JP2015127423A - Lubricating oil additive and lubricating oil composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an overbased salt of an oligomerized alkylhydroxyaromatic compound for use in a lubricating oil composition.SOLUTION: The alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195°C and a final boiling point greater than 325°C and up to about 400°C as measured by ASTM D86. Also provided is a propylene oligomer having an initial boiling point of at least about 195°C and a final boiling point greater than 325°C and up to about 400°C as measured by ASTM D86, where the propylene oligomer contains a distribution of carbon atoms that includes at least about 50 mass% of those having Cto Ccarbon atoms.

Description

  The present invention relates generally to propylene oligomers, lubricating oil additives derived from the propylene oligomers and lubricating oil compositions containing the same.

  There is increasing evidence that certain synthetic or natural chemicals can affect the endocrine system. For example, certain synthetic or natural chemicals may function as agonists or antagonists for cellular receptors such as estrogen receptor, androgen receptor, and thyroid hormone receptor. Agonists bind to cellular receptors and elicit responses, whereas antagonists interfere with agonist function. Natural or synthetic chemicals interfere with hormones naturally present in the body in various ways. These chemicals are called endocrine disruptors. For example, endocrine disruptors (1) can bind to hormone receptors and mimic naturally occurring hormones, and (2) naturally occurring hormones bind to each hormone receptor. May interfere, (3) may change normal levels of hormones, (4) may increase or decrease levels of normal hormones, and (5) may interfere with the pathway in which the hormone travels. is there.

  Chemicals that prevent the estrogen and estrogen receptor from functioning properly are examples of endocrine disruptors. Certain chemicals (called pseudo-estrogens) and natural estrogens have a common mechanism of action. Usually, estrogen activity results from the binding of natural estrogens to the estrogen receptor (ER) inside the cell nucleus and subsequent transcriptional activation of the target gene. Transcriptional activation occurs when the estrogen receptor binds to the promoter sequence within the regulatory region of the target gene. If an endocrine disrupting factor mimicking natural estrogen is present, this endocrine disrupting factor binds to ER, and transcriptional activation by ER occurs even if natural estrogen does not exist. Similarly, endocrine disrupting factors bound to ER may cause antiestrogenic activity. However, this is the case when the endocrine disrupting factor does not activate ER bound to the same extent as natural estrogen. Finally, selective estrogen receptor modulators (SERMs) bind to ER and subsequently activate cellular responses, but are different from those activated by natural estrogens. In general, all but very few molecules that bind to the ER cause some activation of the receptor as estrogen or SERM.

  Alkylphenols and products produced from them have become more closely scrutinized in the context of potential endocrine disrupting chemicals. This is because the degradation intermediates of alkylphenols and alkylphenol products have weak estrogenic activity. Alkylphenols are used commercially and are present, for example, in herbicides, gasoline additives, dyes, polymer additives, surfactants, lubricating oil additives, and antioxidants. In recent years, alkoxylated alkylphenols such as ethoxylated nonylphenol have been criticized for low biodegradability and that biodegradation byproducts of the phenol moiety have high toxicity to aquatic organisms. Therefore, there are increasing concerns that these chemical substances function as endocrine disruptors, for example, function as pseudoestrogens. In some studies, the association between alkylphenols and the decrease in sperm count measured for human males, and the fact that alkylphenols cause detrimental disturbances to the activity of human estrogen and androgen receptors It is shown.

  Specifically, Non-Patent Document 1 compares the estrogenic activity of various alkylphenols with the naturally occurring hormone 17β-estradiol in yeast estrogen-inducible strains. The results show that the highest estrogenic activity is that 4-tert-octylphenol (8 carbon atoms, otherwise 4- (1), where a single branched alkyl group of 6 to 8 carbon atoms has the highest activity. , 1,3,3-tetramethylbutyl) phenol) is located in the para position of the phenol ring without any other steric hindrance. In Non-Patent Document 1, various alkylphenols were tested in the analysis, and the length of the alkyl chain, the degree of branching, the position of the alkyl group in the phenyl ring, and the degree of heterogeneity of the isomer affect the binding efficiency. However, it has been shown that results on structural activity cannot be derived. For example, Non-Patent Document 1 clarifies that the isomer of p-nonylphenol has 22 para isomers by high resolution gas chromatographic analysis and suggests that it will not have similar activity. ing. However, Non-Patent Document 1 does not clarify which one or more isomers are active species.

