CA2179169C - Synthetic ester lubricant stabilizer composition - Google Patents

Synthetic ester lubricant stabilizer composition Download PDF

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Publication number
CA2179169C
CA2179169C CA002179169A CA2179169A CA2179169C CA 2179169 C CA2179169 C CA 2179169C CA 002179169 A CA002179169 A CA 002179169A CA 2179169 A CA2179169 A CA 2179169A CA 2179169 C CA2179169 C CA 2179169C
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Prior art keywords
diphenylamine
naphthylamine
aryl
antioxidant composition
alkyl
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CA002179169A
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CA2179169A1 (en
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John Ta-Yuan Lai
Deborah S. Filla
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Emerald Polymer Additives LLC
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Noveon IP Holdings Corp
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Priority claimed from PCT/US1994/014539 external-priority patent/WO1995016765A2/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01SRADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S5/00Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations
    • G01S5/0009Transmission of position information to remote stations
    • G01S5/0045Transmission from base station to mobile station
    • G01S5/0063Transmission from base station to mobile station of measured values, i.e. measurement on base station and position calculation on mobile
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01SRADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S5/00Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations
    • G01S5/0009Transmission of position information to remote stations
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01SRADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S5/00Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations
    • G01S5/0009Transmission of position information to remote stations
    • G01S5/009Transmission of differential positioning data to mobile
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01SRADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S5/00Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations
    • G01S5/02Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations using radio waves
    • G01S5/10Position of receiver fixed by co-ordinating a plurality of position lines defined by path-difference measurements, e.g. omega or decca systems
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01SRADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S5/00Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations
    • G01S5/02Position-fixing by co-ordinating two or more direction or position line determinations; Position-fixing by co-ordinating two or more distance determinations using radio waves
    • G01S5/14Determining absolute distances from a plurality of spaced points of known location
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04BTRANSMISSION
    • H04B7/00Radio transmission systems, i.e. using radiation field
    • H04B7/14Relay systems
    • H04B7/15Active relay systems
    • H04B7/185Space-based or airborne stations; Stations for satellite systems
    • H04B7/1853Satellite systems for providing telephony service to a mobile station, i.e. mobile satellite service
    • H04B7/18545Arrangements for managing station mobility, i.e. for station registration or localisation
    • H04B7/18547Arrangements for managing station mobility, i.e. for station registration or localisation for geolocalisation of a station
    • H04B7/1855Arrangements for managing station mobility, i.e. for station registration or localisation for geolocalisation of a station using a telephonic control signal, e.g. propagation delay variation, Doppler frequency variation, power variation, beam identification

Abstract

An antioxidant stabilizer composition is disclosed that is the reaction prod uct of a diphenylamine and an N-aryl naphthylamine in the presence of an organic peroxide. The mole ratio of diphenylamine: N-ary l naphthylamine is from 1:1 to 10:1. This results in mo re oligomeric reaction products and significantly less unreacted monomeric resi dual reactants. The resultant product composition compr ises diphenylamine homooligomers and diphenylamine/N-aryl naphthylamine cross oli gomers. The diphenylamine and N-aryl naphthylamine are desirably substituted with alkyl groups having from 1 to 20 carbon atoms or styryl groups. The reaction temperature is preferab ly from about 130.degree. to 150.degree.C. The controlled reaction conditions allow the use of solvents with extractable hydrogen atoms wit hout producing significant amounts of dehydrocondensation between the solvent and the diami nes. The reaction products have superior oxidative resi stance in the Oxidation Corrosion Stability Test (OCS) and Vapor Phase Coker Test o ver products products produced under other conditions.

Description

WO 95116765 pC'flUS94l14539 1~THETIC ESTER LBBRICANT STABILIZER COMPOSITION
FIELD OF INVENTION
The present invention relates to an antioxidant stabilizer composition for lubricants and especially for synthetic'ester lubricants. More particularly, it relates to a reaction product of substituted diphenylamines (DPA) and substituted N-phenyl-a(p)-naphthylamine (PNA). By careful selection of the mole ratio of DPA:PNA and reac-tion conditions, most of the DPA and PNA are converted to oligomeric products having improved properties over the starting materials.
IS
Amine antioxidants have been known and are widely used to improve the thermal-oxidative stability of syn-thetic ester lubricants used in the lubrication of moving parts operated at very high temperature, such as jet , engines and hydraulic systems for military and commercial aircraft. In operation at high temperature in the pres-ence of oxygen and catalytically- active metals, the antioxidants are depleted. Oxidative oil degradation can create acidic by-products that degrade nearby,metals and can form polymers which undesirably increase the viscosity o~ the lubricant. This oxidative degradation can lead to oil insoluble sludge and deposits.
U.S. Patent No. 3,655,559 discloses alkylated diphenylamines, U.S. Patent 3,660,290 discloses alkylated N-aryl naphthylamines., and U.S. Patent No. 3,804,762 discloses alkylated N-phenyl naphthylamines in combination with specific amino compounds which are useful as antioxi ' dants for synthetic ester lubricants. U.S. Patent No.
3,573,206 discloses reaction products from oxidation treatment of N-aryl naphthylamines and diarylamines to form homo-oligomers of PNA and cross oligomers of DPA and PNA and a high percentage of unreacted of DPA and PNA.
These reactions are desirably done in inert solvents such as aromatic hydrocarbon or ketones. These inert solvents S~TUTE SHEET (RULE 26) avoid cross dehydrocondensation reactions described later.
Heretofore it has also been known that the treatment of various compounds with peroxide produces dehydrocondensa-tion products having increased high temperature stability as antioxidants over the monomeric components. U.S.
Patent No. 3,492,233 discloses such a blend of a conven-tional polyester lubricating oil reacted in the presence of diaryl amines with certain organic peroxides to form dehydrocondensation products from the esters and diaryl amines. These reactions require abstractable hydrogens on the polyester lubricants. U.S. Patent No. 3,492,233 discloses a cross-dehydrocohdensed product which consists of the stabilizer, such as-a secondary aromatic amine or a hydroxyaromatic antioxidant, being chemically attached to the lubricating oil or other organic substances that have abstractable hydrogens under these reaction -condi-tions. The product has increased high temperature stabil-ity over simple mixtures of the antioxidant in the oil.
U. S. Patent No. 3,509,214 describes the high temperature air oxidation product or permanganate oxida tion product from N-aryl naphthylamine or a combination thereof-with diphenylamine. An article entitled "Fate of Amine Antioxidants During Thermal Oxidative Aging of Neopentylpolyol Eater Oils" in J. of Synthetic Lubri ration, 4, p 179-201 (1987) discloses that the high temperature air oxidation of diphenylamine yields as a product, phenazine of the structure R
O
R
~STITUTE SHEET (RULE 26) which is an insoluble sludge be avoided. As disclosed by Wieland in Chem. Ber. 39, p. 1499-1506 (1906), the oxidation of diaryl amines with KMn04 results primarily in a dimer of the diarylamines where the nitrogen atoms are bonded together.
It has now been discovered that an amine antioxidant composition having superior high temperature stability in lubricants such as ester fluids, but which has little dehydrocondensation product, can be made by reacting to controlled amounts of organic peroxides with specific molar ratios of a diphenylamine to an N-phenyl-a(,~)-naphthylamine, or their alkyl substituted derivatives.
These reaction products have higher concentrations of oligomer than prior art disclosures in the presence of solvents with highly abstractable hydrogens. The composition is mainly homo-oligomers of DPA and cross oligomers of DPA and PNA. When added to an ester fluid, such as used for aviation lubricants, the inventive antioxidant provides excellent protection against oxidation of the lubricant.
SUMMARY OF THE INVENTION
Effective antioxidants for lubricants are reaction products of various unsubstituted or substituted diphenylamines (DPA), unsubstituted or substituted N-phenyl-naphthylamines (PNA), and organic peroxides. At mole ratios of DPA:PNA of about 1:1 to about 10:1, and at temperatures of about 70 to about 200°C, primarily oligomeric products are formed from the amine molecules, which oligomeric products have enhanced performance as 3o antioxidants over their precursors.

