etc.); polyaiphaolefins such as poly( 1 -hexenes), poly-(1-octenes), poly(1-decenes), etc. and mixtures thereof; aikylbenzenes (e.g., dodecylbenzenes, tetradecy$benzenes, di-nonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyl, aikylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl suif ides and the derivatives, analogs and homologs thereof and the like.

(0028] Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic oils that can be used. Such oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono-and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C38 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.

(0029] Another class of synthetic oils that can be used includes the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyt malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Specific examples of these esters include dibutyl adipate, dl(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthatate, didecyl phthatate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyihexanoic acid and the like.

(0030] Esters useful as synthetic oils also include those made from C5.12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaeiythritol, dipentaerythritol, tripentaerythritol, etc. [0031]Hence, the base oil used to make the compositions as described herein can be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Such base oil groups are as follows: [0032] Group I contain less than 90% saturates and/or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120; Group Il contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120; Group Ill contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120; Group IV are polyalphaolef ins (PAO); and Group V include all other basestocks not included in Group I, II, lii or IV.

(0033] The test methods used in defining the above groups are ASTM 02007 for saturates; ASTM D2270 for viscosity index; and one of ASTM 02622, 4294, 4927 and 3120 for sulfur.

4] Group IV basestocks, i.e. polyalphaolefins (PAO) include hydrogenated oligomers of an alpha-olefin, the most important methods of oligomerisation being free radical processes, Ziegler catalysis, and cationic, Friedel-Crafts catalysis.

[0035) The polyalphaolef ins typically have viscosities in the range of 2 to 100 cSt at 100 C., for example 4 to 8 cSt at 100 C. They can, for example, be oligomers of branched or straight chain alpha-olef ins having from about 2 to about 30 carbon atoms; non-limiting examples include polypropenes, polyisobutenes, poly-1 -butenes, poly-1-hexenes, poly-1-octenes and poly-1-decene. Included are homopolymers, interpolymers and mixtures. *11

(0036] Regarding the balance of the basestock referred to above, a "Group I basestock" also includes a Group I basestock with which basestock(s) from one or more other groups can be admixed, provided that the resulting admixture has characteristics falling within those specified above for Group I basestocks.

(0037] Exemplary basestocks include Group I basestocks and mixtures of Group II basestocks with Group I basestock.

(0038] Basestocks suitable for use herein can be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, otigomerisation, esterification, and re-refining.

(0039] The base oil can be an oil derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons can be made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as the base oil.

For example, the hydrocarbons can be hydroisomerized using processes disclosed in U.S. Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using processes disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using processes disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed using processes disclosed in U.S. Pat. No.6,013,171; 6,080,301; or 6,165,949.

(0040]Unrefined, refined and rerefined oils, either mineral or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the base oils. Unrefined oils are those obtained directly from a mineral or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to obtain refined oils, where the processes are applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.

(0041] The lubricant compositions of the present application can be used in any engine or other combustion systems or mechanical devices that may benefit therefrom. For example, the lubricant compositions can be suitable for use in the crank case of an internal combustion engine.

2] The product compounds of the present application can be included in a lubricant composition in an amount sufficient to improve the antioxidant property of the lubricant. For example, an amount ranging from about 0.05 to about 10 weight percent, such as from about 0.1 to about 4 weight percent, relative to the total amount of the lubricant composition is usually sufficient.

(0043] In some embodiments, the compounds of the present application can be added to the oil in the form of a concentrate additive composition. These are concentrates dissolved in a diluent, such as mineral oil, synthetic hydrocarbon oils, and mixtures thereof. When combined to the base oil, the concentrate additive composition can provide an effective concentration of the additives in the base oil.

The amount of the compounds of the present application in the additive package can vary from about 5 wI % to about 75 wt % of the additive composition, such as from about 10 wt % to about 50 wt.