  Interestingly, Non-Patent Document 2 discloses that when a human estrogen receptor is used, the binding of alkylphenols to the receptor is maximized when the number of carbon atoms of the alkyl group is 9 carbon atoms. It is stated. Non-Patent Document 2 describes the finding that a branched chain nonylphenol and a mixture of isomers (commercially available product containing no n-nonylphenol) have almost the same activity as n-nonylphenol.

  Ethoxylated nonylphenol and ethoxylated octylphenol are widely used as nonionic surfactants. Concerns over the environmental and health effects of such alkoxylated alkylphenols have led to government restrictions on the use of these surfactants in Europe and voluntary restrictions by industry in the United States. Many industries have attempted to replace these preferred alkoxylated alkylphenol surfactants with alkoxylated linear and branched alkyl primary and secondary alcohols. However, the latter alcohols face problems with increasing odor, performance, formulation, and cost. The main focus has been on ethoxylated alkylphenols and their potential problems (mainly degradation byproducts), but other components have been reviewed to reduce negative impacts and similarities Alternatively, there remains a need to select combinations with better performance.

  Nonylphenol and dodecylphenol can be produced by the following steps: propylene oligomerization; separation of propylene trimer and tetramer; and alkylation of phenol by propylene trimer and separation of nonylphenol; or by propylene tetramer Phenol alkylation and dodecylphenol separation.

  Tetrapropenylphenols produced from propylene tetramers are widely used in the lubricating additive industry. Propylene tetramer has an average carbon number of 12 and contains carbon chains with a high degree of methyl branching. Tetramers can generally have a carbon number distribution with 10 to 15 carbon atoms. The tetramer provides compatibility with oil-soluble and other oil-soluble lubricating additive components. Tetramers are olefins that are also effective in terms of production costs. Dodecylphenol derived from propylene tetramer is primarily used as an intermediate in the manufacture of lubricant additives, generally sulfurized alkylphenate detergents. Although slightly, these branched phenate detergents use linear olefins to a minor extent.

Patent Document 1 describes (a) an oil of lubricating viscosity, and (b) (1) an olefin having at least 10 carbon atoms, wherein more than 80 mol% of the olefin is a linear C _{20 to} C ₃₀ n-α olefin. And (2) a reaction of a hydroxy aromatic compound with an olefin in which less than 10 mol% of the olefin is a linear olefin having less than 20 carbon atoms and less than 5 mol% is a branched olefin having 18 carbon atoms or less A lubricating oil composition comprising a detergent comprising a non-sulfurized alkali metal salt or alkaline earth metal salt of the product is disclosed. Comparative Example C of Patent Document 1 discloses a branched pentadecylphenol calcium salt produced by alkylating phenol with a branched C _{14 to} C ₁₈ olefin derived mainly from a propylene pentamer. However, Patent Document 1 discloses that the branched pentadecylphenol calcium salt of Comparative Example C is ineffective in preventing the action of endocrine disrupting factors. Patent Document 1 does not disclose the range of the boiling point of the olefin.

  Patent Document 2 discloses a lubricating oil additive comprising (a) an alkaline earth metal salt of a sulfurized monoalkylcatechol derivative and (b) a sulfurized monoalkylcatechol. Patent Document 2 further discloses that sulfurized monoalkylcatechol is obtained by sulfurization of an alkylated product of catechol produced by reacting catechol with an olefin such as a propylene pentamer in the presence of a catalyst. ing. Patent Document 2 does not disclose an endocrine disrupting action. Patent Document 2 also does not disclose a range of boiling points of olefins used for alkylcatechol.