- 3a -Thus, in one aspect of the invention, there is provided an antioxidant composition comprising the reaction product of:
(a) at least one N-aryl naphthylamine;
(b) at least one diphenylamine; and (c) an organic peroxide free radical source; said N-aryl naphthylamine having up to three alkyl, styryl, or methyl substituted styryl groups, or combinations thereof, on each aryl ring, wherein said alkyl has from 1 to 20 to carbon atoms; said diphenylamine having up to three alkyl, styryl, or methyl substituted styryl groups, or combinations thereof, on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; wherein the mole ratio of said diphenylamine to said N-aryl naphthylamine is from 1:1 to 10:1 and wherein the reaction of (a), (b), and (c) is conducted at temperatures from about 70°C to about 200°C, and wherein said reaction product contains at least 35 mole percent of said diphenylamine and said N-aryl naphthylamine in the form of cross oligomers.
2o In another aspect of the invention, there is provided a process for making an antioxidant composition comprising reacting at least one N-aryl naphthylamine having up to three alkyl, styryl, or methyl styryl groups or combinations thereof on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; with at least one - 3b -diphenylamine having up to three alkyl, styryl, or methyl styryl groups or combinations thereof on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; in the presence of an organic peroxide free radical source, at a mole ratio of said diphenylamine to said N-aryl naphthylamine from 1:1 to 10:1 and at a temperature from 70° to 200°C.
In still another aspect of the invention, there is provided a lubricating oil composition stabilized against to oxidative and thermal degradation comprising:
a) a lubricating oil containing synthetic ester oils subject to oxidative or thermal degradation, and b) from 0.1 to 10 weight percent of an antioxidant composition of the invention.
The amount of peroxide in the antioxidant composition varies from 0.5 to 3 moles per mole of total diaryl amines present. These reaction conditions were found to be critical to producing oligomers with degrees of polymerization in excess of 2, 3 or 4. Relatively low 2o amounts of less active monomers and degradation products are associated with longer reaction times or more austere reaction conditions.

WO 95!16765 217 916 9 PC1'/US94114539 RRTFF DESCRTPTTON OF FIGURES -Figure1 shows the high performance liquid chroma-tography results on Example 2 of this application, this ' data is summarized under Example 2 in the tahle form;
Figure 2 shows the mass spectrum of the product of Example 2, which is the reaction product of p,p'-di-t-octyl diphenylamine (DODPA): N-(p-octylphenyl)-I-naphthyl-amine (OPNA) in a mole ratio of 2:1, the masses have been identified with two numbers in parenthesis which are believed to be the number o~ units of DODPA and OPNA, respectively in the molecule that generated.the mass. An * is used to identify peaks, including the synthetic ester lubricant;
Figure 3-shows the chromatography results on-Example 3, this data is summarized_under Example 3 in table form;
Figure 4 shows the mass spectrum of the components in Example 3, which has a DODPA:OPNA ratio of 3.1, the masses have been identified with three numbers in paren-thesis, the first # represents the number of DODPA units, the second # represents the number of OPNA units, and the * represents the numbers of ester lubricant units;
Figure -5shows the chromatography results on comparison Material A which is a commercial material with at least a 1:2 DODPA:OPNA ratio;
Figure 6 shows the-mass spectrum of the material of Comparison Material A which shows no trace of DODPA homo-oligomers at all, the masses have been identified in parenthesis, with the first # being the number of DODPA
units in the molecule and the second # being the number of OPNA units in the particular molecule, and * represents ester lubricant molecules.
nFTATTFn DESCRTPTTON OF THE TNWNTTON
The antioxidant composition of this invention is the reaction-product of:- ' (a) at least one N-aryl naphthylamine (PNA);
(b) at least one diphenylamine (DPA); and -(c) an organic peroxide.free radical source; said N-aryl naphthylamine having up to three alkyl, atyryl, or ? S~STITUTE SHEET (RULE 26) W095/16765 217 916 9 pCT~T594114339 methyl substituted styryl groups, or combinations thereof, on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; said diphenylamine having up to three alkyl, styryl, or methyl substituted styryl groups, or combing-' S dons thereof, on each aryl ring, each alkyl having from 1 to--20 carbon atoms; wherein the mole ratio of said diphenylamine to said N-aryl naphthylamine is from 1:1 to 10:1 and wherein the reaction of a, b, and c is conducted at temperatures from about 70°C to about 200°C.
The diphenyl amine oligomers can be represented by the following-general formula H

