JP2002534590A - Non-phosphorus non-metal antiwear compounds and friction modifiers - Google Patents

Abstract

  (57) [Summary] A first portion intermediate adduct formed by reacting the second portion with the second portion in the first reaction, and further comprising the intermediate adduct in a third portion from about 1: 2 to about 2: 1. A friction reducing compound is disclosed, wherein the first portion is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil, and the second portion is a gen-conjugated carbon-carbon double bond. And a carboxylic acid moiety or anhydride group, wherein the first reaction is carried out in a molar ratio of about 1: 2 to about 2: 1 at a temperature of about 220 ° C. to about 320 ° C. under an inert atmosphere under the first reaction. Mixing the portion with the second portion; and the third portion is a polyhydroxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention provides a class of novel compounds having anti-friction properties, which compounds are prepared in a two-step process, the first of which is an unsaturated synthetic dienophile base oil.
ic base oil), as well as co-reacting the diene structure with a compound having a carboxylic acid group, the second step involves esterifying the free carboxylic acid group with a polyhydroxy-containing compound to form the desired friction modifier compound. BACKGROUND OF THE INVENTION Phosphorus is a poison for precious metal catalysts in the chemical industry. Similarly, studies conducted by the American Automobile Manufacturers Association (AAMA) have shown that phosphorus poisons today's emission control catalysts. For that reason, AAAA and more recently the International Lubricant Standardijation and Approval Committed
(ILSAC) has imposed a limit on the amount of phosphorus allowed in engine oils with a long-term goal of reducing the phosphorus content to sufficient to be harmless to automotive catalytic converters. Modern standard GF-3 limits phosphorus in motor oil to less than 0.1 wt%.

One problem with removing phosphorus from motor oil formulations is that it imparts polar attractive forces to attach lubricant molecules to metal surfaces and provides an energy absorbing barrier to friction and wear. It is to form. Phosphorus-containing additives work in unique energy bands and provide low friction and high wear protection to metals with light to medium loadings such as found in engine piston rings and cam followers. In addition, phosphorus has the properties of not forming ash, having low toxicity and being non-metallic. Phosphorus restrictions are limited by AAMA / ILSAC designers and motor oil formulators (formul
(Lubes and Greases November 1998).

[0003] Conventional lubricity additives include lead, sulfur, phosphorus, zinc, nitrogen or boron.
You. Lead is now banned. Other additives show ash formation or catalyst poisoning
Was. These additives are thermally activated and form sacrificial chemical bonds on the metal surface.
You. The bonding additive is then added before the metal itself provides protection of the metal surface from wear.
And cut from the metal surface (“shear”). Many additives also form particles during oxidation
Or contribute to sludge. Moreover, the motor oil lubricity additive is SO_x , NO _x And PO_x Can release or poison catalysts used in catalytic converters
Emissions can be formed, increasing particulate and hydrocarbon emissions.

[0004] Therefore, there is a need in the art for lubricating additives which impart the required lubricity properties but impart minimal ash or preferably ashless properties in order to reduce eventual fouling and emission properties. There is a request. The present invention illustrates achieving that goal. SUMMARY OF THE INVENTION The present invention can be reclaimed in the art to provide improved ashless additives to petroleum and vegetable lubricating base oils that provide lubricity and improved wear protection properties. Apply resource technology.

[0005] The goal achieved by the present invention is to provide a fully oil-soluble additive molecule,
It is obtained from renewable resources and does not contain ash or sediment producing elements or catalyst poisons such as sulfur, phosphorus or boron.

[0006] The present invention provides an antiwear agent (ie, a friction reducing compound), comprising a first part intermediate adduct formed by reacting with a second part in a first reaction, and Further, an antiwear compound that esterifies the intermediate adduct with a third portion in a molar ratio of about 1: 2 to about 2: 1, wherein the first portion is an unsaturated synthetic base oil or unsaturated A synthetic dienophile base oil, wherein the second part is a structure having a diene conjugated carbon-carbon double bond, and a carboxylic acid or acid anhydride part, and the first reaction is about 1:
Mixing the first portion with the second portion under an inert atmosphere at a temperature of from about 220 ° C. to about 320 ° C. in a molar ratio of 2 to about 2: 1; Compound.

[0007] Preferably, the first reaction is carried out at a temperature from about 220 ° to about 320 ° C, and
When the third moiety is a polyhydroxy compound, the second reaction is from 150 ° C to about 23 ° C.
It is performed at a temperature of 0 ° C. Preferably, the unsaturated synthetic base oil or unsaturated synthetic die
Nofill base oil is unsaturated C₁₂~ C₅₀Alkene, C₁₂~ C₅₀Diene, naphthenic oil
Base materials; unsaturated liquid oligomers and polymers, unsaturated polyalphaolefins
, Unsaturated polyacrylate, unsaturated dehydrated polyol ester; unsaturated C_Ten~ C _{twenty four} Branched or straight-chain fatty acids; branched or straight-chain mono- or polyunsaturated C_Ten~ C _{twenty four} Fatty acids to C₁ ~ C_{twenty four}With a linear or branched saturated or unsaturated alcohol
Tellurized unsaturated fatty acid esters; mono- or polyunsaturated C_Ten~ C_{twenty four}Branches
Or a linear fatty acid with a polyol (ethylene glycol, polyethylene glycol
Propylene glycol, polypropylene glycol, polyethoxylated aluminum
Cole, trimethylolpropane, pentaerythritol, dimethylolpro
One selected from bread, dipentaerythritol and trimethylolethane)
Unsaturated fatty glycol esters esterified at one or more hydroxyl sites;
Cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene,
3-pyrroline; substituted benzene, substituted toluene, substituted xylene, substituted quinone, substituted
Naphthalene, substituted anthracene, substituted pyrrole, substituted furan, substituted thiophene,
Substituted pyridine, substituted pyrimidine, substituted imidazole, substituted thiazole; X₁ -D
Stele-bonded benzoic acid, X₁ -Ester linked benzyl, X₁ -Ester linked naphthe
N, X₁ -Ester linked phenols; branched or linear mono- or polyunsaturated
C_Ten~ C_{twenty four}Selected from the group consisting of fatty acids; and combinations thereof, wherein
Substitution is mono- or polyunsaturated C_Two ~ C_{twenty five}Branched or straight chain alkenyl,
X₁ The ester bond is C_Two ~ C_{twenty four}Linear or branched carboxylic acid side chain or C₁ ~
C_{twenty four}It is a linear or branched saturated or unsaturated alcohol.

Preferably, the second moiety comprises an unsaturated compound having a diene conjugated carbon double bond and a carboxylic acid moiety or anhydride group.