US Patent Application Publication No. 2007/0049508 US Pat. No. 5510043 Specification

Lautledge, et al., “Structural characteristics of alkylphenolic chemicals related to estrogenic activity”, Journal of Biological Chemistry, February 7, 1997, 272 (6): 3280-8. Taburia, et al., “Structures of paraalkylphenols that bind to estrogen receptors”, European Journal of Biochemistry, 262, 240-245 (1999)

  It would be desirable to develop improved lubricating oil additives derived from alkylphenols for use in lubricating oil compositions.

  In a first aspect of the invention, an overbased salt of an oligomerized alkylhydroxy aromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound has an initial value of at least about 195 ° C. as measured by ASTM D86. An overbased salt of an oligomerized alkylhydroxyaromatic compound derived from an olefin mixture comprising a propylene oligomer having a boiling point and a final boiling point greater than 325 ° C. and less than or equal to about 400 ° C. is provided.

In a second aspect of the invention, there is provided a process for preparing an overbased salt of an oligomerized alkylhydroxyaromatic compound comprising the following steps:
(A) alkylating a hydroxyaromatic compound with an olefin mixture comprising a propylene oligomer having an initial boiling point of at least about 195 ° C. and an end point greater than 325 ° C. and not higher than about 400 ° C. as measured by ASTM D86 And obtaining an alkylhydroxy aromatic compound;
(B) a step of neutralizing the alkylhydroxy aromatic compound of step (a) to obtain a salt of the alkylhydroxyaromatic compound;
(C) oligomerizing the alkylhydroxy aromatic compound salt of step (b) to obtain an oligomerized alkylhydroxy aromatic compound salt; and (d) the oligomerized alkylhydroxy aromatic compound of step (c). A step of obtaining an overbased salt of an alkylhydroxy aromatic compound obtained by overbasing the salt of

  In a third aspect of the present invention, (a) a major amount of oil having a lubricating viscosity and (b) an overbased salt of an oligomerized alkylhydroxyaromatic compound comprising the alkylhydroxyaromatic compound alkyl Oligomerized alkylhydroxys derived from olefin mixtures comprising propylene oligomers having an initial boiling point as measured by ASTM D86 of at least about 195 ° C. and an end point of greater than 325 ° C. and not more than about 400 ° C. Lubricating oil compositions comprising overbased salts of aromatic compounds are provided.

  In a fourth aspect of the present invention, there is provided a method for reducing endocrine disruption as an effect on a lubricating oil composition and a mammal, comprising an overbased salt of an oligomerized alkylhydroxyaromatic compound comprising The alkyl group of the hydroxyaromatic compound is derived from an olefin mixture comprising a propylene oligomer having an initial boiling point of at least about 195 ° C. and an end point of greater than 325 ° C. and not more than about 400 ° C. as measured by ASTM D86. There is provided a method comprising adding an overbased salt of an oligomerized alkylhydroxyaromatic compound to a lubricating oil composition comprising a major amount of oil having a lubricating viscosity.

  In a fifth aspect of the invention, an overbased salt of an oligomerized alkylhydroxy aromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound has an initial value of at least about 195 ° C. as measured by ASTM D86. An overbased salt of an oligomerized alkylhydroxyaromatic compound derived from an olefin mixture comprising a propylene oligomer having a boiling point and an end point greater than 325 ° C. and less than or equal to about 400 ° C. For the purpose of reducing endocrine disrupting properties as an effect on water, it is provided for use as an additive in lubricating oil compositions comprising a major amount of oil having a lubricating viscosity.

  In a sixth aspect of the invention, an overbased salt of an oligomerized alkylhydroxy aromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound has an initial value of at least about 195 ° C. as measured by ASTM D86. Endocrine system as an effect on mammals having lubricating oil compositions with overbased salts derived from olefin mixtures containing propylene pentamers having a boiling point and a final boiling point greater than 325 ° C. and less than or equal to about 400 ° C. It is provided for use as an additive in a lubricating oil composition comprising a major amount of oil having a lubricating viscosity with the aim of reducing the property of disturbing.

