JPH064850B2 - Thermo-oxidatively stable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermooxidatively stable sulfonate-containing compositions. In particular, the present invention relates to thermo-oxidative stabilization of normally thermo-oxidatively labile organic compounds, including both natural and synthetic.

High molecular weight alkaryl and alkali metal and alkaline earth metal salts of petroleum sulfonic acid have long been widely used as dispersants and rust or corrosion inhibitors in numerous applications such as lubricating oils, greases and anticorrosion paints.

It has been reported that alkali metal and alkaline earth metal sulfonates can be combined with carboxylic acids, esters or soaps to enhance corrosion and oxidation inhibition performance. For example, they are US Patents 3,090,750, 3,625,894,
No. 3,684,726, No. 3,763,042, No. 4,201,681 and Japanese Patent Publication No. 48-12238.

Bergen et al., U.S. Pat. A dispersant selected from, a lubricating oil, and an acidic coupling agent are disclosed. However, it has not been shown to increase thermooxidative stability, nor has it been suggested to synergize with antioxidants.

(. Koenig et al) König other during U.S. Patent No. 3,625,894, alkaline earth metal petroleum sulfonates and / or C ₁₀ -C oil-soluble alkaline earth ₃₆ fatty acid metal salts and / or alkyl sulfamide - carboxylic A lubricating composition is described in combination with an oil-soluble alkaline earth metal salt of an acid and a rust inhibitor consisting of benzotriazole. The compositions disclosed in the above U.S. Pat. No. 3,625,894 are said to provide protection against corrosion for lubricants and mineral oils that must withstand extreme temperatures, for example turbine oils, temperatures up to 170 ° C. It is said that
Only 100 ° C and 100 hours have been demonstrated. Furthermore, it does not suggest the use of major antioxidants to provide synergy.

Haak et al., U.S. Pat. It teaches the inclusion of a synergistic mixture of magnesium with a naphthalene salt. However, there is no disclosure in this patent that the thermo-oxidative stability of this type of grease is enhanced.

U.S. Pat. No. 3,763,042 to Gannon et al. Discloses zinc dialkylnaphthalene sulfonates, aliphatic monohydric alcohols and aliphatic C ₁₂ -C ₂₄ monocarboxylic acids,
Described is a clay thickening grease having a synergistic proportion of zinc naphthenate and other additives including certain other antioxidants. However, there is no evidence there for any combination with oxidation inhibitors.

In U.S. Pat.No. 4,201,681, Lipinski et al.
nski et al.) disclose a metalworking lubricant composition comprising mineral oil and an additional combination material of barium lanophosphate soap and barium sulfonate, such as barium didodecylbenzene sulfonate. There is. Although Lipinski et al. Compositions have been tested for a number of properties, such as corrosion, stain and drawability, stacking tests for stain and friction measurements, and visual inspection for wear and galling, improved stability to thermal oxidation has not been investigated. It has not been proved.

CA 79 (26): 1973, as summarized in 147965h.
Japanese Patent Publication No. 48-12238 published on February 15, 2000 discloses a rust preventive oil composition obtained by combining mineral oil with zinc soap of wool fatty acid and barium sulfonate. Although improved rust inhibiting properties and waterproofing and weathering resistance are reported, no mention is made of rust inhibiting compositions having enhanced thermo-oxidative stability.

Stadmiller et al., U.S. Pat.
No. 92,851 discloses a basic zinc dialkyldithiophosphate and 2,6-di-t for stabilizing a paraffinic mineral oil lubricant.
-Discloses the use of the combination with butylphenol.

U.S. Pat.No. 6,265,855 to Dexter et al. Discloses the use of hindered hydroxybenzoic acid and esters of hydroxyphenylalkanonic acid as stabilizers for organic materials that undergo oxidative degradation. Scott U.S. Pat.Nos. 4,213,892 and 4,354,
No. 007 discloses antioxidants as stabilizers for polymers, but neither suggests combining these stabilizers with sulfonates.

A thermooxidatively stable composition, comprising oil-soluble barium, calcium, magnesium or zinc sulphonate, a main antioxidant and optionally an alkyl or alkenyl succinic acid or a partially esterified alkyl or alkenyl succinic acid. Thermal oxidation comprising an alkali metal soap or alkaline earth metal soap or zinc soap or a mixture of any of these, optionally a secondary antioxidant, and optionally a carrier for the thermooxidatively stable composition. It has been unexpectedly discovered that the incorporation of a thermostable composition significantly and very effectively improves the thermooxidative stability of organic compounds that are normally thermooxidatively unstable. When added to organic compounds that are normally thermo-oxidatively unstable, the oxidative degradation and deterioration caused by thermal effects is due to the synergistic effect of the thermo-oxidative stabilizer composition or package components, Alkali metal soaps or alkaline earth metals of alkyl or alkenyl succinic acid or partially esterified alkyl or alkenyl succinic acid stabilized only with / or secondary antioxidants or only with oil soluble metal sulfonates It is suppressed to a much greater extent than is found in prior art compositions containing only oil soluble metal sulfonates stabilized by soaps or zinc soaps or mixtures thereof.

Another object of the invention is to provide a method of stabilizing a normally thermooxidatively unstable organic compound by blending the labile compound with an effective amount of the above thermooxidative stabilizing composition. That is.

The present invention also contemplates a thermo-oxidative stabilizer package comprising only the thermo-oxidative stabilizer composition described above for use in stabilizing a normally thermo-oxidatively unstable organic compound.

In the first main aspect of the invention, (A) a normally thermooxidatively labile organic compound and an effective amount of (B) (i) selected from barium, calcium, magnesium, zinc or a mixture of any of the above. A stabilizer comprising an oil-soluble sulfonate of a metal and (ii) an alkyl or alkenyl succinic acid or a partially esterified alkyl or alkenyl succinic acid alkali metal soap or alkaline earth metal soap or zinc soap, or An effective amount of a mixture of any of the stabilizers, (iii) an effective amount of at least one primary antioxidant, optionally (iv) an effective amount of a secondary antioxidant, and optionally (v) There is provided a thermo-oxidatively stabilized composition comprising a thermo-oxidative stabilizing composition comprising a carrier for the thermo-oxidative stabilizing composition.

In a second main aspect of the invention, (A) a normally thermooxidatively labile organic compound and an effective amount of (B) (i) selected from barium, calcium, magnesium, zinc or a mixture of any of the foregoing. An oil-soluble sulfonate of a metal to be treated, (ii) an effective amount of at least one major antioxidant, optionally (iii) an effective amount of a secondary antioxidant, and optionally (iv) thermooxidative stabilized There is provided a thermo-oxidatively stabilized composition comprising a thermo-oxidative stabilizing composition comprising a carrier for the composition.

The present invention also provides a method for stabilizing a compound, which comprises the step of blending a normally thermooxidatively labile organic compound with an effective amount of any of the above thermooxidatively stabilizing compositions (B). provide.

Further contemplated by the present invention is a thermo-oxidative stabilizer composition comprising only any of the above components (B).

The normally thermo-oxidatively labile organic compounds used in the present invention include naturally occurring as well as synthetic organic compounds. These include, but are not limited to, petroleum products, aliphatic ester type lubricating oils such as dihexyl azelate, di- (2-ethylhexyl) -azelate, di- (3,5,5-trimethylhexyl). ) Glutarate, diisoamyl adipate, pentaerythritol tetracaprolate, triamyl tricarbarate, dipropylene glycol dipelargonate, 1,5-pentanediol di- (2-ethylhexanoate), etc. , For example linseed oil, fat, beef tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, etc., hydrocarbon substances such as gasoline, natural and synthetic diesel oils, mineral oils, fuel oils, naphthenes Petroleum, drying oil, cutting oil, wax, resin, etc., fatty acid, In certain soaps, trimethylolpropane pelargonate, EPT rubber, chlorinated rubber, natural rubber or the like.

Other materials which are thermo-oxidatively stabilized according to the invention are cross-linked and thermoplastic resins which have linear, branched and / or cyclic hydrocarbon sequences in the main or side chain. Things, and in some cases oxygen,
Those substituted by nitrogen and / or phosphorus, thermoplastic polymers and various synthetic organic polymeric substances, such as those produced from the polymerization of vinyl halides, or vinyl halides and unsaturated polymeric compounds, such as vinyl esters, α, β-unsaturated acids, α, β-unsaturated esters, α, β-unsaturated ketones, α, β-unsaturated aldehydes and unsaturated hydrocarbons such as those produced by copolymerization with butadiene and styrene , Poly α-olefin copolymers, poly α containing polyurethanes such as those prepared from polyols and organic polyisocyanates
-Olefins such as polyethylene, polypropylene, polybutylene, polyisoprene, polyamides such as polyhexamethylene adipamide, polyester,
For example, polymethylene terephthalate and polybutylene terephthalate, polycarbonates, polyacetals, polystyrenes, polyethylene oxides, and copolymers such as high-impact polystyrene containing copolymers of butadiene and styrene, as well as copolymerization of acrylonitrile, butadiene and / or styrene. There is something like that generated by.

The barium, calcium, magnesium or zinc metal sulfonates useful in the practice of this invention include a wide range of compounds known to those skilled in the art. Alkaryl or polyalkaryl sulfonates are described in U.S. Pat. No. 2,764,548
No. 3,957,859 and No. 4,201,681.