-2(x-1)H
(R1)m (R2)n x wherein each R1 and R2 independently are H, or branched or straight-chain C,-C,a alkyl radicals, or radicals such as styryl or methyl substituted styryl and preferably t-butyl or t-octyl radicals; and m and n each represents 0, 1, 2, or 3; preferably m and/or n represents 1, and x is from 1 to 8, and preferably 2 to 5, and most preferably 2. .
The cross oligomer from substituted N-phenyl-a(p)-naphthylamines with substituted diphenylamine can be represented by the following general formula SUIBSTlTUTE SHEET (RULE 26) FORMUhA 2 H H
N ~ N
R2~n Y ~R3~~ tR4~p z -2 (y+z-1)H
Wherein y and z are independently up to e, and preferably y is .2-5 and z is 1; wherein R, and R, are independently C,-Coo alkyl radicals or styryl or methyl styryl, desirably C~-C8 substituted radicals, and preferably t-butyl or t-octyl radicals; R3 and R, are independently C1 to Coo alkyl radicals or styryl or methyl styryl, desirably C,-C9 alkyl radicals and preferably t-butyl or t-octyl radicals; and m, n, p, and o are independently 0, 1, 2, or 3, and preferably one or more of m, n, o, p, and 0 are 1.
It is theorized that the bonding between the DPA and PNA may occur between two nitrogen atoms, between a nitrogen atom. in one aryl-naphthylamine or diphenylamine and a carbon atom in another aryl-naphthylamine or diphe-nylamine or between carbon atoms in two diffexent aryl rings from naphthyl or.phenyl radicals. It is anticipated that most of the linkages between the DPA and PNA mole-cules are between a nitrogen in one DPA or PNA and a carbon atom in naphthyl or aryl substituents of another DPA or PNA. The possible linkages are described in detail in U.S. Patent 3,509,214.
Formula 2 is not meant only to imply that the oligomers are block copolymers. The oligomers are be-S1JBSTITUTE SHEET (RULE 26j VVO 95/16765 217 9 i 6 9 pCT~S94J14539 lieved to be very random in the order of DPA and-PNA
incorporation. The subscripts y and z are meant only to indicate the number of DPA or PNA molecules in the cross oligomer.
The antioxidant composition of the present invention is made by reacting diphenylamine (DPA-H), or its alkylated or styrylated derivatives, with N-phenyl-n-aphthylamine (PNA-H), or .its alkylated or styrylated derivatives, in the presence of one or more peroxides at elevated temperature. The reaction can be generalized as follows:
~yg$IpTUTE SHEET (RtfLE 26) _$_ H
H N~(R3)c N
peroxide ' (R1)m (R2)n (R4) P
(DPA-H) (PNA-H) H
/ N. +
-2(x-1)H
(R1)m (R2)n x x x 3s I I
N N
(R1)m (R2)n Y R3)o R4)P z -2(y+z-1)H
One skilled in the art will appreciate that the designation o~ the alkyl group within the benzene ring indicates that the alkyl group may appear at any position on the ring. Similarly, alkyl groups on the naphthylene ring may appear at any position on the ring.
SlIBSTITUfE SHEET (RULE 26), WO 95116765 PCflU594f14539 _ g_ In order to get high conversion of DPA and PNA to ~ the desired oligomers, it is desirable that the DPA:PNA
ratio be from 1:1 to 10:1 or from 1.2:1 to 5:1; more desirably from 1.5:1 to 4:1; and preferably from 1.75.1 to 2.5:1 or 3:1, most preferably 2:1..
The diphenylamine or its alkylated or styryl derivatives are commercially available. It has the chemical structure H
(Rl)m~~~R2)n l~' Jl7-N
where Rl, Ra, m, and n are defined the same as for the diphenylamine homo-oligomers. The preferred diphenyl-amines have tertiary alkyl groups such as octyl on each phenyl group in the para position.
The N-aryl naphthylamines and their alkylated derivatives are also commercially available. They may have the chemical structure H
(R3 ) o~
N
2s (R4)P
where R3, R" o, and p are as defined above for-the cross oligomer. Other N-aryl-naphthylamines would also have substitutes of (R,)° and (R,)p.
The reaction may be conducted in bulk or solution by heating the DPA, PNA, and organic peroxide to temperatures desirably from 70 to 200°C, more desirably from about 90 or 110 to 180°C and preferably from 130 to 150°C, and for from 30 minutes to 30 hours, desirably from about 1 hour to 10 hours, and preferably from 2 to 6 hours. The individual components can be added in any order, in increments, or metered into other components. The reaction may be carried out under vacuum to remove volatiles from the S~I~TITiJTE SHEET (RULE 26) WO 95/16765 2 ~ 7 916 9 PCT~S94I14539 decomposition of the organic peroxides. The DPA and PNA
may be dissolved in suitable organic solvents such- as ' aliphatic hydrocarbons or synthetic ester lubricants, which can have abstractable hydrogens. The reaction may ' also be conducted in the presence of synthetic ester lubricants produced from- condensation of monohydroxy alcohols and/or polyhydroxy alcohols with monocarboxylic or polycarboxylic acids. These ester fluid lubricants are described in detail later in this specification.
These eater lubricants as disclosed in U.S. Patent 3,492,233, can become chemically bonded through dehydro-condensation reactions to the DPA, PNA, or oligomers thereof during the reaction of the DPA, PNA, and organic .
peroxides. However, with careful control of DPA to PNA
ratios, the amount of peroxide used, and the reaction temperature; the amount -of dehydrocondensation bond .
between the lubricant and amine is minimized.
Another useful solvent for the reaction of DPA, PNA, and organic peroxides are the alkane solvents having from 6 to 16 carbon atoms having linear, branched, or cyclic structure. These are also known to form dehydro-condensation products with these amines, but this reaction is limited in this disclosure by the reaction conditions.
These solvents are also easily removed by volatilization.
Subsequent to the reaction of the DPA, PNA, and organic peroxides, it is desirable to raise the tempera-ture to fully decompose the organic peroxides.- This minimizes undesirable oxidation reactions later. Under optimized conditions as disclosed herein, most of the desired reactions which form oligomers and cross oligomera have occurred prior to the residual peroxide decomposition step. It has been determined that no significant change in the molecular weight of the oligomers occurred during the decomposition of residual organic peroxides. Desir-ably, this is conducted at temperatures from 140 to 200°C, and desirably from 160-180°C for from 5 minutes to 2 hours, more desirably 30 minutes to 1 hour, and desirably at S!lBSTIME SHEET (RULE 26) WO 95/16765 2 1 7 9 1 ~ 9 p~~TS94114539 -li-pressures below atmospheric pressure.
Reaction in accordance with the above-described conditions results in greater than 70 mole % of the DPA
and PNA being in oligomeric forms of dimers or higher, desirably greater than 80 mole % in oligomeric forma of dimer or higher, more desirably greater than 90 mole % in oligomeric forms of dimer' or higher, and preferably greater than 95 mole % in oligomeric forms of dimer or higher. The residual portion of the DPA and PNA being.in monomer form or dehydrocondensed with solvent or other molecules present.
Any organic peroxide may be used as a free radical source which has a half life of about one hour at a temperature between from about 70°C to about 200°C.
Desirably the half-life of one hour is at temperatures between from 90 to 160°C, and preferably between from 130 to 150°C. Included in this group are the acyl peroxides, ' peresters, peroxyketals, and alkyl peroxides, all of which are commercially available from Lucidol Penwalt, U.S.A.
Atochem or Akzo Chemicals Inc., by the trademarks or common names indicated. The amount of peroxide used is desirably 0.5 to 2.0 or 3.0 molea/mole of the diaryl amines and is preferably from about 1.0 to 1.5, and most preferred from 1.1 to 1.3.
Included as peroxides are acyl peroxides of the formula O O
R1-C-O-O-C-R' , peroxyketals of the formula (Rl~z C (OOR') z, alkyl peroxides of the formula R1-O-O-R', SUBSTITUTE SHEET (RULE 26) WO 95/16765 2 1 7 ~ 1 6 9 P~~S94114539 and peresters II
Rl-C-O-O-R~ , wherein R1 and R' can be the same or different and alkyl, aromatic, alkyl substituted~aromatic, or aromatic substi-tuted alkyl groups having from 1 to 10 carbon atoms.
Suitable peresters include t-amylperoxy-2-ethyl-hexanoate, t-butylperoxy-2-ethylhexanoate (t-butyl per-octoate, t-butylperoxy-isobutyrate, t-butylperoxy-malefic acid, 00-t-butyl O-isopropyl monoperoxycarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 00-t-butyl-O-(2-ethyl-hexyl)mono peroxycarbonate, 00-t-amyl O-(2-ethyl-hexyl)mono peroxy-carbonate, t-butyl-peroxy acetate, t-amyl-peroxy-acetate, t-butylperoxy benzoate, t-amyl-peroxybenzoate and di-t-butyl-diperoxyphthalate.
Suitable peroxyketals include n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-di(t-butylperoxy)butane, ethyl-3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane and ethyl-3,-3-di(t-amylperoxy) butyrate.
Suitable dialkyl peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumyl peroxide a-bis(t-butylperoxy)diisopropyl-benzene, di-t butyl peroxide, di-t-amyl peroxide and 2,5-dimethyl-2,5 di(t-butylperoxy)hexyne-3. The preferred peroxide is di t-butyl peroxide.
The reaction products are desirably essentially free or free of potassium permanganate catalysts or products of its reduction. These permanganate catalysts result in oligomeric products from diamines having reduced antioxi-dant effect.
The reaction products desirably have 30 mole % or less, desirably 20 mole % or leas, and preferably 10 mole % or less of the diaryl amines reacted into dehydroconden-sation products with any solvent used for making the reaction products. Desirably thereaction products have SUBSTITUTE SHEET (RULf 26) _13_ at least l0 mole %, more desirably about 15 to 30 mole %, and preferably 20-25 mole o of the diaryl amines in r_he form of homo-oligomers of DPA. Desirably at least 35 mole %, more desirably 40 mole %, and preferably 50 mole % of the diaryl amines are in the form of cross oligomers of DPA and NFA. Desirably the reaction product contains less than 30 weight percent of DPA and NPA in monomeric form and more desirably less than 20 or 10 weight percent.
The antioxidant compositions of this invention are useful in ester fluids including lubricating oils, fuels, hydraulic fluids, transmission fluids, especially those ester fluids useful in high temperature avionic (turbine engine oils) applications and/or internal combustion reciprocating or rotary engine oils. The antioxidants are also useful in blended oils for similar purposes that have desirably at least 10, 20, 30 or 50 weight percent ester fluids with the remainder being other lubricants such as hydrocarbon oils.
The ester fluid lubricants which may be used with this invention are esters produced from monohydroxy alcohols and monocarboxylic acids, from polyhydroxy alcohols end monocarboxylic acids, and/or from monohydroxy alcohols and dicarboxylic acids. Such esters are well known, having been described for example in U.S. Patent No. 3,432,433.
Each of the alcohols and acids used in preparing the ester may contain from 1 to 4 functional groups thereby produc-ing mono-, di-, tri-, and tetraesters. Contemplated within this invention are esters of alcohols, diols, triols, and pentaerythritols, said alcohols or polyols having from 2 to 20 carbon atoms, and mono- and dicar-boxylic acids having from 2 to about 20 carbon atoms and preferably 4 to 12.
The above esters may include the monoesters from octyl acetate, decyl acetate, octadecyl acetate, methyl myristate, butyl stearate, methyl oleate, and the like and the polyesters from dibutyl phthalate, di-octyl adipate, SUBSTITUTE SHEET (RULE 2fi) WO 95116765 pCTlUS94114539 2~T~~s~