In a seventh aspect of the present invention, there is provided a propylene oligomer having an initial boiling point of at least about 195 ° C. and an end point of more than 325 ° C. and not more than 400 ° C., as measured by ASTM D86, comprising C _{14 to} C Propylene oligomers having a carbon atom distribution comprising at least about 50% by weight of those having ₂₀ carbon atoms are provided.

In an eighth aspect of the present invention, (a) a liquid phosphoric acid catalyst having an acid strength of about 114% to about 122% is added to a feedstock containing at least about 50% by weight of propylene with respect to the total weight of the oligomerization conditions Contacting in the lower reaction zone; and (b) a propylene oligomer having an initial boiling point as measured by ASTM D86 of at least about 195 ° C and an end point of greater than 325 ° C and less than or equal to about 400 ° C. A process comprising separating a propylene oligomer having a carbon atom distribution comprising at least about 50% by weight of those having C _{14 to} C ₂₀ carbon atoms.

  By using the propylene oligomers of the present invention, the endocrine disrupting effects of lubricating oil additives derived from alkylphenols would be minimized. Thus, a propylene oligomer having an initial boiling point of at least about 195 ° C. and an end point greater than 325 ° C. and not higher than about 400 ° C. appears to minimize potential endocrine disrupting effects. Accordingly, it is believed that the overbased salt of the oligomerized alkylhydroxyaromatic compound of the present invention is substantially free of endocrine disrupting chemicals. For this reason, the overbased salts of the oligomerized alkylhydroxyaromatic compounds of the present invention can be advantageously used in compositions that require minimal endocrine disrupting effects on mammals.

  The present invention is an overbased salt of an oligomerized alkylhydroxy aromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound has an initial boiling point of at least about 195 ° C. and 325 ° C. as measured by ASTM D86. And overbased salts derived from olefin mixtures containing propylene oligomers having a final boiling point greater than about 400 ° C.

  Before discussing the present invention in more detail, the following terms are defined.

[Definition]
As used herein, the following terms have the following meanings unless expressly stated to the contrary.

  As used herein, an “endocrine disruptor” refers to a compound that disrupts the normal regulation of the endocrine system, particularly the endocrine system that regulates the reproductive process.

  “Lime” as used herein means calcium hydroxide, also known as slaked lime or hydrated lime.

  As used herein, “total base number” or “TBN” means the amount of base equivalent to milligrams of potassium hydroxide per gram of sample. Thus, a higher TBN number reflects a more basic product and thus exhibits a higher alkalinity. The sample TBN can be determined by ASTM test number D2896 or other equivalent method.

The overbased salt of the oligomerized alkylhydroxy aromatic compound of the present invention is obtained as follows:
(A) alkylating a hydroxyaromatic compound with an olefin mixture comprising a propylene oligomer having an initial boiling point of at least about 195 ° C. and an end point greater than 325 ° C. and not higher than about 400 ° C. as measured by ASTM D86 And obtaining an alkylhydroxy aromatic compound;
(B) a step of neutralizing the alkylhydroxy aromatic compound of step (a) to obtain a salt of the alkylhydroxyaromatic compound;
(C) oligomerizing the salt of the alkylhydroxy aromatic compound of step (b) to obtain a salt of the oligomerized alkylhydroxyaromatic compound; and (d) the alkylhydroxyaromatic oligomerized in step (c). A step of overbasing a salt of a compound to obtain an overbased salt of an oligomerized alkylhydroxy aromatic compound.