Aromatic organic substrates such as aromatic petroleum fractions and benzene and its homologues such as alkylbenzene, toluene, xylene,
Polyalkylbenzenes and higher alkyl mono- and di- and polysubstituted benzenes, such as nonyl and decyl and dodecyl, straight chain and branched substituted benzenes and the corresponding naphthalenes, are preferentially oil-soluble (selective in organic hydrocarbon solvents, etc.). Sulphonate which is soluble in water) and preferentially water-soluble (and alcohol-soluble, ie selectively extractable with water and alcohol etc.).

As is the case in U.S. Pat. It is preferably used as a water-insoluble substance selected from chlorinated hydrocarbons and the like. The procedure for making those starting materials is fully described in the above-referenced US Pat. No. 2,764,548.

Aromatic mono- and disulfonic acids such as dinonylnaphthalene mono- and polysulfonic acids are fully described in the above-referenced US Pat. No. 3,957,859. Typically,
These alkyl or polyalkylaryl sulfonic acids are 150-2,500 or more, preferably 20
It has a molecular weight in the range of 0 or higher, most preferably 325 or higher. Suitable sulfonates are those having an alkaryl group, such as alkylated benzene or alkylated naphthalene. Examples of this type of sulfonic acid include dioctylbenzene sulfonic acid, didodecyl benzene sulfonic acid, dinonyl naphthalene sulfonic acid, dilauryl benzene sulfonic acid, lauryl cetyl benzene sulfonic acid, polyolefin alkylated benzene sulfonic acids such as polybutylene alkylated There are benzene sulfonic acids and polypropylene alkylated benzene sulfonic acids. Particularly preferred aromatic sulfonates in the practice of the present invention are dinonylnaphthalene sulfonates, nonyl naphthale sulfonates, petroleum sulfonates, dodecylbenzene sulfonates and the like.

Metal salts or sulfonates useful in the present invention are barium, calcium, magnesium, zinc salts or mixtures of any of the foregoing. The metal sulfonate may be produced by conventional methods known to those skilled in the art. The metal salt of an aromatic sulfonic acid may be prepared by reacting an inorganic metal donor compound such as a metal hydroxide, a metal oxide or a metal carbonate with an alkyl or dialkyl or polyalkyl aromatic sulfonic acid. In this way, the reaction of, for example, any of barium hydroxide, calcium oxide, magnesium oxide, zinc hydroxide, etc., with the corresponding alkaryl sulfonic acid will yield the appropriate metal sulfonate. Suitable components of the thermal oxidation stabilizing composition are barium sulfonate, calcium, magnesium or zinc, such as barium dinonylnaphthalene sulfonate, calcium dinonylnaphthalene sulfonate, magnesium dinonylnaphthalene sulfonate, zinc dinonylnaphthalene sulfonate, Barium alkylbenzene sulfonate, especially barium dodecenyl benzene sulfonate, calcium alkyl benzene sulfonate, especially calcium dodecenyl benzene sulfonate, magnesium alkyl benzene sulfonate, especially magnesium dodecenyl benzene sulfonate, zinc alkyl benzene sulfonate, In particular, zinc dodecenylbenzene sulfonate, or a mixture of any of these. Particularly preferred are barium dinonylnaphthalene sulfonate, calcium dinonylnaphthalene sulfonate, magnesium dinonyl naphthalene sulfonate, and zinc dinonyl naphthalene sulfonate, which are each trade names "NA-SUL (trademark) BSN", "NA-
"SUL (TM) CA", "NA-SUL (TM) MG" and "NA-SU"
L (trademark) ZS "under King Industries (king l
ndustries), Norwalk, Connecticut.

Contemplated for use as an optional stabilizer is an alkyl or alkenyl succinic acid partially esterified alkyl or alkenyl succinic acid alkali metal soap or alkaline earth metal soap or zinc soap, or a mixture of any of the foregoing. is there. Preferred are alkyl or alkenyl succinic acids or partially esterified alkyl or alkenyl succinic acids having 6 to about 50 carbon atoms, and most preferably about 10 to about 30 carbon atoms.

Compounds useful as optional stabilizers can be obtained by any known method, but are generally inorganic metal donor compounds such as barium, calcium, magnesium or zinc, etc., suitable alkyl or alkenyl succinic or partially esterified alkyl compounds. Alternatively, it can be obtained by reacting with alkenyl succinic acid. Preference is given to alkenyl succinic acid barium soap, dodecenyl succinic acid half methyl ester barium soap, alkenyl succinic acid calcium soap, dodecenyl succinic acid half methyl ester calcium soap, alkenyl succinic acid magnesium soap, dodecenyl succinic acid It is a magnesium soap of a half methyl ester, a zinc soap of alkenyl succinic acid, a zinc soap of a half methyl ester of dodecenyl succinic acid or a mixture of any of the foregoing. Particularly preferred are barium, calcium, magnesium or zinc soaps of the dodecenylsuccinic acid half-methyl ester.
One convenient method of preparation is to provide an alkyl or alkenyl succinic acid or the corresponding anhydride or partial ester with a metal donor in the presence of a metal sulfonate as described above and a small amount of lubricating oil at ambient to slightly elevated temperatures. , For example, with barium hydroxide monohydrate, calcium oxide, magnesium oxide or zinc hydroxide monohydrate.

Next, the generated soap is heated to dehydrate, and the lubricating oil component is added while stirring.

The primary antioxidant of the present invention may be at least one phenolic antioxidant, at least one aromatic amine antioxidant, or any combination of the foregoing. Monophenols, thiobisphenols and polyphenols are all suitable phenolic antioxidants.
Preferably, the phenolic antioxidant comprises a hindered antioxidant, an ester thereof including those disclosed in U.S. Pat. No. 3,285,855 to Dexter et al., Or a combination of any of the foregoing. That is. Examples of suitable primary antioxidants include methylene bis-
4,4'-2,6-di-t-butylphenol, 4,
There are 4'-dioctyldiphenylamine, alkylated phenyl-α-naphthylamine, t-butylphenol derivatives, alkylated diphenylamine, phenyl-α-naphthylamine, sulfur-containing hindered phenols, or mixtures of any of the foregoing.

The synergistic effect of the metal sulfonate, the optional stabilizer and the main antioxidant component may be enhanced by the additional synergistic effect of the three components optionally with an effective amount of the secondary antioxidant. Secondary antioxidants of this type typically include thiocarbamates, thioesters, or combinations of any of the foregoing, with zinc diamylthiocarbamate being preferred: Where R is C ₅ H ₁₁ or zinc dibutylthiocarbamate: (Wherein R is C ₄ H ₉ ).

Typically, the optional carrier will include synthetic hydrocarbon-based fluids such as poly alpha-olefins or mixtures of various poly alpha-orphines, mineral oils, waxes, esters, halocarbon fluids, polyglycols or mixtures of any of these. Can be composed of Preferred as carriers are crystalline waxes, mineral spirits or kerosene. Particularly preferred as carrier is light mineral oil, poly alpha-olefin or mixtures thereof. Mineral oils useful as carriers in the compositions of the present invention generally have a viscosity of at least about 30 SU at 100 ° F (37.7 ° C).
It has S to about 600 SUS. More particularly, the mineral oil has a viscosity at 100 ° F (37.7 ° C) of about 40 SUS to about 350 SUS, preferably at 100 ° F (37.7 ° C) about 50 SUS to about 150 SUS. In general, the term "light mineral oil" is accepted to mean an oil having a viscosity at 100 ° F of less than about 150 SUS.

Mineral oil can vary widely during refining,
They can be obtained from various raw materials including paraffinic, naphthenic, asphaltic or mixed radicals.
Mineral oils can be processed by any conventional refining process including hydrotreating, acid treatment, extraction and the like, and blends or mixtures of this type of mineral oil can also be used.

Preferred is that component (A) comprises from about 95 to about 99.95 wt% and component (B) comprises from about 5 to about 0.05 wt% based on the sum of (A) and (B). That is.

In embodiments that include an alkali metal soap or alkaline earth metal soap or zinc soap of any alkyl or alkenyl succinic acid or partially esterified alkyl or alkenyl succinic acid, or a mixture of the aforementioned stabilizer components, a preferred combination is The metal sulfonate component is from about 2 to about 25 wt%, the optional stabilizer component is from about 3 to about 15 wt%, and the major antioxidant component is about 5 to 5 components of the thermal oxidation stabilizing composition. 20 to about 90 wt% and the secondary antioxidant component is 0 to about 40
wt%, and the carrier component is composed of 0 to about 30 wt%.

In an embodiment without any stabilizer component, preferred is from about 2 to about 20 wt% metal sulfonate component, from about 40 to about 90 wt% primary antioxidant component, relative to the four components combined, secondary The antioxidant component is 0 to about 50 wt% and the carrier component is 0 to about 30 wt%.
Is to be configured with.

Thermo-oxidative stabilization involves protection against thermal degeneration and oxidative degeneration.

The compositions of the present invention can be used in numerous applications including, but not limited to, compressor oils, engine oils, gear oils, hydraulic oils, rust inhibitors, slashing oils, synthetic lubricating oils and turbine oils. is not. In short, these compositions can be utilized in any application where thermo-oxidative stability is required. These compositions are particularly useful in high temperature applications, such as temperatures above 150 ° C, especially above 180 ° C, and even above 200 ° C for extended periods of time. Many of these compositions also exhibit enhanced rust and corrosion inhibition properties.

According to the present invention, there is also provided a method of stabilizing a normally thermooxidatively unstable organic compound, which comprises a thermooxidatively stable composition of a normally thermooxidatively unstable organic compound. It comprises a step of blending the product or the package described above with any conventional means known to those skilled in the art, for example, mixing, stirring, dispersing and the like.