[0009] Most preferably, the second part is maleic acid, maleic anhydride, sorbic acid, sorbic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic acid, salicylic acid, salicylic anhydride, acrylic acid, acrylic acid anhydride, the aforementioned acid And C _1-10 alkyl, C _2-10 alkenyl, or C _1-10 alkoxy derivatives of acid anhydrides, and combinations thereof.

Preferably, the third portion of the polyhydroxy compound is glycerol, sorbitol, hydroxyquinone, glucose, mannose, hexose, pentose, fructose, pentose, pentaerythritol, catechol, resorcinol, hydroquinone, pyrogallol, 4,4'-dihydroxybiphenyl, 2,4-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, orthohydroxybenzene, one or more phenyl rings and at least two hydroxyl groups, trimethylolpropane, pentaerythritol, dimethylol Substituted alkyl or alkenyl side chains substituted with propane, dipentaerythritol, trimethylolethane, ethylene glycol, polypropylene glycol, polyethylated alcohol (C Selected from the group consisting of polyhydroxyaromatic compounds having one or more 5- to 6-membered aromatic rings having ₂ to ₁₀ ), and combinations thereof. Preferably, the first reaction is carried out under an inert atmosphere at a temperature from 220 ° C to about 320 ° C to produce an intermediate adduct in the Diels-Alder reaction. Preferably, the esterification reaction comprises reaction conditions at about 150 ° C. to about 230 ° C. under an inert atmosphere, and further comprises adding an esterification catalyst.

[0011] Most preferably, the esterification catalyst is an acid catalyst.

[0012] Most preferably, the esterification catalyst is selected from the group consisting of p-toluenesulfonic acid, phosphinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acid clay, solid acid catalyst, acidic zeolite, and combinations thereof.

[0013] Most preferably, the fuel lubricity additive compound is selected from the group consisting of trimethylolpropane trioleate-maleic anhydride-sorbitol, and trimethylolpropane trioleate-sorbic acid-sorbitol in order. Part of the
Made from a second part and a third part.

The present invention further provides a method of synthesizing a friction-reducing compound, wherein (a) the first portion, which is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil, comprises from about 1: 2 to about 2: 1. Reacting in a second part under an inert atmosphere at a temperature of from about 220 ° C. to about 320 ° C. in a molar ratio to form an intermediate adduct in a Diels-Alder reaction, wherein the second part is a diene conjugate A compound having a carbon-carbon double bond and a carboxylic acid moiety or anhydride group; and (b) the intermediate adduct is esterified with a third moiety in a molar ratio of about 1: 2 to about 2: 1. Wherein the third portion is a polyhydroxy compound.

Preferably, the unsaturated synthetic base oil or unsaturated dienophile base oil is an unsaturated C ₁₂ ~ C₅₀Alkene, C₁₂~ C₅₀Diene, naphthenic petroleum base material; unsaturated liquid oil
Gomer and polymer, unsaturated polyalphaolefin, unsaturated polyacrylate
G, unsaturated dehydrated polyol ester; unsaturated C_Ten~ C_{twenty four}Branched or straight chain fatty acids
A branched or straight-chain mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids to C₁ ~ C_{twenty four}Directly
Unsaturated fatty acids esterified with chain or branched saturated or unsaturated alcohols
Ester; mono- or polyunsaturated C_Ten~ C_{twenty four}Branched or straight chain fatty acids
All (ethylene glycol, polyethylene glycol, propylene glycol
, Polypropylene glycol, polyethoxylated alcohol, trimethylol
Lopan, pentaerythritol, dimethyl roll propane, dipentaerythritol
One or more hydroxyl moieties of the thiol and trimethylolethane)
Aliphatic glycol esters esterified to cyclopentene, cyclope
Pentadiene, cyclohexene, cyclohexadiene, 3-pyrroline; substituted benzes
, Substituted toluene, substituted xylene, substituted quinone, substituted naphthalene, substituted anthra
Sen, substituted pyrrole, substituted furan, substituted thiophene, substituted pyridine, substituted pyrimi
Gin, substituted imidazole, substituted thiazole; X₁ -Ester linked benzoic acid, X₁ 
-Ester linked benzyl, X₁ -Ester linked naphthenes, X₁ -Ester bond
Enols; branched or linear mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids;
Selected from the group consisting of:
Saturated C_Two ~ C_{twenty five}A branched or straight chain alkenyl, X₁ The ester bond is C_Two 
~ C_{twenty four}Linear or branched carboxylic acid side chain or C₁ ~ C_{twenty four}Straight or branched
Sum or unsaturated alcohols, and combinations thereof. Preferably the second
Is a diene conjugated carbon-carbon double bond and a carboxylic acid moiety or acid anhydride
Including unsaturated compounds having a group. Most preferably, the second portion is maleic acid,
Water maleic acid, sorbic acid, sorbic anhydride, tetrahydrophthalic anhydride, tet
Lahydrophthalic acid, salicylic acid, salicylic anhydride, acrylic acid, acrylic acid anhydride
Of the above acids and acid anhydrides_1-10 Alkyl, C_2-10 Alkenyl, or
C_1-10 Selected from the group consisting of alkoxy derivatives, and combinations thereof
. Preferably the third portion of the polyhydroxy compound is glycerol, sorbitol
, Hydroxyquinone, glucose, mannose, hexose, pentose, fract
Toose, 5-carbon sugar, pentaerythritol, catechol, resorcinol, hide
Roquinone, pyrogallol, 4,4'-dihydroxybiphenyl, 2,4-dihydrido
Roxybiphenyl, 2,2'-dihydroxybiphenyl, orthohydroxyben
Zen, one or more phenyl rings and at least two hydroxyl groups, trimethylo
Propane, pentaerythritol, dimethylolpropane, dipentaeryth
Litol, trimethylolethane, ethylene glycol, polypropylene glyco
Or substituted alkyl or alkenyl substituted with polyethylated alcohol
Chain (C_2-10 ) Having one or more 5- to 6-membered aromatic ring
It is selected from the group consisting of aromatic compounds and combinations thereof.

Preferably, the first reaction is carried out under an inert atmosphere. Preferably, the esterification reaction comprises reaction conditions at about 150 ° C. to about 230 ° C. under an inert atmosphere, and further comprises adding an esterification catalyst. Most preferably, the esterification catalyst is an acid catalyst.

[0017] Most preferably, the esterification catalyst is selected from the group consisting of p-toluenesulfonic acid, phosphinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acid clay, solid acid catalyst, acidic zeolite, and combinations thereof.