  In general, a method for producing an overbased salt of an oligomerized alkylhydroxy aromatic compound is well known, and in the present invention, a known method for producing an overbased oligomerized alkylhydroxy aromatic salt can be employed. For example, representative methods for producing such salts are described in US Pat. Nos. 3,178,368 and 3,801,507, which disclose overbased sulfurized alkylphenates, overbased alkylphenol / formaldehyde / diaminoalkane condensation products. U.S. Pat. No. 3,429,812, which discloses a product, and U.S. Pat. Nos. 5,281,346 and 5,458,793, which disclose neutralized alkylphenol-glyoxylic acid oligomers which may be overbased. ing. Therefore, the steps employed in the method for producing an overbased salt of an oligomerized alkylhydroxyaromatic compound of the present invention are within a range that can be predicted by those skilled in the art.

In step (a), the hydroxyaromatic compound is alkylated with an olefin mixture containing at least a propylene oligomer. Useful hydroxyaromatic compounds capable of alkylation include mononuclear monohydroxy or polyhydroxy C _{6 to} C ₃₀ aromatic hydrocarbons having 1 to 4 hydroxy groups, and in some embodiments 1 to 3 hydroxy groups. . Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like, and mixtures thereof. In some embodiments, the hydroxy aromatic compound is phenol.

  The olefin mixture used for the alkylation of hydroxyaromatic compounds comprises a propylene oligomer having an initial boiling point as measured by ASTM D86 of at least about 195 ° C and an end point of greater than 325 ° C and not more than about 400 ° C. . In some embodiments, the propylene oligomer has an initial boiling point of at least about 220 ° C. as measured by ASTM D86. In some embodiments, the propylene oligomer has an initial boiling point of at least about 225 ° C. as measured by ASTM D86. In another aspect, the propylene oligomer has an initial boiling point of at least about 235 ° C. as measured by ASTM D86. In yet another aspect, the propylene oligomer has an initial boiling point of at least about 245 ° C. as measured by ASTM D86. In yet another aspect, the propylene oligomer has an initial boiling point of at least about 260 ° C. as measured by ASTM D86. In yet another aspect, the propylene oligomer has an initial boiling point of at least about 280 ° C. as measured by ASTM D86. In another aspect, the propylene oligomer has an initial boiling point of at least about 300 ° C. as measured by ASTM D86.

  In some embodiments, the propylene oligomer has an end point of from about 330 ° C. to about 400 ° C. as measured by ASTM D86. In another aspect, the propylene oligomer has an end point of from about 335 ° C to about 400 ° C. In another embodiment, the propylene oligomer has an end point of from about 330 ° C to about 375 ° C. Further, in some embodiments, the propylene oligomer has an end point of about 335 ° C to about 360 ° C. In the present invention, for propylene oligomers, any combination of the above-described initial and final boiling points is contemplated.

  Propylene oligomers are prepared by contacting a feedstock containing a major amount of propylene with a liquid phosphoric acid catalyst having an acid strength of about 114% to about 122% in a reaction zone under oligomerization conditions, and ASTM. It can be obtained by separating a propylene oligomer having an initial boiling point measured by D86 of at least about 195 ° C and an end point of more than 325 ° C and not more than about 400 ° C.

  The feedstock for use in the production of the propylene oligomer comprises at least about 50% by weight propylene, based on the total weight of the feedstock. In some embodiments, the feedstock comprises at least about 60% by weight propylene relative to the total weight of the feedstock. In another aspect, the feedstock comprises at least about 70% by weight propylene relative to the total weight of the feedstock. In some embodiments, the feedstock comprises at least about 80% by weight propylene relative to the total weight of the feedstock. In yet another aspect, the feedstock comprises about 75 to about 90 wt% propylene with respect to the total weight of the feedstock.

  In some embodiments, the feedstock may contain a relatively small amount (ie substantially free) if it contains any olefin other than propylene, such as butene. In some embodiments, the feedstock can include other olefins such as butene. However, the oligomerized reaction product has an initial boiling point greater than about 195 ° C and an end point greater than 325 ° C and not greater than about 400 ° C. In some embodiments, the feedstock comprises less than about 10% by weight of butene. In another aspect, the feedstock comprises less than about 5% by weight butane. In yet another aspect, the feedstock comprises less than about 2% by weight of butene. The feedstock may also contain relatively small amounts of non-reactive components, typically less than about 10% by weight, such as alkanes such as ethane, propane, butane, isobutane.