4] The additive composition and finished lubricant composition of the present application can contain other additional additives. Examples of such additional additives include dispersants, detergents, anti-wear agents, supplemental antioxidants, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors, anti-swell agents and friction modifiers. Such additives are well known in the art, and choosing effective amounts of additional additives in lubricant compositions would be within the ordinary skill of the art.

(0045] The following examples are presented to illustrate the manner in which the additives of the invention can be prepared and are not to be considered as limiting as to any aspect thereof.

EXAMPLES

Example 1: Method of Making a Com ound (0046] An exemplary process for making an compound of the present application was carried out as follows: (0047] Step 1: A 1 -liter 4-neck flask equipped with nitrogen sub-surface was charged with 236.8g of trimethylolpropane triacrylate (TMPTA), 300g methanol, and 0.8g of laural mercaptan. To this solution 1 92.8g of bis(2-ethylhexylamine) was added dropwise over 4 hr period and then allowed to stir at room temperature for 3 hrs. The temperature was then raised to 65 C to distill methanol and finally vacuum stripped and filtered over Celite. A total of approximately 424g of product was isolated. %N = 2.74% (0048] Step 2: A 500 mL flask was charged with 1 49g of process oil, 64g of 2,6-di-tert butyiphenol and 1 g of potassium hydroxide. The mixture was heated to about 1200 C and then mild vacuum was applied to remove about 1.3 ml of distillate.

Vacuum was removed and the mixture was then heated to 140 C. 161g of the * product isolated from step 1 was then added dropwise over a 2-3 hr period. After the addition was complete, the reaction was held at 140 C for 3 hrs and 8g of talc was added and stirred for 30 mm. The mixture was then filtered over Celite. A total of approximately 235g of product was obtained. %N = 1.27; TBN = 47.2 (00491 Step 3: 1 27.3g of the product obtained from step 2 and 240 ml of butanol were charged to a 500 ml flask and equipped with nitrogen sub-surface and condenser. The mixture was heated to about 80 C and 9.2g of N-phenyiphenylenediamine (NPPDA) was added all at once. The temperature was raised to 120 C and held for approximately 10 hrs. Butanol was removed under vacuum. The product thus obtained was diluted with 34.7g of process oil, allowed to cool to room temperature overnight and then filtered over Celite. %N = 1.43; TBN = 47. The resulting product was tested as an antioxidant as descnbed in Example 3 below.

Examole 2: Method of Making an Compound [0050] Another exemplary process for making a compound of the present application was carried out as follows: (0051] A 500 ml flask was charged with 74g of TMPTA and 240g of butanol.

The flask was equipped with nitrogen sub-surface and reflux condenser and heated to about 80 C. 46g of NPPDA was added in portions over 30 mm and the mixture was then heated to reflux for 8 hrs. 51.5g of 2,6-di-tert butylphenol and 0.7g potassium hydroxide were added and the mixture was again held at ref tux for 7 hrs.

The reflux condenser was replaced with a distillation apparatus and the mixture was heated to 145 C, during which almost 200 ml butanol was removed. The mixture was cooled to 65 C and 60.3g of bis(2-ethylhexyl)amine was added dropwise over a 2 hr period. The mixture was held at 650 C for 3 hrs and then vacuum stripped.

7g of talc was added and stirred for 30 minutes, followed by filteration through paper to remove solids. The filtered product had 4. 22% N and had a TBN of 131.

Examole 3: Evaluation of Engine Oils containing the compound of Example 1 in the Thermo-Oxidation Engine Oil Simulation Test (TEOST MHT-4) (0052] The TEOST MHT-4 is a standard lubricant industry test for the evaluation of the oxidation and carbonaceous deposit-forming characteristics of engine oils. The test is designed to simulate high temperature deposit formation in the piston ring belt area of modern engines. The test utilizes a patented instrument (U.S. Pat. No. 5,401,661 and U.S. Pat. No. 5,287,731; the disclosure of each patent is hereby incorporated by reference in its entirety) with the MHT-4 protocol being a relatively new modification to the test. Details of the test operation and specific MHT-4 conditions have been published by Selby and Florkowski (Selby et al.) in a paper entitled, "The Development of the TEOST Protocol MHT as a Bench Test of Engine Oil Piston Deposit Tendency" presented at the 12th International Colloquium Technische Akademie Esslingen, January 11-13, 2000, Wilfried J. Bartz editor. The Selby et al. paper is hereby incorporated by reference in its entirety.