di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate, and the like.
The most preferred esters are produced from hindered or neopentyl alcohols, that is, those in which the beta carbon atom is completely substituted by other carbon atoms. These esters have the structure R1-C-O-CHZ-C-CHz-O-C-R' CA=Ra wherein each of R1 and R' is individually an alkyl or aryl of 1 to 19 carbon atoms and each of R' and R' is individu-ally hydrogen, alkyl of 1 to 5-carbon atoms or O O
O-C-Rl or -O-C-R' and each of the R1 and RZ groups are as described above.
Such esters include 2,2-dimethylpropane-1,3-diol di-pelargonate, trimethylolpropane trioctanoate, trimethylol-propane tridecanoate, trimethylolbutane trihexanoate, pentaerythritol tetraoctanoate and pentaerythritol tetra-dodecanoate. Mixtures of acids may be used in producing the di-, tri- and tetraesters. For example, a preferred pentaerythritol ester contains a mixture of C, through Clo carboxylic acids. The esters in accordance with this invention include any eater fluid having an abstractable hydrogen atom, although the preferred reaction conditions result in minimal dehydrocondensation between the polyea ters and the amines.
The antioxidant stabilizer made from DPA and PNA is efficient at concentrations from 0.1 to 10 wt. %, desir-ably from 0.5 to 5 wt. %, and preferably from 1.5 to 2.0 wt. % in a lubricant based upon the total weight of the formulated lubricant. These weight percents are of the DPA, PNA, and oligomers thereof and do not include the ~STIIIITE SHEEP fHtJIE 261 synthetic ester lubricants even if they are used as a solvent for the reaction. In the case of synthetic ester lubricants coreacted with DPA and PNA, the weight percents recited above are the calculated weight percents of DPA
and PNA reactants in the final lubricant product. The stabilizer can be used in conjunction with other additives such as detergents, other antioxidants, corrosion inhibi-tors, antifoamants, antiwear additives, extreme pressure additives, hydrolytic stability agents, load additives or viscosity modifiers. One such antioxidant can be the DPA
monomer or oligomers as previously described.
The following non-limiting examples will provide the reader with a more detailed understanding of the inven-tion.
Fxamnle 1 (Comparison with 1:1 DODPA:OPNA) p,p'-Di-t-octyl diphenylamine (DODPA) (393 g, 1 mole), N-(p-octylphenyl)-1-naphthylamine (OPNA) (331.5 g, 1 mole) and 1 liter decane were placed in a 5-liter, 3-.
neck flask equipped with a thermometer, an addition funnel and a distillation column. The mixture was heated to 140°C
under nitrogen and di-t-butyl peroxide (439 g, 3 mole) was added in portions. The reaction continued for 3 hours during which time t-butyl alcohol was collected through the distillation column. The reaction temperature was then raised to 170°C for 1 hour. More t-butyl alcohol was collected. Vacuum was then slowly applied to accelerate the distillation until 2 mm Hg was reached. Residue alcohol and decane were removed under vacuum. The vacuum was released under nitrogen and the mixture was poured into a cold container. The brittle solid produced was then ground into yellow powder.
Examgle 2 (2:1 DODPA:OPNA) p,p'-Di-t-octyl diphenylamine (DODPA) (783 g, 2 ~'f'iflffE SHEET (RULE 26) mole), N-(p-octylphenyl)-1-naphthylamine (OPNA) (331.5 g, 1 mole) and 1114.5 g of an eater mixture consisting of a mixed C,-C9 acid pentaerythritol eater were placed ih a 5-liter 3-neck flask equipped with a thermometer, an addi-tion funnel and a distillation column. The mixture was heated to 140°C under nitrogen. Di-t-butyl peroxide-(526.3 g, 3.6 mole) was added in portions over 45 minutes. The reaction was continued for-3 hours during which time t-butyl alcohol was collected through the distillation column with a head temperature of 80-85°C. The color went from a fluorescent bluish color to a brown color- The reaction temperature was then raised to 170°C over a 1 hour period and was maintained there for 40 minutes. More t-butyl alcohol was collected. The vacuum was then slowly applied to accelerate the distillation until a pressure of 2 mm Hg was reached. The reaction product was held under those conditions 20 minutes to remove all residue alcohol.
The vacuum was released under nitrogen and the mixture was cooled down. The reaction product was then collected as a 50% active antioxidant in the lubricant.
High performance liquid chromatography (HPLC) as shown in Figure 1 based on area percents in the peaks determined with a 270 nm U.V. detector the following:
~1~TIME SHEET (RULE 26) ' R'O 95/1b765 PCTlUS94114539 _ 17-Peak Areas From Figure 1, Example 2.
X,Y = unit of DODPA in homo and cross oligomers re-spectively;
Z = unit of OPNA;
subscripts fadicate number of units in oligomer.
PEAR Elution COMPOSITION PEAR AREA
Time (min) Formula 1 Formula 2 $