The following examples illustrate the invention without limiting it. Unless otherwise indicated, all parts and percentages are by weight. The induction period is the period of protection conferred against increased oxidation and / or acid number.

Thermo-oxidative stability is the change in acid number (mgKHO / g),
It is reflected by color, sludge formation, induction period length, changes in viscosity, infrared absorption or any combination of the foregoing.

ASTM Test Method D4636-86 (Federal Test Methods 5307.1 and 5308.
6 combinations) and a modified version of the 1P48 trial are incorporated in many of the examples below.

The ASTM test method, D4636-86, is conducted as follows. Test sample 200ml in a large glass tube (small container),
Outer diameter of 51 mm and length of about 3 excluding large ground glass joint designed to receive adapter head
Weigh into what has 50 mm. The head, about 100 mm high, houses a standard tapered frosted glass joint for an O-ring compression fit joint for receiving a reflux condenser, thermowell and air supply tube. The thermowell consists of a glass tube with an outer diameter of 5 mm, which is about 425 mm long.
And, it is supposed to be within 35 mm of the bottom of the pipe. The temperature of the sample is type J attached to the remote thermometer
Be monitored using a thermocouple. The air supply tube is made of a glass tube with an outer diameter of 6 mm, which is about 53 in length.
5 mm and inserted within 5 mm of the bottom of the tube. The flange is placed about 15 mm from the bottom of the air tube, and the flange-like test pieces in order from the bottom are washer-shaped aluminum alloy, silver, silicon-iron bronze, grade 1010.
Steel, M50 steel, magnesium and titanium 8% manganese are stacked. These washers have an inner diameter of 6.35 mm ×
Outer diameter 19.05 mm × thickness 0.81 mm, these are ground with silicon carbide paper of grain size # 400 prior to use.
Separate the washers using a glass spacer with an outer diameter of 9 mm and a length of 6 mm. Dry air is passed through the sample at a rate of 10 ± 1 / hour.

The sample vial is immersed in a thermostatically heated hot silicone liquid in a "Sta-Warm" heating bath. The sample is removed through a thermowell joint in the head through a U-shaped tube approximately 600 mm long and reaches the bottom of the main sample tube.

The modified IP48 test is conducted as follows.

36 g of the test sample is weighed into a large glass tube having an outer diameter of 38 mm and a length of about 200 mm excluding the standard tapered ground glass joint at the top. With a glass inlet tube with an outer diameter of 8 mm, the adapter reaching the bottom is inserted into a large glass tube and a reflux condenser is attached to the top. Long copper and iron catalyst materials, each having a length of about 460 mm, are tied around the gas inlet tube to form a tight coil approximately 50 mm in length. The catalyst coil was washed with heptane, air dried, and concentrated hydrochloric acid solution in acetone 15 V / V%
It is activated by immersion in it for 1 minute. After washing with water, then acetone, the coil is air dried.

Immerse the tube in a heating bath for 15 minutes and use O-grade air (zero
grade air) and pass the sample at a rate of 15 / hour.

Procedure A 2 with heating mantle, stirrer, cooler and thermometer
In a 000 ml flask, 750.1 g of 40.5% active zinc zinc dinonylnaphthalenesulfonate in naphthenic petroleum, 161.2 g of dodecenyl succinic anhydride, 4 cSt of a synthetic hydrocarbon-based liquid [poly α-olefin mixture, "Emery ™ 3004
PAO ", Quantum Chemical Corporation (Quan
tum Chemical Corp.), Ohio, Cincinnati] 5
Charge 0 g, 20.8 g zinc oxide, and 200 g methanol and stir. The stirred reaction mixture is heated to reflux temperature and held for 2 hours. The stirred mixture is then heated to 150 ° C. under vacuum to strip methanol and the reaction product is polish filtered. The reaction product "NA-SUL ™ ZS-HT", King Industries] is found to contain 31.36% zinc sulphonate and 18.24% zinc soap of the half-methyl ester of dodecenylsuccinic acid.

Procedure B 1 with heating mantle, stirrer, cooler and thermometer
A 000 ml flask is charged with 339.6 g of a 39.1% solution of dinonylnaphthalene sulfonic acid in heptane and 6.11 g of low density magnesium oxide. Dean-Stark
A Stark) trap is placed between the flask and the reflux condenser and the reaction components are heated to the reflux temperature with stirring. 11
After / 4 hours, water is removed from the reaction mixture via a trap up to a pot temperature of 101 ° C. The reaction product is cooled and light mineral oil (75 seconds solvent extracted naphthenic petroleum, "Telura (TM) 415", Exxon.
Add 165.4 g of Exxon Company, Houghton, Text State, USA. Strip the heptane under vacuum (25 torr) up to a pot temperature of 150 ° C.
The reaction product is cooled to 65 ° C. and dodecenyl succinic anhydride is added.
68.8 g, 100 g of methanol and 5.5 g of low density magnesium oxide are added. The resulting mixture is then heated to reflux temperature and stirred for 2 hours. The stirred reaction mixture is then heated under vacuum to 150 ° C. to distill the methanol,
The reaction product is filtered. This concentrate (“NA-SUL ™”)
MG-HT ", King Industries) is found to contain 34.33% magnesium sulfonate and 20.35% magnesium soap of dodecenyl half-methyl ester of succinic acid.

Procedure C A 72 flask was charged with 13,986 g of a 50.7% solution of calcium dinonylnaphthalene sulfonate in naphthenic petroleum, 3626 g of isohexadecenyl succinic anhydride and 40 parts of methanol.
Charge 00 g and stir for 30 minutes. Calcium hydroxide 53
5.0 g are added and the stirred reaction mixture is heated to reflux temperature. After 41/2 hours at reflux temperature, methanol is stripped under vacuum at 150 ° C. Light mineral oil (7
5 seconds solvent extracted naphthenic petroleum, [Telura (trademark) 41
5 ", Exxon, Company, USA) 2697 g,
The product obtained is filtered. This reaction product (“NA-SUL
(Trademark) CA-HT ", King Industries) by" high amine "titration and HC1 titration and contains 33.94% calcium sulfonate and 25.19% calcium soap of the half methyl ester of isohexadecenylsuccinic acid. Turns out.

Procedure D In a 2000 ml flask, 700 g of a barium dinonylnaphthalenesulfonate 50.5% solution in naphthenic petroleum, 147.4 g of isohexadecenyl succinic anhydride, 200 ml of methanol.
g and light mineral oil (75 seconds solvent extracted naphthenic petroleum, “Te
lura ™ 415 ", Exxon, Company, USA) 100 g and blend. 55.6 g of barium hydroxide monohydrate are added and the stirred mixture is heated and stirred at reflux temperature for 2 hours. Methanol under vacuum at 150 ° C
Strip with. An additional 56 g of light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura (TM) 415") is added and the material is filtered. The reaction product is analyzed by "high amine" titration and HC1 titration and found to contain 33.44% barium sulfonate and 23.42% barium salt of the half-methyl ester of isohexadecenylsuccinic acid.

Procedure E 10 with heating mantle, stirrer, cooler and thermometer
In a 00 ml flask, 75 g of a 60% solution of dodecenyl succinic acid in naphthenic petroleum and an overbase in light mineral oil.
ased) barium dinonylnaphthalene sulfonate having a total alkali number of 48 g and a sulfonate content
225 g with 45.7% (“NA-SUL ™ BSB”, King Industries) are loaded. The contents of the flask are heated to 100 ° C. and held for 1 hour with stirring to react excess base in the sulfonate with acid to form a mixture of barium soap and unreacted acid. The reaction mixture is then heated to 150 ° C. and stripped under vacuum to give 287 g of reaction product. The reaction product was analyzed by acid-base titration as well as "high amine" titration,
It is found to contain 4.23% free carboxylic acid, 16.32% barium soap of dodecenyl succinic acid and 36.42% barium sulfonate. The product obtained is a clear, viscous brown liquid with an acid number of 16.7 mg KOH / g.

Procedure E 10 with heating mantle, stirrer, cooler and thermometer
In a 00 ml flask, 390 g of a 39% solution of dinonylnaphthalenesulfonic acid in heptane, 14.2 g of acid number zinc and 4
cSt Synthetic Hydrocarbon Based Liquid [Poly α-Olefin Mixture, "Emery ™ 3004 PAO", Quantum Chemical Corporation, Cincinnati, Ohio]
Charge 216 g. The contents of the flask are heated to reflux temperature and held for 4 hours with stirring to react the zinc acid number with the sulfonic acid to form the zinc salt of the sulfonic acid. The stirred reaction mixture is then heated to 150 at atmospheric pressure.
Heat to 0 ° C to strip the heptane, then cool to less than 100 ° C, then strip under vacuum to give 214 g of reaction product. The reaction product is analyzed by "high amine" titration and found to contain 40.95% zinc sulfonate. Reaction product [NA-SUL (TM) ZS ", King Industries, Norwalk, CT]
Is a clear, viscous brown liquid.

Procedure G 1 with heating mantle, stirrer, cooler and thermometer
A 2,000 ml flask is charged with 27,066 g of a 38.41% dinonylnaphthalenesulfonic acid solution in heptane and 478 g of low density magnesium oxide (MgO) and stirred. The stirred reaction mixture is heated to reflux temperature. Dean-
A Stark trap is placed between the flask and the reflux condenser and water is removed until the pot temperature is 100 ° C.
The stirred reaction product is cooled and 8400 g of light mineral oil (75 seconds melt extracted naphthenic petroleum, "Telura (TM) 415, Exxon Company, Houston, TX, USA).
Is added. The stirred reaction mixture is heated to 150 ° C. under vacuum to strip off heptane and the resulting clear concentrate is filtered. The reaction product [“NA-SUL ™ MG” King Industries] was analyzed by “high amine” titration and found to contain 50.28% magnesium sulfonate.