(0053] Oil Blends A, B, and C were evaluated using the TEOST MHT-4 with the results shown in the attached Table 1. Blend A was the baseline to which 0.5 and 1 wt% of the compound of Example 1 were combined to make blends B and C, respectively.

TABLE 1

Blend A Blend B 1 Blend C Core Pack "A" of 90 90 I additives ___________ ____________ _____________ Alkylated 0.8 0.8 0.8 diphenylamines ___________ _____________ _____________ Compound of 0 0.5 1.0 Example_1 ___________ ____________ ____________ Motiva 5cst base 9.2 8.7 8.2 stock ___________ _____________ _____________ Total wt% 100 100 100 TEOST (MHT-4), 38 23.7 16 mg ________ _________ _________ [00541 As shown in Table I above, blends B and C showed lower deposits (in mg) than blend A. These results demonstrate improved antioxidant performance from the compound of Example 1, as compared with blend A, which did not contain a compound of the present application.

(0055] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

(0056] It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the," include plural referentsunless expressly and unequivocally limited to one referent. Thus, for example, reference to "an acid" includes two or more different acids. As used herein, the term "include" and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.

(0057] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art.

Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMS: 1. A compound that is the reaction product of (i) a

polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.
2. The compound of claim 1, wherein the polyacrylate is a compound of the formula I, 0 R A' (OCH2)q where A' is an aliphatic or aromatic group, A2 is hydrogen or methyl and q is an integer from about 2 to about 4.
3. The compound of claim 1, wherein the polyacrylate is a compound chosen from trimethylolpropane triacrylate (TMPTA), hydroquinone diacrylate, hydroquinone dimethacrylate, pyrogallol diacrylate, pyrogallol dimethacrylate, pyrogallol triacrylate, resorcinol diacrylate, resorcinol dimethacrylate, glycol diacrytate, glycol dimethacrylate, glycerol diacrylate, glycerol trimethacrylate, 1,1,1-trimethylol ethane triacrylate, glucose polyacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, and propyleneglycol diacrylate.
4. The compound of any of claims 1 to 3, wherein the hindered phenol is a compound of the formula II,

OH A3

II

where A3 and A4 are independently chosen from hydrogen or a linear or branched Ci to C12 alkyl group, with the proviso that at least one of A3 and A4 is a branched C3 to C12 alkyl group.
5. The compound of any of claims 1 to 3, whereIn the hindered phenol is a compound chosen from 2-tert-butyiphenol; 2,6-ditert-butylphenol; 2-isopropylphenol; 2,6-diisopropylphenol; 2-sec-butylphenol; 2,6 di-sec-butytphenol; 2-tert-hexyiphenol; 2,6-ditert-hexyiphenol; 2-tert-butyl-o-cresol; 2-tert-dodecyiphenol; 2-tert-decyl-o-cresol and 2-tert-butyl-6-isopropylphenol.
6. The compound of any of claims 1 to 3, wherein the hindered phenol is 2,6 di-tert butyl phenol.
7. The compound of any of claims 1 to 6, wherein the diaryldiamine is a compound of the formula Ill, R-Ar-Ill where Ar and Ar' each independently represent a substituted or unsubtituted aryl group having from about 6 to about 50 carbon atoms; and
8. The compound of claim 7, wherein A5 is a substituent chosen from -NH2, [NH(CH2)n)mNH2, -(CH2)NH2, and -CH2-aryl-NH2, in which n and m are each an integer having a value of from about 1 to about 10.
9. The compound of claim 7 or claim 8, wherein at least one of Ar and Ar' is substituted with one or more substituents in addition to A5, the one or more additional subtituents being chosen from primary amine substituents, aliphatic hydrocarbon groups, hydroxyl groups, carboxyl groups, and nitro groups.
10. The compound of any of claims 7 to 9, wherein Ar and Ar' are phenyl groups.
11. The compound of any of claims 1 to 10, wherein the diaryldiamine is a compound chosen from N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine, and N-phenyl-1,4-phenylenediamine.
12. The compound of any of claims 1 to 11, wherein the compound is the reaction product of (I), (ii), (iii) and (iv), the alkyl amine being a compound of the formula IV,