A 1.14 X1 4.0 B 6.19-7.23 Xi 21.1 C 13.29-14.81 X3 Y2 Z1 32.9 D' 17.05-17.80 Y3 Z1+Y~Zz 13.0 E 19.54-20.08 Yq21+Y3Zz+Y2Z~ 9.2 * At the 27D nm wavelength used, the peak areas are close to the weight percent of each component in the sample. For the peaks C, D, and E, the mass spec-trum indicates the cross oligomers with excess DODPA
over OPNA units predominate over those with more than one OPNA unit. Dehydrocondensation products between the ester and the diaryl amines were less than or equal to 15%.
' :1 DODPA:OPNA
p,p'-Di-t-octyl diphenylamine (23.6 g, 0.06 mole), N-(p-octylphenyl)-1-naphthylamine (6.63 g, 0.02 mole) were mixed with 30.2 g mixed ester lubricant in a 250 ml 3-neck round bottom flask equipped with a thermometer, addition funnel and magnetic stirrer. While-heating to 140°C under nitrogen, t-butyl peroxide (14.04 g, 0.096 mole) was added in portions during a half-hour period. The reaction was stirred at 140°C for a total of 7 hours, then at 170°C for 45 min. Vacuum (2mm Hg) was applied at the end for 20 min. at 170°C. High performance liquid chromatography as shown in Figure 3 based on area percent of the peaks determined with a 270 nm U.V. detector the following:
$UBST11U'fE SHEET (RULE 26~