  In the process of the present invention, the conversion of starting olefin (% by weight of oligomerized product / total weight of starting olefin) is at least about 70% by weight. In some embodiments, the conversion of the starting olefin is at least about 75% by weight. In another embodiment, the starting olefin conversion is at least about 80% by weight. In another embodiment, the starting olefin conversion is at least about 85% by weight.

In general, liquid phosphoric acid catalysts for use in a process for producing propylene oligomers are known, for example, liquid phosphoric acid catalysts disclosed in US Pat. Nos. 2,592,428, 2,814,655, and 3,887,634. Please refer to. Although the acid strength of the phosphoric acid catalyst can vary, it produces a propylene oligomer having an initial boiling point as measured by ASTM D86 of at least about 195 ° C and a final boiling point of greater than 325 ° C and less than about 400 ° C. Must be enough to Useful liquid phosphoric acid catalysts used in the present invention have an acid strength of about 114% to about 122%. In some embodiments, useful liquid phosphoric acid catalysts have an acid strength of about 114% to about 118%. In some embodiments, useful liquid phosphoric acid catalysts have an acid strength of about 114% to about 116%. The acid strength of the phosphoric acid catalyst can be calculated from the peak of polyphosphoric acid measured using NMR (nuclear magnetic resonance spectroscopy). The acid strength of the phosphoric acid catalyst can be expressed as a proportion of P ₂ O ₅ that is greater than the amount required for the hydrolysis reaction to produce orthophosphoric acid (H ₃ PO ₄ ). The acid strength of orthophosphoric acid is 100%, the acid strength of pyrophosphoric acid (H ₄ P ₂ O ₇ ) is 110%, and the acid strength of polyphosphoric acid H ₄ P ₂ O ₇ (HPO ₃ ) _n is n 114% when = 1, and 116% when n = 2.

  The feedstock and liquid phosphoric acid catalyst are contacted in a reaction zone that is normally at a temperature and pressure sufficient to maintain the gaseous feedstock in a liquid state. In general, when contacting the feedstock and the liquid phosphoric acid catalyst, the temperature of the reaction zone can be maintained from about 75 ° C. to about 175 ° C. and the pressure from about 200 psig to about 1600 psig. In some embodiments, the temperature may be in the range of about 85 ° C to about 150 ° C. In another aspect, the temperature may be in the range of 100 ° C to about 150 ° C. In some embodiments, the temperature may be in the range of about 110 ° C to about 125 ° C. In some embodiments, the pressure in the reaction zone can be in the range of about 400 psig to about 1000 psig. In another aspect, the pressure may range from about 500 psig to about 850 psig. In another aspect, the pressure may be in the range of 550 psig to about 800 psig. In the present invention, all combinations of the temperature range and pressure range described above are contemplated.

  Generally, the time for contacting the feedstock and the liquid phosphoric acid catalyst is in the range of about 5 minutes to about 45 minutes.

A feedstock and a liquid phosphoric acid catalyst are contacted in a reaction zone under oligomerization conditions and have an initial boiling point as measured by ASTM D86 of at least about 195 ° C. and a final boiling point of greater than 325 ° C. and less than about 400 ° C. And a propylene oligomer having a carbon atom distribution comprising at least about 50% by weight of C _{14 to} C ₂₀ carbon atoms is separated by techniques known in the art, such as distillation.

In some embodiments, the propylene oligomer used in the present invention may have a carbon atom distribution that includes no more than about 25% by weight of those having ₁₄ or less carbon atoms. In some embodiments, the propylene oligomers for use in the present invention may have a carbon atom distribution comprising about 20 wt% or less having a C ₁₄ or fewer carbon atoms. In another embodiment, the propylene oligomers for use in the present invention may have a carbon atom distribution comprising about 15 wt% or less having a C ₁₄ or fewer carbon atoms. In some embodiments, the propylene oligomer used in the present invention may have a carbon atom distribution that includes no more than about 5% by weight of those having ₁₄ or less carbon atoms.