[0018] The present invention further provides antiwear supplement compositions (crankcase oils, gear lubricants, hydraulic fluids, total loss lubricants) for addition to lubricant formulations. , Metal working fluids, etc., from about 1.0 wt% to about 50 wt% of a non-phosphorus anti-wear compound, and from about 0 wt% of a phosphorus additive.
About 25 wt%, extreme pressure additive about 0 wt% to about 10 wt%, dissolution stabilizer about 0 wt% to about 25 wt%
% Of the base oil carrier, and wherein the non-phosphorus antiwear compound comprises an intermediate adduct of the first portion formed by reacting with the second portion in the first reaction. And further comprising the intermediate adduct in a third portion from about 1: 2 to about 2: 1
Wherein the first portion is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil, the second portion is a diene conjugated carbon-carbon double bond, and a carboxylic acid moiety or A compound having an acid anhydride group, the first reaction being carried out in a molar ratio of about 1: 2 to about 2: 1 at a temperature of about 220 ° C. to about 320 ° C. under an inert atmosphere under a first part. And mixing with the second part; and the third part is a polyhydroxy compound.

Preferably, the unsaturated synthetic base oil or unsaturated dienophile base oil is unsaturated
C₁₂~ C₅₀Alkene, C₁₂~ C₅₀Diene, naphthenic petroleum base material; unsaturated liquid
Rigomers and polymers, unsaturated polyalphaolefins, unsaturated polyacryles
, Unsaturated dehydrated polyol ester; unsaturated C_Ten~ C_{twenty four}Branched or straight-chain fat
Acids; branched or straight-chain mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids to C₁ ~ C_{twenty four}of
Unsaturated fats esterified with linear or branched saturated or unsaturated alcohols
Acid ester; mono- or polyunsaturated C_Ten~ C_{twenty four}With branched or straight chain fatty acids
Riol (ethylene glycol, polyethylene glycol, propylene glycol
, Polypropylene glycol, polyethoxylated alcohol, trimethylol
Propane, pentaerythritol, dimethylol propane, dipentaerythritol
One or more hydroxyl moieties selected from toll and trimethylolethane)
Unsaturated fatty glycol ester esterified at the 2-position; cyclopentene, cyclo
Pentadiene, cyclohexene, cyclohexadiene, 3-pyrroline; substituted ben
Zen, substituted toluene, substituted xylene, substituted quinone, substituted naphthalene, substituted ant
Helix, substituted pyrrole, substituted furan, substituted thiophene, substituted pyridine, substituted pyri
Midine, substituted imidazole, substituted thiazole; X₁ -Ester linked benzoic acid, X ₁ -Ester linked benzyl, X₁ -Ester linked naphthenes, X₁ -Ester bond
Phenol; branched or linear mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids;
And combinations thereof, wherein the substitution is mono- or poly-
Unsaturated C_Two ~ C_{twenty five}A branched or straight chain alkenyl, X₁ The ester bond is C _Two ~ C_{twenty four}Linear or branched carboxylic acid side chain or C₁ ~ C_{twenty four}Straight or branched
It is a saturated or unsaturated alcohol.

Preferably, the second moiety comprises an unsaturated compound having a diene conjugated carbon-carbon double bond, and a carboxylic acid moiety or anhydride group. Most preferably, the second part is maleic acid, maleic anhydride, sorbic acid, sorbic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic acid, salicylic acid, salicylic anhydride, acrylic acid, acrylic acid anhydride, the aforementioned acids and acid anhydrides Selected from the group consisting of C _1-10 alkyl, C _2-10 alkenyl, or C _1-10 alkoxy derivatives, and combinations thereof.

Preferably, the third portion of the polyhydroxy compound is glycerol, sorbitol, hydroxyquinone, glucose, mannose, hexose, pentose, fructose, pentose, pentaerythritol, orthohydroxybenzene, one or more Selected from the group consisting of polyhydroxyaromatic compounds having a phenyl ring and at least two hydroxyl groups (eg, having phenyl substituted in the aforementioned polyhydroxy compounds), trimethylolpropane, polyethylated alcohols, and combinations thereof. It is. Preferably, the first reaction is performed with continuous mixing. Preferably, the esterification reaction comprises reaction conditions at about 150 ° C. to about 230 ° C. under an inert atmosphere, and further comprises adding an esterification catalyst. Most preferably, the esterification catalyst is an acid catalyst.

Most preferably, the esterification catalyst is p-toluenesulfonic acid, phosphinic acid,
Sulfuric acid, hydrochloric acid, phosphoric acid, acid clay, solid acid catalyst, acidic zeolite, and their
Selected from the group consisting of combinations. Detailed description of the inventionProduct-by-process The present invention relates to abrasion resistance (ie, the product of a two-step reaction comprising three starting materials)
Friction modifying) compounds, each comprising a first class of agents (combinations within that class)
A second type of agent (including combinations within that type);
It is selected from three types of agents. The first reagent is the Diels-Alder reaction.
And an unsaturated synthetic base oil or unsaturated synthetic dienoate that reacts with a second type of agent.
Fill base oil. Unsaturated synthetic base oils or unsaturated synthetic dienophile base oils
Saturated C₁₂~ C₅₀Alkene, C₁₂~ C₅₀Diene, naphthenic petroleum base material;
Realpha olefin, unsaturated polyacrylate, unsaturated dehydrated polyol ester
Unsaturated liquid oligomers and polymers, such as_Ten~ C_{twenty four}Branch or
Is a linear fatty acid; branched or linear mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids to C ₁ ~ C_{twenty four}Esterified with a linear or branched saturated or unsaturated alcohol of
Unsaturated fatty acid esters: ethylene glycol, polyethylene glycol, propylene
Len glycol, polypropylene glycol, polyethoxylated alcohol,
Limethylolpropane, pentaerythritol, dimethylolpropane, dipe
One or more polyols such as antaerythritol and trimethylolethane
Mono- or polyunsaturated C esterified at the hydroxyl site of_Ten~ C_{twenty four}Branch
Or unsaturated fatty glycol esters having straight-chain fatty acids; cyclopentene,
Including cyclopentadiene, cyclohexene, cyclohexadiene, 3-pyrroline
Unsaturated cyclic aliphatic rings; cycloaliphatic compounds having unsaturated branches or straight side chains;
Aromatic compounds benzene, toluene, xylene, quinone, naphthalene, anthracene
, Pyrrole, furan, thiophene, pyridine, pyrimidine, imidazole,
And thiazoles; mono- and polyunsaturated C_Two ~ C_{twenty five}Branched and straight-chain alkyl side chains
Aromatic compounds such as benzoic acid, benzyl, naphthenic acid
Esters of group acids and C_Two ~ C_{twenty four}Having a linear or branched carboxylic acid side chain
Aromatic compounds, and phenol or C₁ ~ C_{twenty four}Straight or branched, saturated
Sum or unsaturated alcohols; phenol and branched or straight-chain mono- or
Polyunsaturated C_Ten~ C_{twenty four}Aromatic esters of fatty acids; and combinations thereof, or
It can be broadly shown to be selected from the group consisting of: Preferably, the second part is a diene
Unsaturated with conjugated carbon-carbon double bonds and carboxylic acid moieties or acid anhydride groups
Including sum compounds. Most preferably, the second part is maleic acid, maleic anhydride
, Sorbic acid, sorbic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalate
Acid, salicylic acid, salicylic anhydride, acrylic acid, acrylic acid anhydride,
And acid anhydride C_1-10 Alkyl, C_2-10 Alkenyl or C_1-10 Al
It is selected from the group consisting of coxy derivatives and combinations thereof.