H

R -N IV where A and A7 are substituents independently chosen from hydrogen and saturated or olefinically unsaturated aliphatic alkyl groups, with the proviso that at least one of R8 and A7 is not hydrogen.
13. The compound of any of claims 1 to 11, wherein the compound is the reaction product of (i), (ii), (iii) and (iv), the alkyl amine being a compound chosen from di-iso-amylamine, di-n-octylamine, di-(2ethylhexyl)amine, di-(tert-octyl)amine, di-n-nonylamine, dilauryl amine, di-hexadecylamine, di-octadecylamine, di-oleylamine; n-octylamine, 2-ethyihexylamine, tert-octylamine, n-decylamine, n undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecytamine, decenylamine, dodecenylamine, palmitoleylam ne, oleylamine, linoleylamine, and eicosenylamine..
14. A compound of formula V, OHY_R1_Y_tR5_Ar__Ar V A6 A7 where V is a group having a formula VI, II I 2 VI -0-c--c-c -

H

A' is an aliphatic or aromatic group, A2 is hydrogen or methyl, A3 and A4 are independently chosen from hydrogen or a linear or branched C, to C12 alkyl group, with the proviso that at least one of A3 and A4 is a branched C3 to C,2 alkyl group, A5 is a secondary amine substituent; A6 and A7 are independently chosen from saturated or olefinically unsaturated aliphatic alkyl groups, and Ar and Ar' are groups independently chosen from substituted or unsubtituted aryl groups having from 6 to 50 carbon atoms.
15. A process for forming a first compound, the process comprising combining (I) a polyacrylate, (ii) a hindered phenol, (iii)a diaryldiamine and optionally (iv) an alkyl amine.
16. The process of claim 15, wherein: the polyacrylate is a compound of the formula I, 0R2 R' (0CCCH2)q where R1 is an aliphatic or aromatic group, A2 is hydrogen or methyl and q is an integer from 2 to 4; the hindered phenol is a compound of the formula Il,

OH A3

II

where A3 and A4 are independently chosen from hydrogen or a linear or branched C1 to C12 alkyl group, with the proviso that at least one of A3 and A4 is a branched C3 to C,2 alkyl group; and the diaryldiamine is a compound of the formula Ill,

H

R5-Ar----N Ar' Ill where Ar and Ar' each independently represent a substituted or unsubtituted aryl group having from 6 to 50 carbon atoms, and R5 is an amine substituent.
17. The process of claim 16, wherein the first compound is prepared by combining the alkyl amine with (i), (ii) and (iii), the alkyl amine being a compound of the formula IV, R6_F!J fl7 IV where A6 and A7 are substituents independently chosen from hydrogen and saturated or oletinically unsaturated aliphatic alkyl groups, with the proviso that at least one of A6 and A7 is not hydrogen.
18. A lubricant composition comprising: a base oil; and a first compound that is the reaction product of (I) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.
19. The lubricant composition of claim 18, wherein the concentration of the compound ranges from about 0.05 wt % to about 10 wt % of the lubricant composition.
20. The lubricant composition of claim 18 or claim 19, further comprising one or more additional additives chosen from dispersants, detergents, anti-wear agents, supplemental antioxidants, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors, anti-swell agents and friction modifiers.
21. The lubricant of any of claims 18 to 20, wherein: the polyacrylate is a compound of the formula I, 0 R R' (O!CH2)q where A1 is an aliphatic or aromatic group, A2 is hydrogen or methyl and q is an integer from about 2 to about 4; the hindered phenol is a compound of the formula II,