-18 _ Peak areas from Figure 3, Example 3 X,Y = unit of DODPA in homo and cross oligomer respec-tively;
Z = unit Of OPNA;
subscripts indicate number of units in oligomer.
PEAK Elution COMPOSITION PEAK AREA
Time (min) Formula 1 Formula 2 A 1.16 X1 3.5 B 6.47- 7.58 X2 25.4 C 13.63-15.09 X~ + YzZl 29.1 D 17.60-18.23 Y321+Y2Zz 11_1 E. 19.75-20.28 Y,Z,+Y3Z2+Y2Z3 9.0 * At the 270 nm wavelength used, the peak areas are close to the weight percent of each-compo-nent in the sample. For the peaks C, D, and E, the mass spectrum indicates the cross oligomers with excess DODPA over OPNA units predominate over those with more than one OPNA unit.
Dehydrocondensation products between the ester and the diaryl amines were less than 20%.
4 (4:1 DODPA:OPNA
p,p'-Di-t-octyl diphenylamine (314.4 g, 0.8 mole), N-(p-octylphenyl)-1-naphthylamine (66.3 g, 0.2 mole) were heated with a 500 ml paraffin solvent (boiling point 179-189°C) at 140°C. t-Butyl peroxide (175.4 g, 1.2 mole) was added over 30 min. The reaction was then stirred at 140°C
for 3 hours, then at 170°C for 1 hour. The paraffin solvent was distilled off and the residue was cooled to a brittle solid. It can be ground into a yellow powder.
Example 5 The procedure in Example 3 is used except N-(p-octylphenyl)-1-naphthylamine is replaced by 0.02 mole of N-(p-nonylphenyl)-1-naphthylamine. An oligomeric product was produced.
Example 6 Same procedure as in Example 4 except p,p'-di-t-SUBSTITUTE SHEET (RULE 26j R'O 95/16765 PCTlUS94114539 octyl diphenylamine was replaced by p-octyl diphenylamine.
An oligomeric product was produced.
Example 7 Same procedures as in Example 2 except p,p'-di-t-octyl diphenylamine was replaced by a mixture containing p-p'-di-butyl diphenylamine~, p,p'-di-octyl diphenylamine;
p-t-butyl-p'-t-octyl diphenylamine; p-t-butyl diphenyl-amine; p-t-octyl diphenylamine and diphenylamine. An oligomeric product was produced.
Examz~le 8 Same procedure as in Example 2 except p,p'-di-t octyl diphenylamine was replaced by a mixture of diphenyl amine substituted with- styryl and t-octyl groups. An oligomeric product was produced.
pxidat~on Corrosion Stabilitv Test The reaction products of Example 1 and 3 were evaluated in oxidation corrosion stability (OCS) teats in the presence of various metals at different temperatures.
Commercial product A represents a commercial material made from a mixture having at least a 1:2 molar ratio of DODPA:OPNA being present at 2.0 wt. % in an ester lubri cant. High performance liquid chromatography shown in Figure 5 indicate this commercial product has essentially no (DODPA)2, but contains a rather complex mixture of (DODPA)Y (OPNA)~ where y > z dominates. The products of Examples 1 and 3 were evaluated at 2 wt. % in an ester lubricant. The OCS test is the exposure of a synthetic ester lubricant (condensation product of pentaerythritol and mixed C,-C9 carboxylic acid) to temperature of 400 or 425°C for 72 hours while metals are present. It determines the ability of the antioxidants to inhibit oxidation of the lubricant and formation of acid species. It measures the change in viscosity of the lubricant as a % of the initial viscosity and the change in total acid number 5lfSSTiTiTfE SHEET (RULE 26j R'O 95/16765 PC17US94114539 (STAN). The viscosity is measured as kinematic viscosity at 100°F. The results in Table I below show the change in viscosity (D vis %) and change in total acid number (~
TAN) for each example with the different metals present.
The D TAN is calculated fram the moles of additional base required to titrate or neutralize 100 g of sample multi-plied times 561.
TABLE I
Experiment Measure Ex. 1 Ex. 3 Commercial Material A

OCS 400F ~Vis% 5.5 3.9 10.0 Cu,Mg, STAN 0.15 0.06 0.51 -Fe,Al,Ag OCS 425F AVis% 30.5 13.3 36.0 Cu,Mg, STAN 5.7 1.99 4.7 Fe, Al,Ag OCS 425F ~Vis% 26.95 9.7 20.84 T1, Ti, STAN- 11.7 0.86 3.35 Fe, A1, Ag OCS 450F ~Vie% Not 72.5 127,70 Available Cu, Mg, STAN Not 4.8 8.01 Fe, Al,Ag Available The data in Table I shows that the material of Example 3 using a 3:1 DODPA:OPNA ratio, a low temperature, and a controlled amount of peroxide performs better in the OCS test than the Commercial Material A, which has around a 1:2 DODPA:OPNA ratio and the antioxidant of Example 1, which has a 1:1 molar ratio of DODPA to OPNA. Effective antioxidants give low D vis % values indicating they prevent crosslinking and condensation between the mole-cules of the lubricant. The effectiveness of an antioxi-dant can also be measured by its ability to prevent the oxidation of the lubricant to carboxylic acid type species. The generation of the acid species are measured by the D TAN values in the OCS tests.
Example 1 has a DODPA:OPNA ratio of 1:1 which is between that of Example 3 and the Comparison Material A.
~STITUTE SHEET (RULE 26}