An unsaturated synthetic base oil or unsaturated synthetic dienophile base oil is reacted with the second part. Preferably, the second moiety comprises an unsaturated compound having a diene conjugated carbon-carbon double bond and a carboxylic acid moiety or anhydride group. Most preferably, the second part is maleic acid, maleic anhydride, sorbic acid, sorbic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic acid, salicylic acid, salicylic anhydride, acrylic acid, acrylic acid anhydride, the aforementioned acids and acid anhydrides C _1-10 alkyl, C _2-10
It is selected from the group consisting of alkenyl or _C1-10 alkoxy derivatives, and combinations thereof. The first and second parts are for intermediate products.

The intermediate product is isolated and reacted with a third part. Preferably, the polyhydroxy compound of the third part is glycerol, sorbitol, hydroxyquinone, glucose, mannose, hexose, pentose, fructose, pentose, pentaerythritol, catechol, resorcinol, hydroquinone, pyrogallol,
4,4'-dihydroxybiphenyl, 2,4-dihydroxybiphenyl, 2,2
'-Dihydroxybiphenyl, orthohydroxybenzene, one or more phenyl rings and at least two hydroxyl groups, trimethylolpropane, pentaerythritol, dimethylolpropane, dipentaerythritol, trimethylolethane, ethylene glycol, polypropylene glycol, polyethylated 1 having a substituted alkyl or alkenyl side chain (C _2-10 ) substituted with an alcohol
It is selected from the group consisting of polyhydroxyaromatic compounds having one or more 5- or 6-membered aromatic rings, and combinations thereof. Synthetic Process The synthetic method for the preparation of the non-phosphorus abrasion resistant (ie, friction modifying) compounds of the present invention is a two step process. In the first step, the unsaturated synthetic base oil or unsaturated synthetic dienophile base oil is reacted with the dienophile in a Diels-Alder reaction. In this first step, the unsaturated site of an unsaturated synthetic base oil or unsaturated synthetic dienophile base oil such as trimethylolpropane trioleate (TMP-TO) has a double bond conjugate and a carboxylic acid group. This is an addition reaction achieved by reacting with dienophile. Examples of dieneoids are maleic anhydride, acrylic acid, sorbic acid, and ascorbic acid (vitamin C). All adducts are characterized by having a conjugated double bond moiety that is sterically unhindered for the Diels-Alder reaction, as well as a free carboxylic acid moiety available for reaction in the second process step.

For example, the Diels-Alder reaction is initiated by mixing the unsaturated synthetic dienophile base oil and dienophile in a 1: 1 molar ratio and heating (range 220 ° C. to 320 ° C.). The Diels-Alder reaction continued until there was a clear single phase with sufficient acid number indicating completion without any unreacted added components. Table 1 shows the results of the first reaction step using TMP-TO as an unsaturated synthetic dienophile base oil and styrene, maleic anhydride, acrylic acid or sorbic acid in various molar ratios.

[0026]

[Table 1]

The second step is to react the carboxylic acid moiety on the aliphatic ring intermediate with the polyol polarity reactivity in an esterification reaction to produce the desired product as a lubricant. Exemplary polyols include glycerol (three hydroxyl groups) and sugar-derived sorbitol having six chiral hydroxyl groups. The second reaction step involves the presence of phosphinic acid (and may include a solid acid such as, for example, silica gel, alumina or acid clay, or a combination thereof) and an optional esterification catalyst (preferably at a relatively low reaction temperature). Below, at a temperature ranging from about 150C to about 230C.

The Diels-Alder product, which retains the acid functionality, is a Four Ball test (Four Ball test).
test) was a basic material for the ester reaction used to add functional polar compounds to acid sites exhibiting abrasion and rub resistance properties. The second process step involves the reaction of the active carboxylic acid moiety on the intermediate product with a polyol to produce a friction resistant product. Two of the polyols were chosen to illustrate the breadth of chemistry involved. The first example shows several active sites, while the second example shows many active sites. Glycerin (three hydroxyl groups) was selected as having some active sites on the polyol, and sorbitol (six hydroxyl groups) was used as a reagent with many active sites.

The esterification reaction of the polyol is carried out in the presence of phosphinic acid and an esterification catalyst in the presence of 15
It is carried out at a temperature in the range from 0 to 230 ° C. Sorbitol is added as a solid,
Heated to about 120 ° C. under a nitrogen atmosphere. Then the catalyst was added and heating was continued to obtain the reaction temperature. A vacuum of at least 26 mm Hg was used to facilitate ice removal. The end point of the esterification reaction was reached when TAN dropped to a level of less than 8 mg KOH / g sample. The resulting sorbitol ester was not clear and a small amount of polymerized sorbitol (about 0.2 wt%) was filtered off from the solution. The viscosity of the obtained product was 450 cps at 40 ° C. Without being bound by commercial application and formulation theory, the antiwear and lubricating effects of the compounds of the present invention did not compete with the phosphorus and sulfur based lubricating additives generally used in the art. In contrast, sulfur (often used together in averaged additive formulations)
Antiwear agents and phosphorus (antifrictional agents) are competitive with each other in their respective operating ranges. This means that reduced phosphorus loading in lubricants requiring extreme pressure lubrication can perform relatively well in the extreme pressure range with the composition where sulfur composition is not a concern, or equivalent performance reduced both phosphorus and sulfur Indicates that it can be held at a level. These data indicate that the lubricity additive of the present invention is synergistic with conventional phosphorus and sulfur based additives and can significantly reduce the required levels of sulfur and phosphorus used. Furthermore, not only can the phosphorus concentration be reduced by more than 50%, the resulting lubricating additive composition has better antiwear performance and better thermal stability. Accordingly, lubricating additive compositions containing the present compounds together with conventional phosphorus-based or ion-based antiwear and friction modifying compounds have a synergistic effect. Furthermore, the reduced phosphorus content of the lubricant additive package makes the resulting formulation less harmful to the waste gas catalyst and more environmentally friendly.