OH A3

II

where B3 and A4 are independently chosen from hydrogen or a linear or branched C1 to C12 alkyl group, with the proviso that at least one of A3 and R4 is a branched C3 to C,2 at kyl group; and the diaryldiamine is a compound of the formula Ill, R-Ar-Ar Ill where Ar and Ar' each independently represent a substituted or unsubtituted aryl group having from about 6 to about 50 carbon atoms; and
22. The lubricant of claim 21, wherein R5 is a substituent chosen from -NH2, [NH(CH2)n]mNH2, -(CH2)NH2, and -CH2-aryl-NH2, in which n and m are each an integer having a value of from about Ito about 10.
23. The lubricant of claim 21 or claim 22, wherein Ar and Ar' are phenyl groups.
24. The lubricant of any of claims 18 to 23, wherein the first compound is the reaction product of (I), (ii), (iii), and (iv), the alkyl amine being a compound of the formula IV, R6_,L R7 IV where R6 and R7 are substituents independently chosen from hydrogen and saturated or olefinically unsaturated aliphatic alkyl groups, with the proviso that at least one of R6 and R7 is not hydrogen.
25. The lubricant of claim 18, wherein: the polyacrylate is a compound chosen from trimethylolpropane triacrylate (TMPTA), hydroquinone diacrylate, hydroquinone dimethacrylate, pyrogallol diacrylate, pyrogallol dimethacrylate, pyrogallol triacrylate, resorcinol diacrylate, resorcinol dimethacrylate, glycol diacrylate, glycol dimethacrylate, glycerol diacrylate, glycerol trimethacrylate, 1,1,1 -trimethylol ethane tnacrylate, glucose polyacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, and propyleneglycol diacrylate; the hindered phenol is a compound chosen from 2-tert-butyiphenol; 2,6-ditert-butyiphenol; 2-isopropyiphenol; 2,6-dilsopropyiphenol; 2-sec-butyl phenol; 2,6 di-sec- butylphenot; 2-tert-hexylphenol; 2,6-ditert-hexyiphenol; 2-tert-butyl-o-cresol; 2-tert-dodecylphenol; 2-tert-decyl-o-cresol and 2-tert-butyl-6-isopropytphenol; and the diaryldiamine is a compound chosen from N-phenyl-1,3- phenylenediamine, N-phenyl-1.2-phenylenediam me, and N-phenyl-1,4-phenylenediamine.
26. The lubricant of claim 25, wherein the first compound is the reaction product of (i), (ii), (iii) and (iv), the alkyl amine being a compound chosen from di-iso- amylamine, di-n-octylamine, di-(2ethylhexyl)amine, di-(tert-octyl)amine, di-n- nonylamine, dilauryl amine, di-hexadecylamine, di-octadecytamine, di-oleylamine; n-octylamine, 2-ethyihexylamine, tert-octylamine, n-decylamine, n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, decenylamine, dodecenylamine, palmitoleylamine, oleylamine, linoleylam ne, and eicosenylamine.
27. The lubricant of claim 25, wherein: the polyacrylate is TMPTA; the hindered phenol is 2,6 di-tert butyl phenol; and the diaryldiamine is a compound chosen from N-phenyl-1,3- phenylenediammne, N-phenyl-1,2-phenylenediamine, and N-phenyl-1,4-phenylenediamine.
28. A lubricant composition comprising: a base oil; and the compound of claim 14.
29. An additive package comprising: a diluent; and a first compound that is the reaction product of (i) a polyacrylate, (ii) a hindered phenol, (iii) a diaryldiamine and optionally (iv) an alkyl amine.
30. The additive package of claim 29, wherein the concentration of the compound ranges from about 5 wt % to about 75 wt % of the additive package.
31. The additive package composition of claim 29 or claim 30, further comprising one or more additional additives chosen from dispersants, detergents, anti-wear agents, supplemental antioxidants, viscosity Index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors, anti-swell agents and friction modifiers.
32. The additive package of any of claims 29 to 31, wherein: the polyacrylate is a compound of the formula I, 0 R2 P1 (_Ot!CH2)q where R' is an aliphatic or aromatic group, R2 is hydrogen or methyl and q is an integer from about 2 to about 4; the hindered phenol is a compound of the formula II,