Example 1 Product prepared by the method of procedure A [0.67 g zinc dinonyltanaphthalene sulfonate, 0.38 g zinc soap of half methyl ester of dodecenyl succinic acid, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture , "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation) 1.12 g. (NA-SUL ™ ZS-HT, King Industries) 2.17 g and major antioxidant (methylenebis-4,4′-2,6-di-t-butylphenol “Ethanox ™ 702”, Ethyl Corporation (Baton Rouge, LA) 0.56 g of solvent-refined heavy paraffinic distillate (petroleum “Sunpar ™ LW110”, Sun Refining
And Marketing Company (Sun Refining
and Marketing Company), Philadelphia, PA) blended by dissolving in 217.2 g. 200 ml of this blend is placed in a test vial which is then subjected to 150 D under ASTM D4636-86 conditions.
Expose to a temperature of ° C. The initial blend had an acid value of 0.78 mg K
It is a light brown flowing liquid having an OH / g and a kinematic viscosity of 22.04 cSt at 40 ° C. The induction period lasts 185 hours. After 185 hours of exposure, the acid number is 0.83 mg KOH / g and the viscosity at 40 ° C. is 21.80 cSt.

Comparative Example 1A * 200 ml of solvent refined heavy paraffinic distillate (petroleum "Sunpar (TM) LW110", Sun Refining & Marketing Company) was placed in a test vial which was then ASTM D4636. 150 ° C under -86 condition
Exposure to temperature. The initial sample had an initial acid value of 0.16 mg KOH / g
And a colorless flowable liquid having a kinematic viscosity of 20.67 cSt at 40 ° C. After 16 hours, the sample turning orange has an acid number of 3.67 mg KOH / g and a viscosity of 27.30 cSt at 40 ° C.

Comparative Example 1B * 200 ml solvent-purified heavy paraffinic distillate (petroleum “Sunpar ™ LW110”, Sun Refining & Marketing Company) and main antioxidant (methylenebis-4,4′-2, A blend is prepared by mixing 0.4169 g of 6-t-butylphenol “Ethanox ™ 702”, Ethyl Corporation). Place 200 ml of this blend in a test container,
It is then exposed to a temperature of 150 ° C under ASTM D4636-86 conditions. The initial blend is a nearly colorless flowable liquid with an acid value of 0.16 mg KOH / g and a kinematic viscosity at 40 ° C. of 20.7 cSt. The induction period is 83 hours. After 185 hours of exposure, the acid value was 23.39 mg KOH / g and the viscosity was 1 at 40 ° C.
It is 19.77 cSt.

Example 2 Product of Procedure A [Zinc dinonylnaphthalene sulfonate.
67g, 0.38g zinc soap of dodecenyl succinic acid half methyl ester, 4cSt synthetic hydrocarbon-based liquid (poly α-
Olefin mixture, "Emery ™ 3004 PAO", Quantum Chemical Corporation 1.12 g, ("NA
-SUL ™ ZS-HT ", King Industries)] 2.7 g and main antioxidant (4,4'-dioctyldiphenylamine" Vanlube ™ 81 ", RT Vanderbilt Company (RTVanderb).
ilt Co.), Norwalk, Conn.) 0.56 g of solvent refined heavy paraffinic distillate (petroleum “Sunpar ™”).
LW110 ", Sun Refining and Marketing Company) 217.2 g to prepare a blend. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under ASTM D4636-86 conditions. The initial blend had an acid value of 0.76 mg KOH / g and a kinematic viscosity of 22.09 cSt at 40 ° C.
It is a light brown fluid oil having a. The induction period lasts 185 hours. After 185 hours of exposure, the sample, which turned into a brown transparent liquid, had an acid value of 0.89 mg KOH / g and a viscosity at 40 ° C.
It has 22.26 cSt.

Example 3 Product prepared by the method of Procedure A [0.174 g zinc dinonylnaphthalene sulfonate, 0.098 g zinc soap of half methyl ester of dodecenyl succinic acid, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 0.288 g, (" NA-SUL (trademark) ZS-HT ", King Industries)] 0.56 g and main antioxidant (4,4'-dioctyldiphenylamine" Vanlube
(Trademark) 81 ”, 0.55 g of RT Vanderbilt Company) 218.9 g of solvent refined heavy paraffinic distillate (petroleum“ Sunpar (trademark) LW110 ”, Sun Refining and Marketing Company)
The blend is prepared by dissolving in. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under ASTM D4636-86 conditions.

The initial blend is a nearly colorless flowable liquid with an acid number of 0.32 mg KOH / g and a kinematic viscosity at 40 ° C of 21.35 cSt. The induction period lasts 88 hours. After 88 hours of exposure, the sample, which turns into a brown flowing liquid, has an acid number of 0.41 mg KOH / g and a viscosity of 22.49 cSt at 40 ° C.

Example 4 Product of Step B [1.12 g magnesium dinonylnaphthalene sulfonate, 0.442 g magnesium soap of half methyl ester of dodecenyl succinic acid, light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura (TM) 415", Exxon
Company, USA) 0.708 g, ("NA-SUL (TM) MG-
HT ", King Industries)] and 0.55 g of a main antioxidant (4,4'-dioctyldiphenylamine" Vanlube (trademark) 81 ", RT Tea Vanderbilt Company) are solvent-purified heavy paraffin-based distillation. Goods (Petroleum "Sunpar (trademark) LW110", Sun Refining & Marketing Company)
A blend is prepared by dissolving in 217.2 g. Place 200 ml of this blend in a test container,
It is then exposed to a temperature of 150 ° C under ASTM D4636-86 conditions.

The initial blend is a light brown flowing liquid with an acid number of 0.25 mg KOH / g and a kinematic viscosity of 20.75 cSt at 40 ° C. The induction period lasts 72 hours. After 72 hours of exposure, the sample, which turns into a brown flowing liquid, has an acid number of 0.62 mg KOH / g and a viscosity of 21.13 cSt at 40 ° C.

Example 5 Product of Procedure C [calcium dinonylnaphthalene sulfonate 0.76 g, dodecenyl succinic acid half methyl ester calcium soap 0.45 g, light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura ™ 415", Exxon Company, USA) 0.99 g, (“NA-SUL ™ CA-HT”,
King Industries)] 2.2 g and major antioxidant (4,4'-dioctyldiphenylamine "Vanlub
e ™ 81 ", RT Tea Vanderbilt
Company) 0.55 g from solvent-refined heavy paraffinic distillate (petroleum "Sunpar (trademark) LW110", Sun Refining & Marketing Company) 217.2 g
The blend is prepared by dissolving in. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under ASTM D4636-86 conditions.

The initial blend has an acid number of 0.32 mg KOH / g and a kinematic viscosity at 40 ° C. of 20.66 cSt. The induction period lasts 16 hours. After 16 hours of exposure, the acid value is 3.86 mg KOH / g and the viscosity is 24.45 cSt.

Comparative Example 5A * 200 ml of solvent refined heavy paraffinic distillate (petroleum "Sunpar (TM) LW110", Sun Refining & Marketing Company) and main antioxidant (4,4'-dioctyldiphenylamine "Vanlube").
A blend is prepared by mixing 0.3793 g of TM 81 ", RT Tea Vanderbilt Company). 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C under ASTM D4636-86 conditions. The initial blend had an acid value of 0.14 mg KOH /
and a kinematic viscosity at 40 ° C. of 20.83 cSt.
The induction period lasts 8 hours. 16 hours after exposure, acid value is 2.97
The mg KOH / g and the viscosity are 25.92 cSt.

Example 6 0.86 g calcium dinonylnaphthalene sulfonate and calcium soap of hexadecenyl succinic acid monomethyl ester in 1.0604 g light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura ™ 415", Exxon Company, USA) Stock solution consisting of 0.60 g ("NA-SUL (trademark) CA
-HT ", King Industries), major antioxidants (sulfur-containing hindered bisphenol" Irganox (TM) L115 ", Chiver Geigy Corporation, Hawthorne, NY) 0.6291 g, and light mineral oil (7
5 seconds solvent extracted naphthenic petroleum, "Telura (trademark) 41
5 ") is blended to give a blend consisting of 1%" NA-SUL ™ CA-HT "and 0.25% primary antioxidant. Approximately 36 g of this blend is placed in each of five identical test containers, which are 150 ° C under modified IP48 test conditions.
Exposure to temperatures. Test tube from test bath 16, 21,
Remove after 26, 31 and 36 hours. Acid value (mg KOH /
The changes in g) are -0.02, 0.13, 1.02, 1.21 respectively.
And 1.32. No sludge was found during the 16 or 21 hour test, but during the 26 hour test there was sludge exhibiting an induction period, which lasted for 21 hours.

Comparative Example 6A * A major antioxidant (sulfur-containing hindered bisphenol "Irganox ™") dissolved in 249.1 g of light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura ™ 415", Exxon Company, USA). 415 ", Chiver Geigy Corporation). About 36 g of this blend is placed in each of 5 identical test vials and they are exposed to a temperature of 150 ° C. under modified IP48 test conditions. Test tube from test bath 16,22.5,27.5,3
Remove after 2 and 37.5 hours. The changes in acid value (mg KOH / g) were 0.41, 1.12, 1.66, 1.89 and 2. respectively.
It is 13. 16-hour sample contains 22.5 sludge traces
The time sample has a film of sludge on the wall of the test tube.