Further, while not being bound by theory, the assistance with the sulfur and phosphorus lubricating additive is that a strong film on the metal surface allows the concentration of the sulfur and phosphorus components of the lubricating additive formulation to be concentrated at the metal surface. Is assumed. The net effect is that relatively small amounts of the sulfur and phosphorus components are required in the lubricant formulation to achieve the same amount of antiwear protection. Similarly, such formulations containing a sulfur and phosphorus component along with the antiwear agent of the present invention have superior properties compared to conventional sulfur and phosphorus content, or superior effects at reduced sulfur or phosphorus or both content, Can be achieved.

The present invention further provides an antiwear composition for addition to lubricant formulations (such as crankcase oils, gear lubricants, hydraulic fluids, total loss lubricants, metalworking fluids, etc.). About 1.0 wt% to about 50 wt% of a non-phosphorus antiwear compound, about 0 wt% to about 25 wt% of a phosphorus additive, about 0 wt% to about 10 wt% of an extreme pressure additive, and about 0 wt% of a dissolution stabilizer.
About 25 wt%, and from about 25 wt% to about 75 wt% of a base oil carrier, wherein the non-phosphorus antiwear compound is an intermediate of the first portion formed by reacting with the second portion in the first reaction. Adduct, and further comprising the intermediate adduct in a third portion of about 1: 2-
Esterifying in a molar ratio of about 2: 1 wherein the first portion is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil, the second portion is a diene conjugated carbon-carbon double bond, and A compound having a carboxylic acid moiety or an anhydride group, the first reaction being carried out in a molar ratio of about 1: 2 to about 2: 1 at a temperature of about 220 ° C. to about 320 ° C. under an inert atmosphere under an inert atmosphere. And the third portion is a polyhydroxy compound.

Preferably, the unsaturated synthetic base oil or unsaturated dienophile base oil is unsaturated
C₁₂~ C₅₀Alkene, C₁₂~ C₅₀Diene, naphthenic petroleum base material; unsaturated liquid
Rigomers and polymers, unsaturated polyalphaolefins, unsaturated polyacryles
, Unsaturated dehydrated polyol ester; unsaturated C_Ten~ C_{twenty four}Branched or straight-chain fat
Acids; branched or straight-chain mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids to C₁ ~ C_{twenty four}of
Unsaturated fats esterified with linear or branched saturated or unsaturated alcohols
Acid ester; mono- or polyunsaturated C_Ten~ C_{twenty four}Use branched or straight chain fatty acids
Riol (ethylene glycol, polyethylene glycol, propylene glycol
, Polypropylene glycol, polyethoxylated alcohol, trimethylol
Propane, pentaerythritol, dimethylol propane, dipentaerythritol
One or more hydroxyl moieties selected from toll and trimethylolethane)
Unsaturated fatty glycol ester esterified at the 2-position; cyclopentene, cyclo
Pentadiene, cyclohexene, cyclohexadiene, 3-pyrroline; substituted ben
Zen, substituted toluene, substituted xylene, substituted quinone, substituted naphthalene, substituted ant
Helix, substituted pyrrole, substituted furan, substituted thiophene, substituted pyridine, substituted pyri
Midine, substituted imidazole, substituted thiazole; X₁ -Ester linked benzoic acid, X ₁ -Ester linked benzyl, X₁ -Ester linked naphthenes, X₁ -Ester bond
Phenol; branched or linear mono- or polyunsaturated C_Ten~ C_{twenty four}Fatty acids;
And combinations thereof, wherein the substitution is mono- or poly-
Unsaturated C_Two ~ C_{twenty five}A branched or straight chain alkenyl, X₁ The ester bond is C _Two ~ C_{twenty four}Linear or branched carboxylic acid side chain or C₁ ~ C_{twenty four}Straight or branched
It is a saturated or unsaturated alcohol. Preferably the second part is a diene conjugated carbon
-Unsaturated compounds having a carbon double bond and a carboxylic acid moiety or acid anhydride group
including. Most preferably the second part is maleic acid, maleic anhydride, sorbin
Acid, sorbic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic acid, sari
Tylic acid, salicylic anhydride, acrylic acid, acrylic anhydride, the aforementioned acids and acid anhydrides
Thing C_1-10 Alkyl, C_2-10 Alkenyl or C_1-10 Alkoxy induction
Selected from the group consisting of bodies, and combinations thereof.

Preferably, the third portion of the polyhydroxy compound is glycerol, sorbitol, hydroxyquinone, glucose, mannose, hexose, pentose, fructose, pentose, pentaerythritol, orthohydroxybenzene, one or more phenyl It is selected from the group consisting of polyhydroxyaromatic compounds having a ring and at least two hydroxyl groups (eg, the phenyl moiety is substituted with the aforementioned polyhydroxy compound), trimethylolpropane, and combinations thereof. Preferably, the first reaction is performed with continuous mixing. Preferably, the esterification reaction includes reaction conditions at about 150 ° C. to about 230 ° C. under an inert atmosphere, and further includes adding an esterification catalyst. Most preferably, the esterification catalyst is an acid catalyst. Most preferably, the esterification catalyst is selected from the group consisting of p-toluenesulfonic acid, phosphinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acid clay, solid acid catalyst, acidic zeolite, and combinations thereof.

Other components that may be present in the present invention include from about 0 wt% to about 25 wt% of a phosphorus additive, from about 0 wt% to about 10 wt% of an extreme pressure additive, from about 0 wt% to about 25 wt% of a dissolution stabilizer, and The oil carrier comprises from about 25% to about 75% by weight. Examples of phosphorus additives are alkylamine phosphate, tricresyl phosphate, and diethyl hydrogen phosphite. Examples of extreme pressure additives are lard sulfide, polyisobutene sulfide and chlorinated paraffin. Examples of solubility stabilizers are alkyl esters, liquid wax esters and phosphate esters. Examples of base oil carriers are petroleum, synthetic esters and polyalphaolefins.

The antiwear composition of the present invention for addition to a lubricant formulation can be added to a variety of different lubricating end product applications. Table 2 shows the invention with different product applications, the concentration range of the antiwear aid to be added (wt%) and the TMOSS (trimethylolpropane trioleate-sorbitol-sorbate) used as an exemplary compound. The final concentration range of the final lubricant formulation range of the compound is shown.