OH A3

II

where A3 and R4 are independently chosen from hydrogen or a linear or branched C1 to C12 alkyl group, with the proviso that at least one of A3 and R4 is a branched C3 to C12 alkyl group; and the diaryldiamine is a compound of the formula III, Re-Ar-! A Ill where Ar and Ar' each independently represent a substituted or unsubtituted aryl group having from about 6 to about 50 carbon atoms; and
33. The additive package of claim 32, wherein A5 is a substituent chosen from NH2, 4NH(CH2)n]mNH2, -(CH2)NH2, and -CH2-aryl-NH2, in which n and m are each an integer having a value of from about 1 to about 10.
34. The additive package of claim 32 or claim 33, wherein Ar and Ar' are phenyl groups.
35. The additive package of any of claims 29 to 34, wherein the first compound is the reaction product of (i), (ii), (iii) and (iv), the alkyl amine being a compound of the formula IV, R6_) R7 where A6 and A7 are substituents independently chosen from hydrogen and saturated or olefinically unsaturated aliphatic alkyl groups, with the proviso that at least one of A6 and R7 is not hydrogen.
36. The additive package of claim 29, wherein: the polyacrylate is a compound chosen from trimethylolpropane triacrylate I hyd roquinone diacrylate, hydroquinone dimethacrylate, pyrogallol diacrylate, pyrogallol dimethacrylate, pyrogallol triacrylate, resorcinol diacrylate, resorcinol dimethacrylate, glycol diacrylate, glycol dimethacrylate, glycerol diacrylate, glycerol trimethacrylate, 1,1,1 -trimethylol ethane triacrylate, glucose polyacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, diethyleneglycol diacrylate, triethylenegIyco dimethacrytate, and propyteneglycol diacrytate; the hindered phenol is a compound chosen from 2-tert-butyiphenol; 2,6-ditert-butyiphenol; 2-isopropylphenol; 2,6-diisopropylphenol; 2-sec-butylphenol; 2,6 di-sec- butyiphenol; 2-tert-hexyiphenol; 2,6-ditert-hexylphenol; 2-tert-butyl-o-cresol; 2-tert-dodecyiphenol; 2-tert-decyl-o-cresol and 2-tert-butyl-6-isopropylphenol; and the diaryldiamine is a compound chosen from N-phenyl-1,3- phenylenediamine, N-phenyl-1,2-phenylenediamine, and N-phenyl-1,4-phenylenediamine.
37. The additive package of claim 36, wherein the first compound is the reaction product of (i), (ii), (iii) and (iv), the alkyl amine being a compound chosen from di-iso-amylamine, di-n-octylamine, di-(2ethylhexyl)amine, di-(tert-octyl)amine, di-n*nonylamine, dilauryl amine, di-hexadecylamine, di-octadecylam me, di- oleylamine; n-octylamine, 2-ethylhexylamine, tert-octylamine, n-decylamine, n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, decenylam me, dodecenylam in palmitoleylamine, oleylamine, linoleylamine, and eicosenylamlne.
38. The additive package of claim 36, wherein: the polyacrylate is TMPTA; the hindered phenol is 2,6 di-tert butyl phenol; and the diaryldiamine is a compound chosen from N-phenyl-1,3- phenylenediam me, N-phenyl-1,2-phenylenediamine, and N-phenyl-1,4-phenylenediam me.
39. An additive package composition comprising: a base oil; and the compound of claim 14.
40. A method for reducing the oxidation of a lubricating oil, the method comprising placing in the crankcase of an internal combustion engine a lubricating composition according to any of claims 18 to 28.