Comparative Example 6B * Light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura (trademark) 415", Exxon Company, USA) Main antioxidant (2,6-di-t-butylphenol derivative "dissolved in 99.75 g" 0.2471 g of a blend consisting of Irganox ™ L130 ", Chiver Geigy Corporation, 0.1212 g and alkylated phenyl-α-naphthylamine" Irganox ™ L57 ", Chiver Geigy Corporation, 0.1259 g) is prepared. About 35.16 g of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under modified IP48 test conditions. The initial blend is a clear, amber, flowable liquid with an acid number of 0.16 mg KOH / g. After 65 hours of exposure, the acid value is 3.5 mg KOH / g,
A large amount of black sludge approximately 1 mm thick covers an area of about 20 cm ² at the bottom of the test container.

Example 7 Barium dinonylnaphthalene sulfonate, dissolved in 700.0 g of light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura ™ 415", Exxon Company, USA) 2.
A stock solution is prepared consisting of a blend of 47 g and 1.41 g barium soap of the half-methyl ester of dodecenylsuccinic acid in 3.16 g of naphthenic petroleum ("NA-SUL ™ BSN-HT", King Industries). In 99.75 g of this stock solution, the main antioxidant (2,6-di-t-butylphenol derivative "Irganox (trademark) L130", Chiver Geigy Corporation, 0.1251 g and alkylated phenyl-α was used.
0.2505 g of naphthylamine "Irganox (TM) L57", Chivergeigy Corporation, 0.1259 g) is dissolved to give a blend containing 1% "NA-SUL (TM) BSN-HT" and 0.5% of main antioxidant. This blend about 3
Place 5.01g in the test container, then modify it
48. Exposed to a temperature of 150 ° C under test conditions. The initial blend is a clear, amber, flowable liquid with an acid number of 0.35 mg KOH / g. 65 hours after exposure, the acid value is 2.39 mg KOH /
g, a small amount of black sludge is present at the bottom of the test container in the region of less than 1 mm thickness and less than 3 cm ² .

Example 8 Product of Procedure D [0.75 g barium dinonylnaphthalene sulfonate, 0.44 g barium soap of dodecenyl succinic acid half methyl ester, light mineral oil (75 sec solvent extracted naphthenic petroleum, "Telura ™ 415", Exxon Company, USA) 1.01 g, ("NA-SUL (TM) BSN-HT", King Industries) 2.2 g and major antioxidant (4,4'-dioctyldiphenylamine "Vanlube"
(Trademark) 81 ”, 0.55 g of RT Vanderbilt Company) 217.2 g of solvent refined heavy paraffinic distillate (petroleum“ Sunpar (trademark) LW110 ”, Sun Refining and Marketing Company)
The blend is prepared by dissolving in. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under ASTM D4636-86 conditions. The initial blend had an acid number of 0.34 mg KOH / g and 40
It has a kinematic viscosity of 20.80 cSt at ° C. 16 induction periods
Continue for hours. 16 hours after exposure, the acid value is 2.72 mg KOH /
g, viscosity at 40 ° C. is 23.40 cSt.

Example 9 Product of Procedure E [Partially Neutralized Barium Sulfonate
36.42%, dodecenyl succinic acid composition barium soap 16.
32% (“NA-SUL ™ BSB-DA”, King Industries)] 2.2 g and main antioxidant ((4,4 ′
-Dioctyldiphenylamine "Vanlube ™ 8
1 ", 0.55 g of RT Vanderbilt Company) dissolved in 217.2 g of solvent refined heavy paraffinic distillate (petroleum" Sunpar (TM) LW110 ", Sun Refining & Marketing Company) To prepare the blend. Place 200 ml of this blend in a test vial and then add this to the AS
Exposed to a temperature of 150 ° C. under TM D4636-86 conditions. The initial blend has an acid number of 0.45 mg KOH / g and a kinematic viscosity at 40 ° C. of 20.71 cSt. The induction period lasts 16 hours. 16 hours after exposure, acid value is 3.12mg KOH / g, 40 ℃
The viscosity at is 23.95 cSt.

Examples 1, 2, 3, 4, 6 and 7 relate to the thermo-oxidative stability of petroleum compounds and mineral oils. Figure 4 shows the synergistic effect of the metal sulfonate according to the invention, the stabilizer and the main antioxidant component. Comparative Examples 1A *, 1B *, 5A *, 6
Compared to A * and 6B *, the synergistic effect of these components is that the composition does not contain any of the metal sulfonates, stabilizers or major antioxidant components, or contains only major antioxidants. It clearly shows that it provides enhanced thermo-oxidative stability.

Example 6 gives better results than Example 5. Example 6 is conducted under different test conditions for a more labile organic compound different from Example 5. Example 7 gives better results than Examples 8 and 9. Example 7 is likewise carried out under different test conditions with a more labile organic compound different from Examples 8 and 9.

Example 10 Product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, zinc soap of half methyl ester of dodecenyl succinic acid 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries)] 1 wt%, main antioxidant (alkylated phenyl-α-naphthylamine" Irganox
(Trademark) L06 ", Chiver Geigy Corporation)
0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, "Emery ™ 3004 PAO",
Quantum Chemical Corporation 98.75wt%
A blend consisting of is prepared. 200 ml of this blend is placed in a test vial which is then ASTM D4636-86.
Exposure to a temperature of 175 ° C. under conditions. The induction period lasts for 88 hours. After 87 hours of exposure, the acid value did not increase at all and decreased by 0.1% in the year at 40 ° C. The intermediate and final changes in acid number are shown graphically in FIG.

Comparative Example 10A * 200 ml of 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery ™ 3004 PAO", Quantum Chemical Corporation) was placed in a test vial, which was then ASTM D4636-. 175 under 86 conditions
Expose to a temperature of ° C. There is no induction period. Exposure 8
After 7 hours, the actual increase in acid number is 7.68 mg KOH / g and at 40 ° C. the viscosity has increased by 261.3%. The intermediate and final changes in acid number are shown graphically in FIG.

Comparative Example 10B * The product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture , "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT "King Industries)] 1 wt% and 4 cSt of synthetic hydrocarbon-based liquid (poly α-olefin mixture, "Emer
y ™ 3004 PAO ") 99 wt% blend is prepared. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. There is no induction period. After 87 hours of exposure, the actual increase in acid number was 6.86 mg KOH / g at 40 ° C.
The viscosity increases by 23.8%. The intermediate and final changes in acid number are shown graphically in FIG.

Comparative Example 10C * A major hydrocarbon (alkylated phenyl-α-naphthylamine “Irganox ™ L06”, Chiver Geigy Corporation) 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, “Emery ™”). ) 3
004 PAO ", Quantum Chemical Corporation) 99.75 wt% is prepared. Place 200 ml of this blend in a test vial and then
Exposed to a temperature of 175 ° C under ASTM D4636-86 conditions. The induction period is 28 hours. After 88 hours of exposure, the actual increase in acid number is 5.47, with a viscosity increase of 77.3% at 40 ° C. The intermediate and final changes in acid number are shown graphically in FIG.

Example 11 Product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, zinc soap of half methyl ester of dodecenyl succinic acid 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries)] 1 wt%, main antioxidant (alkylated phenyl-α-naphthylamine" Irganox
(Trademark) L06 ", Chiver Geigy Corporation)
0.10 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, “Emery ™ 3004 PAO”,
A Quantum Chemical Corporation) 99.9 wt% blend is prepared. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The induction period lasts for 88 hours. After 87 hours of exposure, the actual increase in acid number was 4.
It is 00 mg KOH / g. The intermediate and final changes in acid number are shown graphically in FIG.

Example 12 Product prepared by the method of Procedure A [Zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries)] 1 wt%, main antioxidant (4,4'-dioctyldiphenylamine" Vanlube
™ 81 ", RT Vanderbilt Company) 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture," Emery ™ 300 ").
4 PAO ") prepare a blend consisting of 98.75 wt%. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The induction period lasts for 88 hours. After 88 hours of exposure, the actual increase in acid number was 0.01 mg KOH / g at 40 ° C.
The viscosity increases by 0.29%.

Comparative Example 12A * A major hydrocarbon (4,4′-dioctyldiphenylamine “Vanlube ™ 81”, RT Vanderbilt Company) 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture). , "Emer
y ™ 3004 PAO ", Quantum Chemical Corporation) 99.75 wt% blend is prepared.
200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. There is no induction period. After 88 hours of exposure, the actual increase in acid number was 6.21 and the viscosity at 40 ° C was 121.
Increase by 1%.

Example 13 Product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 1 wt%, main antioxidant (2,6-di-t- Butylphenol derivative "Irganox
(Trademark) L130 ", Chiver Geigy Corporation)
0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery ™ 3004 PAO") 9
A blend consisting of 8.75 wt% is prepared. This blend 2
Place 00 ml in a test vial, which is then ASTM D
Expose to a temperature of 175 ° C under 4636-86 conditions. The induction period lasts for 76 hours. After 88 hours of exposure, the actual increase in acid number was 2.14 mg KOH / g and the viscosity at 40 ° C was
8.4% increase.

Comparative Example 13A * A major hydrocarbon (2,6-di-t-butylphenol derivative "Irganox (TM) L130", Chiver Geigy Corporation) 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly [alpha] -olefin mixture, " A blend of 99.75 wt% Emery ™ 3004 PAO ", Quantum Chemical Corporation) is prepared. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions.
The induction period lasts 26 hours. After 88 hours of exposure, the actual increase in acid number is 5.61 mg KOH / g and at 40 ° C the viscosity increases by 95.9%.