[0036]

[Table 2]

In particular, the compounds of the present invention are useful for their antiwear and antiwear properties in crankcase oils such as for gasoline engines. Compositions for gasoline engine crankcase oils include, for example, from about 0.1 to about 10% of the antiwear compound of the present invention (for example: TMOSS) (all percentages are wt%), from about 0 to about 10 0
. 2%, extreme pressure additive about 0 to about 1%, viscosity index improver about 3% to about 10%, antioxidant about 0.1 to about 1.0%, pour point depressant about 0.1 to about 1.0%, about 2.0% dispersant
~ About 5%, about 1.0% to about 5.0% surfactant, and about 80% base oil carrier.
About 95%. Examples of phosphorus additives include alkylamine phosphate, tricresyl phosphate, and diethyl hydrogen phosphite. Examples of extreme pressure additives are lard sulfide,
Contains sulfurized polyisobutene, and chlorinated paraffin. Examples of viscosity index improvers include
Including ABS polymers, acrylic polymers and olefin copolymers. Examples of antioxidants include alkyl hydroquinone, phenylamine compounds, and phenol compounds. Examples of pour point depressants include ethylene vinyl acetate polymers, acrylic polymers, and methacrylic polymers. Examples of dispersants include polyisobutyl succinamide. Examples of surfactants include metal petroleum sulfonates and metal phenates. Examples of base oil carriers include petroleum, synthetic esters and polyalphaolefins. Example 1 This example illustrates the synthesis of trimethylolpropane trioleate-sorbitol-sorbate (TMOSS), which was dried at 260 ° C. for 6 hours under a blanket of nitrogen with constant stirring. And a product obtained by supplying and reacting sorbic acid to degassed TMPTO until a 1: 1 molar mixture is obtained. The reaction was continued with temperature and stirring to produce an intermediate adduct. The reaction was terminated when the adduct was clear at room temperature and TAN was greater than the 55 mg KOH / g sample. The second reaction of the intermediate adduct with sorbitol is carried out in the reactor at 0 sorbitol per mole of intermediate.
. It is carried out by adding 9 mol and heating to 120 ° C. When this temperature is reached, the phosphinic acid catalyst is added at a content of 0.5 wt% and the temperature is 200
° C. Sufficient vacuum was obtained through a cold water condenser installed to separate the water produced by the condensation reaction that produced the TMOSS. The reaction is TAN <
Finished when the sample was 8 mg KOH / g. The product was cloudy with less than 0.5% insoluble polysorbate solids. These were filtered to give a clear golden liquid product. Example 2 This example demonstrates the oxidative stability of the TMOSS prepared in Example 1 except that the vegetable oil (soy oil) was used in place of the unsaturated synthetic dienophile base oil. And a fuel lubricating compound obtained by the same method. Both compounds were prepared by vigorous hydrotreatment and isomerization of a paraffinic petroleum lubricant base material having a viscosity index of 114-119 and a Noack volatility of 16 or less than 5 wt% for each, It was dissolved in a volatile and highly stable 5cSt engine oil base. The mixture was exposed to air and catalytic metal surfaces at 135 ° C. for 168 hours to simulate prolonged engine oxidative stress. The motor oil formulations were both tested for oxidative damage by comparing the improved amount of the TMOSS formulation to the fuel lubricity additive formulation.

Sample standard Improvement of TMOSS after 135 ° C. and 168 hours Viscosity increase No difference TAN increase No difference Sludge generation Sludge generation 99.8% decrease in TMOSS Lubricity change 3% super wear improvement in TMOSS These data show that It is as effective in abrasion resistance as an additive made from soybean oil in the same process, but at high temperatures, such as those found in engine crankcases.
Shows much more stability under oxidizing conditions. High stability is demonstrated by the hypothetical removal of sludge precipitated from the sample based on soybean oil. Therefore, TM
OSS was much more suitable for use in crankcase oils and other formulations used in high temperature, oxidizing conditions. Example 3 This example demonstrates that the wear retention characteristics of the TMOSS prepared in Example 1 were identical to those of Example 1 except that soybean oil was used in place of the unsaturated synthetic base oil or unsaturated synthetic dienophile base oil. A comparison is made with a fuel lubricating compound obtained by a method similar to that of TMOSS. Both compounds have low volatility and high stability, prepared by vigorous hydrotreatment and isomerization of paraffinic petroleum lubricant base materials having a viscosity index of 114-119 and a Noack volatility of 16 or less. 5cSt engine base oil. Both motor oil formulations were tested in a four-ball wear test according to ASTM D4172 method. At 5 wt% concentration both additives show improved wear resistance.

Test Product Wear Scar Diameter (mm) Motor Base Oil 0.90 Fuel Lubricity Additive 0.41 TMOSS 0.39 At 5 wt% concentration, both additives have significantly improved wear resistance compared to petroleum base oil Showed sex. The improvement was uniform within the limits of the test. Example 4 This example illustrates the friction reducing properties of the TMOSS produced in Example 1 and the scratch protection of steel. TMOSS was dissolved at 5 wt% in a fully formulated commercial 85W140, GL-5 automotive gear oil. Gear oil with and without TMOSS was tested on a Falex Pin and Vee Block device according to the ASTM D323 method. The TMOSS addition showed an impressive increase in lubricity.

Test Product 250 lb Tightening Force Torque (lb) Tightening Force at Break (lb) Gear Oil Alone 12 1300 TMOSS Addition 9 1550 These data show that small additions of TMOSS have a metal-to-metal sliding contact with a load of 250 lbs. Reduce the friction and mean more efficient power use, and increase the ultimate load required to damage metal surfaces, implying a longer equipment life. This improvement occurs even in fully formulated, commercially available lubricants containing additives for friction and wear reduction. Example 5 This example illustrates the abrasion reduction aid between the TMOSS prepared in Example 1 and an anti-wear additive containing 4 wt% phosphorus bound to a fatty acid ester. The three samples are
Each of the two aforementioned antiwear components alone or a 50:50 mixture of both, is a paraffinic petroleum lubricant base material (viscosity index 114-119, Noa
(such as ck volatility less than 16) was dissolved in a low volatility, high stability 5cSt engine base oil produced by vigorous hydrotreatment and isomerization. 3
All four samples were tested in a four-ball wear test according to the ASTM D4172 method.