R'O 95/16765 PCflUS94114539 ~1791b9 The performance of-Example 1 in the first two OCS teats is midway between that of- Example 3 and the Comparison Material. In the OCS test with Tl, Ti, Fe, Al, and Ag present Example 1 material had poor D Vis % and D TAN.
Example 9 The materials of Examples 1, 3, and Comparison Material A were also tested in the U.S. Navy Vapor Phase Coker Test. This test is fully described in publication NAPTC-PE-71 of the Naval Air Propulsion Test Center. The test is designed to simulate part of a gas turbine engine where hot surfaces are contacted by oil mists or vapors.
It consists of a round bottom flask held at 400°F into which 0.027 scfm of dry air is bubbled for 18 hours. The vapor and mist formed from the bubbling air flow up into a metal tube which is in an oven held at 700°F. The tube is tared before the test, and weighed afterwards to measure the mist and vapor deposit formed. A low value in this test is desirable as it indicates a lubricant with minimized tendency to form undesirable vapor/mist deposit in gas turbine engines. The average test results for the product of Example 1 were 180 mg; the test results for the product of Example 3 were 138 mg, and the test results from Commercial Material A were 295 mg. These tests indicate that an antioxidant of the invention (Example 3) produces less of the undesirable deposits during high temperature use than related antioxidants (Example 1 and Commercial Material A) which are not antioxidants of the invention.
Example 10 To study the effect of reaction conditions and DODPA:OPNA ratio on the performance of oligomeric amine reaction products, several examples from U.S. Patent 3,573,206 were made replacing N-phenyl-2-naphthylamine with the more effective t-octyl N-phenyl-1-naphthylamine and replacing diphenylamine with the more effective p,p'-~STI1UTE SHffT (RULE 26) di-t-octyl-diphenylamine used in this application on a molar basis. Example B is from U.S. Patent 3,573,206, Ex.
5, and Example-C is from the same patent, Ex. 9. Both examples use the more effective alkyl substituted amines so as to be more comparable to Examples 2-and 3 of this disclosure. Ex. B used just the OPNA, while Ex. C used an equimolar blend of DODPA and OPNA. Both used potassium permanganate to cause oxidation.- As disclosed in the issued patent, the unreacted amines were greater than 40 weight percent of the reaction products using the perman-ganate oxidation technology.
In Example 5 of that patent, about one-half of the reaction product was dimer of the PNA and one-half was unreacted PNA. In Example 9, about 44% of the reaction product was the diaryl amine starting materials, about 35%
was the dimer of PNA, about 15% was a desirable cross-oligomer, and about 5% was an unidentified side product.
The antioxidants of Examples 2, 3, and 10 (B and C) were subjected to the OCS Test at 425°F for 72 hours. The results are given below in Table II.
TABLE II
OCS Test at 425F, 72 Hours 2 Wt. % in Ester DODPA:OPNA D Vis % D TAN

Example 2 2:1 18.8 5.65 B of Example 10 0:1 41.5 7.15 C of Example 10 1:1 41.0 12.4 Example 3 - 3:1 24.3 4.39 Table II shows that the compositions of Examples 2 and 3 perform better at prevention of oxidative changes in the lubricant compositions than do Examples B and C made with permanganate oxidation. This shows that the ratio of DODPA:OPNA and the reaction conditions such as peroxides versus potassium permanganate have an observable-effect on the performance of the reaction products.
SHEET (RI I~E fig) W095/Ifi7fi5 21 l 91 ~ 9 PCTIUS94114539 Example 11 To study the effect of dehydrocondensation between the solvent and the diamines, Examples D and E were prepared. Example D was made with a mole ratio DODPA:OPNA
of 1:1 in 1-decane solvent with enough t-butyl peroxide to cause greater than 90 mole % of the diaryl amines to go through dehydrocondensation with the 1 decane. Example E
was made with a mole ratio DODPA:OPNA of 2:1 in a penta-erythritol ester of C~-C9, linear and branched fatty acids.
Example E was made with t-butyl peroxide in a similar fashion as in Ex. i of U.S. Patent 3,492,233, where about 70 mole % of the diarylamine was dehydrocondensed with the ester. - -Table III shows the results of using these antioxidants in oxidation stability tests.
TABLE III
OCS Tests ~1 425F, 72 Hours A1, Ti, Ag, Steel Present DODPA:PNA (2 Wt.%) p Vis 0 TAN
%

Example 2 2:1 27.8 2.41 D of Example 11 1:1 78.0 11.26 E of Example 11 2:1 68.3 10.71 I