Example 14 Product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ”, Quantum Chemical Corporation 50.40%, (“ NA-SUL (trademark) ZS-HT ”, King Industries) 1 wt%, main antioxidant [phenyl-α-naphthylamine“ PANA ” , Aldrich Chemical Compan
y), Milwaukee, Wisconsin, recrystallized] 0.2
5 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-
Olefin mixture, "Emery ™ 3004 PAO") 98.75
A blend consisting of wt% is prepared. This blend 200
Place ml in the test vial, which is then ASTM D4636
Expose to a temperature of 175 ° C under -86 conditions. Induction period is 88
Continue over time. After 88 hours of exposure, the actual reduction in acid number was 0.05 mg KOH / g and the viscosity at 40 ° C was 3.9.
%To increase.

Comparative Example 14A * Main antioxidant [phenyl-α-naphthylamine "PAN
A ", Aldrich Chemical Company, Milwaukee, WI, recrystallized] 0.25 wt% and 4
A blend consisting of 99.75 wt% of a synthetic hydrocarbon-based liquid of cSt (poly alpha-olefin mixture, "Emery ™ 3004 PAO", Quantum Chemical Corporation) is prepared. 200 ml of this blend is placed in a test vial which is then placed under ASTM D4636-86 conditions at 175 ° C.
Exposure to temperatures. The induction period lasts 48 hours. Exposure 8
After 8 hours, the actual increase in acid number was 4.27 mg KOH / g,
At 40 ° C the viscosity increases by 53.8%.

Example 15 Product prepared by the method of Procedure A [Zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 1 wt%, main antioxidant [alkylated diphenylamine" Irganox (trademark) " L5
7 ", Chiver Geigy Corporation, and sulfur-containing hindered bisphenol" Irganox (TM) L115 ",
1: 1 wt ratio blend with Ciba Geigy Corporation] 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, "Emery ™ 3004
PAO ") prepare a blend consisting of 98.75 wt%. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions.
The induction period lasts for 111 hours. After 166 hours of exposure, the actual increase in acid number was 4.81 mg KOH / g at 40 ° C.
The viscosity increases by 30.4%.

Comparative Example 15A * Main antioxidant [alkylated diphenylamine "Irgano
x (TM) L57 ", Chiver Geigy Corporation,
1: 1 wt ratio blend of sulphur-containing hindered bisphenol "Irganox ™ L115", Chiver Geigy Corporation] 0.25 wt% and 4 cSt of a synthetic hydrocarbon-based liquid (poly α-olefin mixture, "Emery
(Trademark) 3004 PAO ") a blend of 99.75 wt% is prepared. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The induction period lasts 70 hours. Exposure 166
After hours, the actual increase in acid number was 8.36 mg KOH / g, 4
At 0 ° C the viscosity increases by 78.1%.

Examples 10, 12, 13, 14 and 15 demonstrate the use of different primary antioxidants in achieving the synergistic effects of the present invention as well as the application of the thermal oxidative stabilized package of the present invention in synthetic hydrocarbon based liquids. ing.

Example 10 is a comparative example 10A *, 10B * and 10C.
When compared to *, the synergistic effect of the metal sulfonate, the stabilizer and the main antioxidant component (Example 10) results in better thermo-oxidative stability than that obtained from the simple combined effect of these components. Is clearly shown. In Comparative Example 10B *, the combination of the metal sulfonate component and the stabilizer component alone has a lower acid value than the unstable organic compound,
It gave only 0.82 mg KOH / g, showing no induction period and a significant increase in viscosity at 40 ° C. Example 10C * shows only 2.21 mg K less than the labile organic compound with the main antioxidant component alone.
It is shown that only a low OH / g acid number results in no induction period and a significant increase in viscosity at 40 ° C. However, Example 10 does not result in any increase in acid number, but an induction period of 88 hours and a decrease in viscosity. The metal sulfonate, stabilizer and major antioxidant component (Example 10)
Synergistic effect of is greater than the simple combined effect in Comparative Examples 10B * and 10C *.

Example 11 shows that when compared to Example 10, the components are not present in sufficient synergistic effect when present in less than the recommended amounts.

Example 16 Polyethylene ["AC6" Allied Signal Corp., Morristown, NJ] 75 g and another polyethylene ("AC8", Allied Signal Corporation)
A blend consisting of 75 g is prepared. The Brookfield viscosity at 140 ° C. is measured at 350-40 cps. This blend has a major antioxidant (methylene bis-4,4 '
0.1503 g of 2,6-di-t-butylphenol "Ethanox ™ 702", ethyl corporation) and the product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, half of dodecenyl succinic acid] Methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, “Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries)] 0.1529 g is added. Place the resulting blend in a test vial, which is then
Exposed to a temperature of 175 ° C under ASTM D4636-86 conditions. The initial sample of this resulting blend was at 1723 cm ^-1 , at 0.
It has an infrared absorption of 040. The induction period exceeds 24 hours. After 24 hours of exposure, this sample was 0.06 at 1718 cm ^-1 .
It has an infrared absorption of 6.

Comparative Example 16A * Polyethylene [“AC6” Allied Signal Corporation) 75 g and another polyethylene (“AC8”,
Allied Signal Corporation) 75g blend prepared and placed in a test vial,
It is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The initial sample has an infrared absorption of 0.039 at 1722 cm ^-1, which is characteristic of the carbonyl group of a carboxylic acid. The induction period is less than 16 hours. After 16 hours of exposure, this sample shows increased carboxylic acid levels of 0. 2 at 1722 cm ^-1 .
It has an infrared absorption of 382.

Comparative Example 16B * Polyethylene [“AC6” Allied Signal Corporation) 75 g, another polyethylene (“AC8”, Allied Signal Corporation) 75 g and the main antioxidant (methylenebis-4,4′-2,6-di). -T
-Butylphenol "Ethanox (trademark) 702", ethyl
A blend consisting of (Corporation) is prepared, placed in a test vial and then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. Initially the sample has an infrared absorption of 0.039 at 1722 cm ^-1 . The induction period is less than 16 hours. After 16 hours of exposure, this sample has an infrared absorption of 0.190 at 1720 cm ^-1 .

Example 16 and Comparative Examples 16A * and 16B *
A metal sulfonate when blended with a thermoplastic polymer,
It shows the synergistic properties of stabilizers and major antioxidant components.

Example 17 Product prepared by the method of Procedure A [Zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 0.2 wt%, main antioxidant (4,4'-dioctyldiphenylamine) "Vanlube
(Trademark) 81 ", RT Vanderbilt Company) 0.15 wt%, secondary antioxidant (zinc diamyldithiocarbamate, 50% active in oil," Vanlube (trademark) AZ ", RT Tea. Vanderbilt Company) 0.10 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, “Emery ™ 3004 PA
O ") prepare a blend consisting of 99.65 wt%. Place 200 ml of this blend in a test vial and then
Exposed to a temperature of 175 ° C under ASTM D4636-86 conditions. The initial blend is a colorless flowable liquid with an acid number of 0.33 mg KOH / g and a kinematic viscosity of 16.94 cSt at 40 ° C.
The induction period lasts for 88 hours. After 88 hours of exposure, the acid value is 0.36 mg KOH / g and the viscosity at 40 ° C. is 16.93 cSt.

Comparative Example 17A * The product prepared by the method of Procedure A [zinc dinonylnaphthalene sulfonate 31.36%, zinc soap of half methyl ester of dodecenyl succinic acid 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture , "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 1 wt%, secondary antioxidant (zinc diamyldithiocarbamate, 50% active in oil,
"Vanlube ™ AZ", RT Vanderbilt Company) 0.25 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
™ 3004 PAO ") 98.75 wt% blend is prepared. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The initial blend had an acid value of 0.82 mg KOH / g
And a foam-brown flowing liquid with a kinematic viscosity of 16.96 cSt at 40 ° C. The induction period lasts 5 hours. After 5 hours of exposure, the acid value was 6.47 mg KOH / g and the viscosity at 40 ° C was 2
It is 0.67 cSt.

Example 18 Product prepared by the method of Procedure A [Zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 0.05 wt%, main antioxidant (4,4'-dioctyldiphenylamine) "Vanlube
(Trademark) 81 ", RT Vanderbilt Company) 0.15 wt%, secondary antioxidant (zinc diamyldithiocarbamate, 50% active in oil," Vanlube (trademark) AZ ", RT Tea. Vanderbilt Company) 0.10 wt% and 4 cSt synthetic hydrocarbon-based liquid (poly α-olefin mixture, “Emery ™ 3004 PA
O ") prepare a blend consisting of 99.70 wt%. Place 200 ml of this blend in a test vial and then
Exposed to a temperature of 175 ° C under ASTM D4636-86 conditions. The initial blend is a colorless flowable liquid with an acid number of 0.21 mg KOH / g and a kinematic viscosity of 16.94 cSt at 40 ° C.
The induction period lasts 72 hours. 72 hours after exposure, the acid value is 3.
The viscosity at 18 ° C. KOH / g, 40 ° C. is 19.29 cSt.