Test Products Wear Scar Diameter (mm) Petroleum Base Oil 0.90 Phosphorus Antiwear Additive 0.45 TMOSS 0.39 50:50 Mixture of Phosphorus and TMOSS 0.31 These data are typical The compounds of the present invention (eg, TMOSS) used in conjunction with a phosphorus antiwear agent are synergistic and require at least 50% or less phosphorus content in the lubricant composition or lubricant additive package, and at the same time Alternatively, it provides better wear resistance and greater thermal stability. Phosphorus and sulfur used in EP / abrasion resistant packages often compete with each other in their operating ranges. Thus, reduced phosphorus loading in lubrication that requires EP lubrication achieves the extreme pressure range better with unchanged sulfur composition, or with the addition of the compounds of the present invention (eg, TMOSS), both reduced phosphorus and sulfur. Equivalent performance can be provided. Example 6 This example illustrates the preparation of the T-water prepared in Example 1 in an oil-in-water emulsion metalworking fluid.
5 gives a comparison of the lubricity of MOSS. TMOSS is dissolved at 5 wt% in the oil phase of a metalworking fluid formulation consisting of extreme pressure agents, alkalinity additives and emulsifiers based on sulfur, all dissolved in a medium viscosity index petroleum oil. The emulsion was emulsified in water at a dilution ratio of 1 part of the oil mixture to 40 parts of water. Emulsions with and without TMOSS were prepared according to ASTM D3233 by Falex Pin and Vee Blo
Tested with a ck device. The TMOSS addition showed an impressive increase in lubricity.
Test product Force at break (lbs) Emulsion alone 1200 Emulsion with TMOSS 1750 These data show that TMOSS is surface active on metal surfaces and acts as a lubricant, even in very polar water based media. Is shown. The fact that the emulsion was stable with TMOSS is also important in that it indicates that TMOSS is an effective additive for phosphorus-free metalworking fluids. further. Most water-based metalworking fluid formulations are alkaline to inhibit bacterial growth and stabilize the emulsion. Therefore, no acidic phosphorus compound is usually used. Compounds of the invention having an essentially neutral pH (eg, TMOSS
) Is less susceptible to basic environments than any ester material. Example 7 This example demonstrates a TMO measured under severe conditions and measured on a non-ferrous metal surface.
5 gives a comparison of the lubricity of SS lubricating additives. The tested lubricant had a viscosity index of 114
-119, a low volatility and high stability 5cSt engine base oil control produced by vigorous hydrotreatment and isomerization of a paraffinic petroleum lubricant base stock such that the Noack volatility is 16 or less. It was a sample. Prior to this rigorous treatment, the engine base oil was added with 0.5 wt% of TMOSS. Four 1/2 inch diameter brass (copper and zinc alloy) spheres are held in the stationary position of the fixture,
Used for the 4-ball EP method ASTM D1. Fixtures are either a strictly treated control lubricant or the same control but 0.5% TMOSS prior to severe treatment.
Was added. The load was 36 kg. The apparatus was operated for 20 seconds and the wear scar was measured. Test Sample Wear Scar Diameter (mm) Control 2.85 0.5% TMOSS loading 0.58 These data indicate that TMOSS protected the brass ball surface from test wear. Wear protection of copper alloys is particularly important for brass bushings and brass worm gears. Conventional phosphorus and sulfur lubricants have not been used in these applications due to the reactivity of copper. TMOSS and other compounds of the present invention protect these metals from abrasion without the disadvantage of corrosion and pitting. Example 8 This example provides a comparison of the lubricity of the TMOSS lubricity additive at different concentration additions measured against brass metal surface iron, treated under harsh conditions. This test was designed to mimic the wear conditions typically found where a copper shaft rotates with a brass bushing. The test lubricant is a low volatility, high volatility lubricant prepared by severe hydrotreatment and isomerization of a paraffinic petroleum lubricant base material having a viscosity index of 114-119 and a Noack volatility of 16 or less. A control sample of a stable 5cSt engine base oil. Prior to this rigorous treatment, the engine base oil was added with different amounts (mass) of TMOSS. Three 1/2 inch diameter brass (copper and zinc alloy) spheres and one similarly sized copper sphere were held in a stationary position on the fixture and used for the four-ball EP method ASTM D1. The fixture was filled with a severely treated control lubricant or the same control but with the addition of 0.5% TMOSS prior to severe treatment. The load was 360 kg. The apparatus was operated for 30 seconds and the wear scar was measured. Test sample Wear scar diameter (mm) Control 4.19 5.0% TMOSS addition 1.23 1.0% TMOSS addition 1.23 0.25% TMOSS addition 1.25 These data indicate that It shows that not only is the compound of the invention effective, but even at the lowest concentration.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 135/32 C10M 135/32 137/02 137/02 137/04 137/04 // C10N 30:06 C10N 30:06 40:04 40:04 40:08 40:08 40:20 40:20 Z 40:22 40:22 40:25 40:25 40:32 40:32 50:10 50:10 (81) Designation Country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), AU, BR, CA, IL, JP, MX, NO, NZ F term (reference) 4H104 BA02R BA06R BB04R BB06R BB22R BB31C BB34R BE26C BE26R BG02C BG04C BG17C BG17R BH02C BH03C CB08R CB09R DB01C LA03 PA02 PA05 PA21

Claims (14)