As can be seen from Table III, the amine antioxi-dants which have dehydrocondensed with the solvent (Examples D and E) are dramatically less efficient antioxidants in terms of D Vis % or D TAN.
Example E with'the higher more preferred DODPA ratio produced slightly better results but was not comparable to Example 2 with the same DODPA:OPNA ratio.
~T~fIITE SHEET (RULE 26j R'O 95/16765 a ~ ~ ~ ~ ~ PC1'/ITS94114539 Examg],e 12 To better illustrate the differences from the prior art such as U.S. Patent 3,573,206, antioxidants were prepared from diphenylamine and N-phenyl-naphthylamine.
A sample was prepared according to Example 9 of U.S.
Patent 3,573,206 using unsubstituted forma of diphenyl-amine and N-phenylnaphthylamine in a 1:1 mole ratio. When this antioxidant was used in synthetic ester oils in the 400 and 425°C oxidation corrosion stability (OCS) tests for 72 hours the test samples developed heavy sludge deposits.
Thereafter the antioxidants of Table IV were prepared using substituted forms ofthe diarylamines. Thesamples of Table IV were tested in the (OCS) tests for 72 hours at 400 and at 425°F. The results are shown in TableV.
Samples A through J were tested using antioxidants A through J in an amount equal to 2 wt. % of the reaction product of-the diarylamines. The amounts recited in Table V differ from 2 wt. % because those values include the ester lubricant used in preparing the antioxidant-sample.
In Table V the synthetic ester oil samples from antioxi-dants A, B, and -C made using an organic peroxide have significantly less sludge in the OCS test 72 hrs at 425'°F
than the other samples.
Samples D through -J were made with alternative oxidizing agents disclosed in U. S. Patent 3,573,206.
Sample J resulted in large losses of magnesium metal which is unacceptable. Samples D and E used KMnO, as the oxidizing agent to -promote oligomerization -of the diarylamines and resulted in inferior performance to samples A, B, and C in the OCS test as measured by the change in viscosity and TAN at both 400 and 425°F.' Samples D and E had inferior performance to samples A, B, and C in the OCS test as measured by sludge after aging at 425°F.
Samples F through J generally resulted in -inferior performance in the OCS test to samples A, B, and C.
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W O 95/16765 PCTlUS94f 14539 -27~
Examp~, a 13 p,p~-Di-a-methylstyryl diphenylamine (11..31 g, 0.03 mole), p-t,,-octyl-N-phenyl-1-naphthylamine (9.95 g, 0.03 mole), ester lubricant (21.26 g) were mixed and heated to 140oC. ~-Butylperoxide (10.53 g, 0.072 mole) was adde~3 dropwise under nitrogen gas. The addition took about 30 minutes. The reaction was kept at 140-145oC for 3 hours while the ,~-butyl alcohol formed was being distilled. The reaction temperature was then raised to 170-175oC and kept there for ~5 minutes. Vacuum was applied at 170-175oC for 25 minutes to remove any residual t-butyl alcohol. HPLC
of the resultant product showed that it is a mixture of p,p~-di-methylstyryl diphenylamine homo-oligomers and p,p~-di-methylstyryl diphenylamine and p-~-octyl-N-1-naphthylamine cross oligomers.
Although the invention has been described in terms of specific embodiments of a manner the invention may be practiced, this is by way of illustration only and the invention is not necessarily limited thereto since alternative embodiments and operating techniques will become apparent to- those skilled in the art. Accordingly, modifications are contemplated which can be made without departing from the spirit of the.described invention.
While inaccordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.

Claims (19)

CLAIMS:
1. An antioxidant composition comprising the reaction product of:
(a) at least one N-aryl naphthylamine;
(b) at least one diphenylamine; and (c) an organic peroxide free radical source; said N-aryl naphthylamine having up to three alkyl, styryl, or methyl substituted styryl groups, or combinations thereof, on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; said diphenylamine having up to three alkyl, styryl, or methyl substituted styryl groups, or combinations thereof, on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; wherein the mole ratio of said diphenylamine to said N-aryl naphthylamine is from 1:1 to 10:1 and wherein the reaction of (a), (b), and (c) is conducted at temperatures from about 70°C to about 200°C, and wherein said reaction product contains at least 35 mole percent of said diphenylamine and said N-aryl naphthylamine in the form of cross oligomers.
2. An antioxidant composition of claim 1, wherein the mole ratio of diphenylamine to N-aryl naphthylamine is from 1.2:1 to 5:1.
3. An antioxidant composition of claim 2, wherein the mole ratio of diphenylamine to N-aryl naphthylamine is from 1.5:1 to 4:1.
4. An antioxidant composition of claim 1, 2 or 3, wherein said groups on the diphenylamine are independently C4 to C8 alkyl radicals or styryl or methyl substituted styryl groups, and said groups on the N-aryl naphthylamine are independently C4 to C8 alkyl radicals or styryl or methyl substituted styryl groups.
5. An antioxidant composition of claim 4, wherein the alkyl groups on said diphenylamine and N-aryl naphthylamine are t-butyl or t-octyl groups.
6. An antioxidant composition of any one of claims 1 to 5, wherein the N-aryl naphthylamine is a N-phenyl-naphthylamine.
7. An antioxidant composition of any one of claims 1 to 6, wherein said organic peroxide free radical source is present in amounts from 0.5 to 3 moles per mole of combined moles of diphenylamine and N-aryl naphthylamine.
8. An antioxidant composition of claim 7, wherein they organic peroxide free radical source is present in amounts from 1.0 to 1.5 moles per mole of combined moles of diphenylamine and N-aryl naphthylamine.
9. An antioxidant composition of any one of claims 1 to 8, wherein said reaction product contains less than 30 weight % of diphenylamine and N-aryl naphthylamine in monomeric form.
10. An antioxidant composition of any one of claims 1 to 9, wherein said reaction product contains at least 10 mole percent of said diphenylamine and said N-aryl naphthylamine in the form of homooligomers of diphenylamine.
11. An antioxidant composition of any one of claims 1 to 3, wherein said at least one N-aryl naphthylamine is unsubstituted.
12. An antioxidant composition of any one of claims 1 to 3, wherein said at least one N-aryl naphthylamine is substituted.
13. An antioxidant composition of claim 1, 2, 3, 11 or 12, wherein said at least one diphenylamine is unsubstituted.
14. An antioxidant composition of claim 1, 2, 3, 11 or 12, wherein said at least one diphenylamine is substituted.
15. A process for making an antioxidant composition comprising reacting at least one N-aryl naphthylamine having up to three alkyl, styryl, or methyl styryl groups or combinations thereof on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; with at least one diphenylamine having up to three alkyl, styryl, or methyl styryl groups or combinations thereof on each aryl ring, wherein said alkyl has from 1 to 20 carbon atoms; in the presence of an organic peroxide free radical source, at a mole ratio of said diphenylamine to said N-aryl naphthylamine from 1:1 to 10:1 and at a temperature from 70° to 200°C.
16. A process of claim 15, wherein the reaction is conducted at a temperature of from 130° to 150°C.
17. A process of claim 15 or 16, wherein the process is conducted in the presence of a solvent.
18. A process of claim 17, wherein the solvent is a synthetic ester lubricant.
19. A lubricating oil composition stabilized against oxidative and thermal degradation comprising:
a) a lubricating oil containing synthetic ester oils subject to oxidative or thermal degradation, and b) from 0.1 to 10 weight percent of an antioxidant composition of any one of claims 1 to 14.
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US5689270A (en) 1997-11-18
US5499032A (en) 1996-03-12

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