Example 19 Product prepared by the method of Procedure A [Zinc dinonylnaphthalene sulfonate 31.36%, dodecenyl succinic acid half methyl ester zinc soap 18.24%, 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery
(Trademark) 3004 PAO ", Quantum Chemical Corporation 50.40%, (" NA-SUL (trademark) ZS-HT ", King Industries) 1 wt%, main antioxidant (alkylated phenyl-α-naphthylamine" Irganox
(Trademark) L06 ", Chiver Geigy Corporation)
0.25 wt%, secondary antioxidant (zinc diamyldithiocarbamate, "Vanlube ™ AZ", RT Tea
Vanderbilt Company) 0.25wt% and 4cSt
A blend consisting of 98.5 wt% of a synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery ™ 3004 PAO") is prepared. 200 ml of this blend is placed in a test vial which is then placed under ASTM D4636-86 conditions at 1
Expose to a temperature of 75 ° C. The initial blend had an acid number of 0.79
It is a light brown, flowable liquid with mg KOH / g and a kinematic viscosity of 17.23 cSt at 40 ° C. The induction period lasts for 88 hours. 88 hours after exposure, the acid value was 0.9 mg KOH / g, 4
The viscosity at 0 ° C is 16.71 cSt.

Examples 17, 18 and 19 and Comparative Example 17A *
Show an additional synergistic effect when using a secondary antioxidant in conjunction with a metal sulfonate, a stabilizer and a major antioxidant component.

Example 20 Synthetic hydrocarbon-based liquid of 0.89 g of zinc dinonylnaphthalene sulfonate and 4 cSt prepared by the method of Procedure F (poly alpha-olefin mixture, "Emery ™ 3004 PAO", Quantum Chemical. Corporation) 1.33 g, ("NA-SUL (trademark) ZS", King Industries) 2.2 g and main antioxidant (4
4'-Dioctyldiphenylamine "Vanlube ™ 8
1 ", Art Vanderbilt Company, Norwalk, Conn.) 0.56 g solvent-purified heavy paraffinic distillate (petroleum" Sunpar ™ LW11
0 ", Sun Refining and Marketing Company, Philadelphia, PA) to prepare a blend by dissolving in 217.2 g. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C under ASTM D4636-86 conditions.

The initial blend is a light brown flowing liquid with an acid number of 0.64 mg KOH / g and a kinematic viscosity at 40 ° C. of 20.87 cSt. The induction period lasts for 185 hours. Exposure 185
After a period of time, the sample, which turns into a brown transparent liquid, has an acid value of
It has a viscosity of 0.78 mg KOH / g and a viscosity of 20.94 cSt at 40 ° C.

Example 21 Product prepared by the method of Procedure G [1.11 g magnesium dinonylnaphthalene sulfonate and light mineral oil (75
Second solvent extraction naphthenic petroleum, "Telura (trademark) 415",
Exxon Company, USA 1.09g, ("NA-SUL
(Trademark) MG "King Industries)] and 0.55 g of main antioxidant (4,4'-dioctyldiphenylamine" Vanlube (trademark) 81 ", RT Tea Vanderbilt Company) are solvent-purified heavy paraffin. System distillate (petroleum "Sunpar (trademark) LW110", Sun.
A blend is prepared by dissolving in 217.2 g of Refining and Marketing Company. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 150 ° C under ASTM D4636-86 conditions. The initial blend is a light brown flowing liquid with an acid number of 0.21 mg KOH / g and a kinematic viscosity at 40 ° C of 21.30 cSt. The induction period lasts for 185 hours. After 185 hours of exposure, the sample, which turns into a brown transparent liquid, has an acid number of 0.71 mg KOH / g and a viscosity of 21.07 cSt.

Example 22 1.0754 g of a 50% active solution of calcium dinonylnaphthalene sulfonate in light mineral oil ("NA-SUL (TM) 729", King Industries) is the base liquid and the major antioxidant [t- Butylphenol derivative (“Irgano
x (TM) L130 ", Chiver-Geigy Corporation, 1.74 g, blended with alkylated diphenylamine (" Irganox (TM) L57 ", Chiver-Geigy Corporation, Hawthorne, NY) 1.74 g] 3.5
g of heavy naphthenic distillate (“Sunthene ™ 108”, Sun Refining.
And Marketing Company) A blend is prepared by dissolving in 99.02 g of what is obtained by dissolving in 696.41 g. 52.04 g of the resulting blend is placed in a test vial which is then exposed to a temperature of 150 ° C. under modified IP48 test conditions. The initial sample is a light brown flowing liquid with an acid value of 0.16 mg KOH / g. After 24 hours of exposure, the resulting blend had an acid number of 0.
It is a clear, bright free-flowing liquid with 31 mg KOH / g.

Comparative Example 22A * Main antioxidant [t-butylphenol derivative (“Irga
3.03 g of alkylated diphenylamine (“Irganox ™ L57”, Ciba-Geigy Corporation) 1.50 g] blended with nox ™ L130 ”, Ciba-Geigy Corporation 1.53 g], and heavy hydrogenated naphthene-based distillate of 3.03 g A base liquid is prepared by dissolving in 597.0 g of the product (“Sunthene ™ 108”, Sun Refining and Marketing Company). 52.06 g of this base liquid is placed in a test vial which is then exposed to a temperature of 150 ° C. under modified IP48 test conditions. The initial sample is a nearly colorless, clear, flowing liquid with an acid value of 0.18 mg KOH / g. After 24 hours of exposure, this sample, which turns into a dark liquid, has a black sludge layer with a thickness of about 5 mm and an acid number of 5.92 mg KOH / g.

Example 23 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "" Emery (TM) 3004 PAO ", Quantum-
12.53 g of a 39.19% solution of zinc dinonylnaphthalene sulfonate in Chemical Corporation was added to 4 cSt of a synthetic hydrocarbon-based liquid (poly α-olefin mixture,
A stock solution is prepared by dissolving in 1240 g of "Emery ™ 3004 PAO". A blend is prepared consisting of 3.44 g of the main antioxidant (alkylated phenyl-α-naphthylamine "Irganox ™ L06", Chiver Geigy Corporation) dissolved in 1033 g of this stock solution. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The initial sample is a light brown flowing liquid with an acid number of 0.48 mg KOH / g and a kinematic viscosity of 17.13 cSt at 40 ° C. The induction period lasts for 88 hours. 88 hours after exposure, the acid value was 0.51 mg KOH / g and the viscosity at 40 ° C was 17.3.
It is 7 cSt.

Comparative Example 23 A * 4 cSt synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery (TM) 3004 PAO", Quantum Chemical Corporation) 219.51 g of the main antioxidant (alkylated phenyl-alpha-naphthylamine). Irgano
x (TM) L06 ", Chiver Geigy Corporation)
A blend is prepared by dissolving 0.5530 g. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions.
The initial blend has an acid number of 0.17 mg KOH / g and a kinematic viscosity at 40 ° C. of 16.96 cSt. The induction period is less than 40 hours. 89 hours after exposure, the acid value was 5.6 mg KOH / g,
The viscosity at 40 ° C. is 30.07 cSt.

Example 24 2.2010 g of a 39.19% solution of zinc dinonylnaphthalene sulfonate in 4 cSt of a synthetic hydrocarbon-based liquid (poly alpha-olefin mixture, "Emery ™ 3004 PAO", Quantum Chemical Corporation), major oxidation. Inhibitor (alkylated phenyl-α-naphthylamine “Ir
ganox (TM) L06 ", Chiver Geigy Corporation, 0.5623 g and 4 cSt synthetic hydrocarbon-based liquid (poly [alpha] -olefin mixture," Emery (TM) 3004 PA.
O ") secondary antioxidant dissolved in 216.7 g (zinc diamyldithiocarbamate, 50% active in oil," Vanlub
e (trademark) AZ ", RT Tea Vanderbilt
Company) to prepare a blend consisting of 0.5547 g. 200 ml of this blend is placed in a test vial which is then exposed to a temperature of 175 ° C. under ASTM D4636-86 conditions. The initial blend had an acid number of 0.64 mg KOH / g and 40
It is a light brown, flowing liquid with a kinematic viscosity of 17.14 cSt at ° C. The induction period lasts for 88 hours. 88 hours after exposure, the acid value was 0.67 mg KOH / g and the viscosity at 40 ° C was 1
It is 7.47 cSt.

Examples 20, 21, 22, and 23 show a synergistic effect, where the metal sulfonate and the main antioxidant component are
It has thermo-oxidative stability to natural and synthetic organic compounds that are normally thermo-oxidatively unstable. Comparative Examples 1A *, 1B
*, 5A *, 10A * 12A *, 13A *, 14A *,
When compared to 15A *, 22A * and 23A *, they were found that only the major antioxidants did not confer thermooxidative stability, and the major antioxidants and barium, calcium, magnesium or zinc oil soluble sulfonates It is shown that the synergistic effect of (3) imparts thermooxidative stability to an organic compound which is usually thermooxidatively unstable.

Example 24 demonstrates the greater synergism provided by the secondary antioxidant.

The patents and test methods mentioned above are hereby incorporated by reference.

Many modifications will suggest themselves to those skilled in this art in light of the above detailed description. For example, it is possible to use other sulfonates, such as octyl, decyl, undecyl, dodecyl, etc., in place of petroleum sulfonates in the dinonylnaphthalene sulfonate, alkylbenzene sulfonate or metal sulfonate components. Similarly, sulfonated diphenylalkanes can be used. Obviously, instead of the diacid, the corresponding anhydrides and half-esters could be utilized. Instead of mineral oil and poly α-olefin as a carrier component, other carrier such as microwax, dioctyl adipate, silicone oil and the like can be substituted. Other customary additives may be added in customary doses, for example extreme pressure additives, dispersants and the like. All these obvious modifications are entirely within the scope of the intended claims.