[Claims] 1. The method of claim 1, wherein the first reaction comprises an intermediate adduct of the first part formed by reacting with the second part, and further comprising the intermediate adduct in the third part at about 1: 2.
An antiwear compound esterified in a molar ratio of about 2: 1 wherein the first portion is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil and the second portion is a diene conjugated carbon- A structure having a carbon double bond and a carboxylic acid or acid anhydride moiety, wherein the first reaction is carried out at a molar ratio of about 1: 2 to about 2: 1 at about 220 ° C. to about 3
An antiwear compound wherein the first part is mixed with the second part under an inert atmosphere at a temperature of 20 ° C .; and the third part is a polyhydroxy compound. 2. A method of synthesizing an antiwear compound, comprising: (a) a first portion which is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil in a molar ratio of about 1: 2 to about 2: 1; Reacting in a second part under an inert atmosphere at a temperature of about 220 ° C. to about 320 ° C. to form an intermediate adduct in a Diels-Alder reaction, wherein the second part is a diene conjugated carbon-carbon A compound having a structure having a heavy bond and a carboxylic acid or anhydride moiety; and (b) esterifying the intermediate adduct with a third moiety in a molar ratio of about 1: 2 to about 2: 1. Wherein the third portion is a polyhydroxy compound. 3. An anti-wear supplement composition for addition to a lubricant formulation, comprising from about 1.0 wt% to about 50 wt% of a non-phosphorus anti-wear compound, from about 0 wt% to about 25 wt% of a phosphorus additive,
An extreme pressure additive comprising from about 0% to about 10% by weight, a dissolution stabilizer from about 0% to about 25% by weight, and a base oil carrier from about 25% to about 75% by weight, wherein the non-phosphorus antiwear compound comprises
Comprising an intermediate adduct of the first part formed by reaction with the second part in the reaction of
And further comprising esterifying the intermediate adduct with a third portion in a molar ratio of about 1: 2 to about 2: 1, wherein the first portion is an unsaturated synthetic base oil or unsaturated synthetic dienophile base oil. Wherein the second moiety is a compound having a diene conjugated carbon-carbon double bond and a carboxylic acid moiety or anhydride group, and the first reaction is about 1: 2-
Mixing the first part with the second part under an inert atmosphere at a temperature of about 220 ° C. to about 320 ° C. in a molar ratio of about 2: 1; and the third part is a polyhydroxy compound. Some compositions. 4. A crankcase oil formulation, wherein the non-phosphorus antiwear compound has a concentration of about 0.
1 to about 10%, phosphorus additive about 0 to about 0.2%, extreme pressure additive about 0 to about 1%, viscosity index improver about 3% to about 10%, antioxidant about 0.1 to about 1.0%, pour point depressant about 0
. 1% to about 1.0%, dispersant about 2.0% to about 5%, surfactant about 1.0% to about 5%
. 0%, and about 80% to about 95% of a base oil carrier, wherein the non-phosphorus antiwear compound is an intermediate addition of a first portion formed by reacting with a second portion in a first reaction. And the intermediate adduct in a third portion from about 1: 2 to about 2: 1
Wherein the first portion is an unsaturated synthetic base oil or an unsaturated synthetic dienophile base oil, the second portion is a diene conjugated carbon-carbon double bond, and a carboxylic acid moiety or A compound having an acid anhydride group, wherein the first reaction is carried out in a molar ratio of about 1: 2 to about 2: 1 at a temperature of about 220 ° C. to 320 ° C. under an inert atmosphere under a first part. And a third part is a polyhydroxy compound. 4. The antiwear compound, method, antiwear composition or crankcase oil formulation of claim 1, 2, 3 or 4, wherein the unsaturated synthetic base oil or unsaturated synthetic dienophile base oil is: unsaturated C ₁₂ -C ₅₀ alkene, C ₁₂ -C ₅₀ diene, naphthenic petroleum base material, unsaturated liquid oligomers and polymers, unsaturated polyalphaolefins, unsaturated polyacrylates, unsaturated dehydrated polyol ester; unsaturated C ₁₀ ~ C ₂₄ branched or straight chain fatty acids; branched or straight-chain mono- or polyunsaturated C ₁₀ -C ₂₄ fatty acid linear or branched saturated or unsaturated alcohols esterified with unsaturated fatty acids of C ₁ -C ₂₄ esters; mono- or polyunsaturated C ₁₀ -C ₂₄ branched or straight chain fatty acids, polyol (ethylene glycol, polyethylene glycol, Unsaturated glycol glycol esterified to one or more hydroxyl sites of propylene glycol, polypropylene glycol, polyethoxylated alcohol, trimethylolpropane, pentaerythritol, dimethylolpropane, dipentaerythritol and trimethylolethane Cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, 3-pyrroline; substituted benzene, substituted toluene, substituted xylene,
Substituted quinone, substituted naphthalene, substituted anthracene, substituted pyrrole, substituted furan,
Substituted thiophene, substituted pyridine, substituted pyrimidine, substituted imidazole, substituted thiazole; X ₁ -ester linked benzoic acid, X ₁ -ester linked benzyl, X ₁ -ester linked naphthene, X ₁ -ester linked phenol; or polyunsaturated C ₁₀ -C ₂₄ fatty acid; and combinations thereof, selected from the group consisting of, wherein the substituents are mono or polyunsaturated C ₂ -C ₂₅ branched or straight chain alkenyl, X ₁ - The ester linkage is a C ₂ -C ₂₄ straight or branched carboxylic acid side chain or a C ₁ -C ₂₄ straight or branched saturated or unsaturated alcohol. 5. An antiwear compound, an antiwear composition or crankcase oil according to claim 1, wherein the second part comprises an unsaturated compound having a free carboxylic acid or acid anhydride group. Formulation. 6. The method according to claim 6, wherein the second part is maleic acid, maleic anhydride, sorbic acid,
Water sorbic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, salicylic acid
, Salicylic anhydride, acrylic acid, acrylic acid anhydride, the aforementioned acids and acid anhydrides C _1-10 Alkyl, C_2-10 Alkenyl or C_1-10 Alkoxy derivative
6. The anti-wear compound according to claim 5, wherein the anti-wear compound is selected from the group consisting of combinations thereof.
, Methods, antiwear compositions or crankcase formulations. 7. The polyhydroxy compound of the third part is glycerol, sorbitol, hydroxyquinone, glucose, mannose, hexose, pentose,
Fructose, pentose, pentaerythritol, catechol, resorcinol,
Hydroquinone, pyrogallol, 4,4'-dihydroxybiphenyl, 2,4-
Dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, orthohydroxybenzene, one or more phenyl rings and at least two hydroxyl groups, trimethylolpropane, pentaerythritol, dimethylolpropane, dipentaerythritol, trimethylolethane, ethylene glycol , Polypropylene glycol, polyhydroxyaromatic compounds having one or more 5- to 6-membered aromatic rings having substituted alkyl or alkenyl side chains ( _C2-10 ) substituted by polyethylated alcohols, and combinations thereof The anti-wear compound, method, auxiliary anti-wear composition or crankcase oil formulation of claim 1, 2, 3, or 4 selected from the group consisting of: 8. The method of claim 1, wherein the first reaction is carried out with continuous mixing.
Or the antiwear compound, method, auxiliary antiwear composition or crankcase oil formulation of 4. 9. The method of claim 1, wherein the esterification reaction comprises reaction conditions at about 150 ° C. to about 230 ° C. under an inert atmosphere, and further comprising adding an esterification catalyst.
5. An antiwear compound, method, auxiliary antiwear composition or crankcase oil formulation according to 3 or 4. 10. The antiwear compound, method, auxiliary antiwear composition or crankcase oil formulation of claim 9, wherein the esterification catalyst is an acid catalyst. 11. The esterification catalyst is selected from the group consisting of p-toluenesulfonic acid, phosphinic acid, sulfuric acid, hydrochloric acid, phosphoric acid, acid clay, solid acid catalyst, acidic zeolite, and combinations thereof. Described antiwear compound, method,
An antiwear composition or a crankcase oil formulation. 12. A fuel lubricating additive compound comprising: trimethylolpropane trioleate-maleic anhydride-sorbitol, trimethylolpropanetrioleic acid-maleic anhydride-ethylenediamine, and trimethylolpropane-trioleate. -Made from a first part, a second part and a third part, selected from the group consisting of-maleic anhydride-hydroquinone.
5. An antiwear compound, a method, an antiwear auxiliary composition or a crankcase oil formulation according to 3 and 4. 13. The method according to claim 2, wherein the first reaction is carried out in an inert atmosphere with a sufficient vacuum. 14. The esterification reaction is carried out at about 150 ° C. to about 230 ° C. under an inert atmosphere.
The method for synthesizing an antiwear compound according to claim 2, which comprises a reaction condition of ° C and further comprising adding an esterification catalyst.