[Brief description of drawings]

FIG. 1 shows an unstable poly α-olefin mixture and “NA-SUL ™ ZS-HT” (Zinc dinonylnaphthalene sulfonate of King Industries and zinc soap of half methyl ester of dodecenyl succinic acid component). Or poly alpha blended with any of the major antioxidants
Between "NA-SUL ™ ZS-HT" and the main antioxidant in a thermo-oxidative stabilizing composition measured as change in acid number (mg KOH / g) over time in comparison with an olefin mixture It is a graph which shows a synergistic effect.

Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area // (C10M 141/08 135: 10 129: 42 129: 76 129: 10 133: 12 135: 18) C10N 10 : 02 10:04 30:10 50:10 (72) Inventor Robert, Lewis, Kugel No. 43, Stonecrop Road, Norwalk, 06851, Connecticut, USA

Claims (26)

[Claims] 1. An (A) normally thermo-oxidatively labile organic compound, and an effective amount of (B) (i) a metal selected from barium, calcium, magnesium, zinc or mixtures of any of the foregoing. A stabilizer comprising an oil-soluble sulfonate and (ii) an alkyl or alkenyl succinic acid or a partially esterified alkyl or alkenyl succinic acid alkali metal soap or alkaline earth metal soap or zinc soap, or any of the foregoing. An effective amount of a mixture of stabilizers, and (iii) an effective amount of at least one major antioxidant,
A composition comprising a thermo-oxidative stabilizing composition, optionally comprising (iv) an effective amount of a secondary antioxidant and optionally (v) a carrier for the thermo-oxidative stabilizing composition. 2. An (A) normally thermo-oxidatively labile organic compound, and an effective amount of (B) (i) a metal selected from barium, calcium, magnesium, zinc or mixtures of any of the foregoing. An oil-soluble sulfonate, (ii) an effective amount of at least one primary antioxidant, optionally (iii) an effective amount of a secondary antioxidant, and optionally (iv) for a thermal oxidation stabilizing composition. A composition comprising a thermo-oxidative stabilizing composition comprising a carrier. 3. The normally thermooxidatively unstable organic compound is a wax, ester, hydrocarbon fluid, halocarbon fluid, poly alpha-olefin, polyglycol, mineral oil, thermoplastic polymer, thermosetting polymer, A composition according to claim 1 or 2, selected from the group consisting of copolymers of olefins and non-olefins, or mixtures of any of the foregoing. 4. The composition according to claim 1, wherein the metal sulfonate comprises an oil-soluble barium, calcium, magnesium or zinc salt of an alkylaryl sulfonic acid or petroleum sulfonic acid having a molecular weight of about 325 or higher. object. 5. The composition of claim 4, wherein the metal sulfonate comprises a barium, calcium, magnesium or zinc salt of a dialkylaryl sulfonic acid. 6. The composition of claim 5, wherein the metal sulfonate comprises a barium, calcium, magnesium or zinc salt of dinonylnaphthalene sulfonic acid. 7. The metal sulfonate is barium dinonylnaphthalene sulfonate, calcium dinonyl naphthalene sulfonate, magnesium dinonyl naphthalene sulfonate, zinc dinonyl naphthalene sulfonate, barium alkylbenzene sulfonate, calcium alkylbenzene sulfonate, alkylbenzene. A composition according to any of claims 1 or 2 selected from the group consisting of magnesium sulfonate, zinc alkylbenzene sulfonate, or a mixture of any of the foregoing. 8. An alkali metal soap or alkaline earth metal soap or zinc soap of said alkyl or alkenyl succinic acid or partially esterified alkyl or alkenyl succinic acid, or a mixture of any of the aforementioned stabilizers, having about 10 carbon atoms. Alkali metal soaps or alkaline earth metal soaps or zinc soaps of 6 to about 50 alkyl or alkenyl succinic acids or partially esterified alkyl or alkenyl succinic acids of 6 to about 50 carbons or zinc soaps or mixtures of any of the foregoing. The composition of claim 1 selected from: 9. The stabilizer is an alkali metal soap or an alkaline earth metal soap of alkyl or alkenyl succinic acid having about 10 to 30 carbon atoms or partially esterified alkyl or alkenyl succinic acid having about 10 to about 30 carbon atoms. 9. A composition according to claim 8 which is alternatively selected from the group consisting of zinc soaps or mixtures of any of the foregoing. 10. A composition according to claim 8 wherein said stabilizer comprises an alkaline earth metal soap of alkenyl succinic acid. 11. The stabilizer is selected from the group consisting of alkyl or alkenyl succinic acids, barium, calcium, magnesium or zinc soaps of partially esterified alkyl or alkenyl succinic acids or mixtures of any of the foregoing. 8. The composition according to 8. 12. The stabilizer is barium soap of alkenyl succinic acid, calcium soap of alkenyl succinic acid, magnesium soap of alkenyl succinic acid, zinc soap of alkenyl succinic acid, barium soap of partially esterified alkenyl succinic acid, partial. 12. A calcium ester of partially esterified alkenyl succinate, a magnesium soap of partially esterified alkenyl succinic acid, a zinc soap of partially esterified alkenyl succinic acid, or a mixture of any of the foregoing. Composition. 13. The stabilizer comprises barium soap of half-methyl ester of dodecenyl succinic acid, calcium soap of half-methyl ester of dodecenyl succinic acid, magnesium soap of half-methyl ester of dodecenyl succinic acid, half-methyl ester of dodecenyl succinic acid. 13. The zinc soap of claim 1 or a mixture of any of the foregoing.
The mixture described. 14. The primary antioxidant comprises a phenolic antioxidant or an aromatic amine antioxidant.
Or the composition according to any one of 2). 15. The composition of claim 14, wherein the phenolic antioxidant comprises a hindered phenolic antioxidant. 16. The main antioxidant is methylenebis-
4,4'-2,6-di-t-butylphenol, 4,
Claims selected from the group consisting of 4'-dioctyldiphenylamine, alkylated phenyl-α-naphthylamine, t-butylphenol derivatives, alkylated diphenylamine, phenyl-α-naphthylamine, sulfur-containing hindered bisphenols, or mixtures of any of the foregoing. Item 15. The composition according to Item 14. 17. The composition according to claim 1, wherein the secondary antioxidant comprises thiocarbamate. 18. The composition of claim 17, wherein the secondary antioxidant comprises zinc diamyldithiocarbamate. 19. The carrier is wax, ester, halocarbon fluid, poly α-olefin, polyglycol,
A composition according to claim 1 or 2 selected from the group consisting of mineral oils or mixtures of any of the foregoing. 20. The component relative to the sum of the components (A) and (B)
A composition according to claim 1 or 2, wherein (A) comprises from about 95 to about 99.95 wt% and component (B) comprises from about 5 to about 0.05%. 21. Components (B) (i), (B) (ii), (B) (iii), (B) (i
v) and (B) (v), the component (B) (i) comprises about 2 to about 25 wt% and the component (B) (ii) about 3 to about 15 w.
The component (B) (iii) comprises about 20 to about 90 wt.
%. Component (B) (iv) comprises 0 to about 40 wt% and component (B) (v) comprises 0 to about 30 wt%. 22. A composition which stabilizes a normally thermooxidatively unstable organic compound thermooxidatively, selected from (i) barium, calcium, magnesium, zinc or a mixture of any of the foregoing. A metal oil-soluble sulfonate and (ii) a stabilizer containing an alkali metal soap or an alkaline earth metal soap or zinc soap of alkyl or alkenyl succinic acid or partially esterified alkyl or alkenyl succinic acid, or An effective amount of a mixture of any of the stabilizers, and (iii) an effective amount of at least one major antioxidant.
Usually comprising a step of blending with (iv) an effective amount of a secondary antioxidant and optionally (v) an effective amount of a carrier for the thermo-oxidative stabilizing composition, usually thermo-oxidatively A method for stabilizing a stable organic compound. 23. (i) an oil soluble sulfonate of a metal selected from barium, calcium, magnesium, zinc or mixtures of any of the foregoing, and (ii) an alkyl or alkenyl succinic acid or partially esterified alkyl. Or an effective amount of a stabilizer comprising an alkali metal soap or alkaline earth metal soap or zinc soap of alkenyl succinic acid, or a mixture of any of the foregoing, and (iii) an effective amount of at least one primary antioxidant.
A thermo-oxidative stabilizing composition, optionally comprising (iv) an effective amount of a secondary antioxidant and optionally (v) a carrier for the thermo-oxidative stabilizing composition. 24. The component (B) (i) is about 2 to the total amount of the components (B) (i), (B) (ii), (B) (iii), and (B) (iv). About 20w
% of component (B) (ii) is about 40 to about 90 wt%
The composition of claim 2 wherein said component (B) (iii) comprises 0 to about 50 wt% and component (B) (iv) comprises 0 to about 30 wt%. 25. A composition which stabilizes a thermo-oxidatively labile organic compound, which is usually thermo-oxidatively stable, selected from (i) barium, calcium, magnesium, zinc or a mixture of any of the foregoing. An oil-soluble sulfonate of a metal, (ii) an effective amount of at least one primary antioxidant, optionally (iii) an effective amount of a secondary antioxidant, and optionally (iv) the thermooxidative stabilization A method for stabilizing a normally thermooxidatively labile organic compound comprising the step of blending with an effective amount of a carrier for the composition. 26. (i) an oil-soluble sulfonate of a metal selected from barium, calcium, magnesium, zinc or mixtures of any of the foregoing, and (ii) an effective amount of at least one major antioxidant. By (iii) an effective amount of a secondary antioxidant, and optionally (iv) a carrier for a thermooxidative stabilizing composition, a thermooxidative stabilizing composition.