In some embodiments, the propylene oligomers for use in the present invention may have a carbon atom distribution comprising less than about 3 wt% having a C ₁₃ or fewer carbon atoms. In some embodiments, the propylene oligomers for use in the present invention may have a carbon atom distribution including less than about 2 wt% having a C ₁₃ or fewer carbon atoms. In some embodiments, the propylene oligomers for use in the present invention may have a carbon atom distribution comprising less than about 1 wt% having a C ₁₃ or fewer carbon atoms. In some embodiments, the propylene oligomers for use in the present invention do not include those having a C ₁₃ or fewer carbon atoms substantially.

In one embodiment, the propylene oligomer used in the present invention may have a carbon atom distribution comprising at least about 50% by weight having from C _{14 to} C ₂₀ carbon atoms. In another embodiment, the propylene oligomers for use in the present invention may have a carbon atom distribution including at least about 55% by weight of those having carbon atoms of C ₁₅ to C _20.

In one embodiment, the propylene oligomer used in the present invention may have a carbon atom distribution comprising at least about 10% by weight having from C _{21 to} C ₂₆ carbon atoms. In another embodiment, the propylene oligomer used in the present invention may have a carbon atom distribution comprising at least about 1% by weight of those having C ₂₇₊ carbon atoms. In another embodiment, the propylene oligomer used in the present invention may have a carbon atom distribution comprising about 1% to 5% by weight of those having C ₂₇₊ carbon atoms.

In another aspect, the propylene oligomer used in the present invention is at least about 50% by weight having from C _{14 to} C ₂₀ carbon atoms, at least about 10% by weight having from C _{21 to} C ₂₆ carbon atoms, and It may have a carbon atom distribution comprising at least about 1% by weight having C ₂₇₊ carbon atoms. In another aspect, the propylene oligomer used in the present invention is at least about 55% by weight having from C _{14 to} C ₂₀ carbon atoms, at least about 10% by weight having from C _{21 to} C ₂₆ carbon atoms, and It may have a carbon atom distribution comprising at least about 1% by weight having C ₂₇₊ carbon atoms.

  In the present invention, all combinations of the above-described carbon atom distributions are intended for propylene oligomers.

The propylene oligomers of the present invention can include any amount of low molecular weight propylene oligomers such as propylene trimers or tetramers, so long as the initial boiling point of the mixture of propylene oligomers is at least about 195 ° C. The propylene oligomer of the present invention can also contain any amount of a high molecular weight propylene oligomer such as C ₂₇₊ as long as the end point as measured by ASTM D86 is greater than 325 ° C. and not greater than about 400 ° C. In some embodiments, the propylene oligomers of the present invention can include tetramers, pentamers, hexamers, heptamers, octamers, nonamers, and mixtures thereof.

Generally, the olefin mixture contains the major amounts of propylene oligomers described above. However, the olefin mixture may contain other olefins, as will be readily understood by those skilled in the art. For example, other olefins that can be used in the olefin mixture include linear olefins, cyclic olefins, branched olefins other than propylene oligomers such as butylene or isobutylene oligomers, arylalkylenes, and the like, and mixtures thereof. Suitable linear olefins include 1-hexene, 1-nonene, 1-decene, 1-dodecene, others, and mixtures thereof. Particularly suitable linear olefins are high molecular weight n-α olefins such as C _{16 to} C ₃₀ n-α olefins. These linear olefins can be obtained by methods such as ethylene oligomerization and wax cracking. Suitable cyclic olefins include cyclohexene, cyclopentene, cyclooctene, etc., and mixtures thereof. Suitable branched olefins include butylene dimers or trimers, or higher molecular weight isobutylene oligomers, others, and mixtures thereof. Suitable arylalkylenes include styrene, methylstyrene, 3-phenylpropene, 2-phenyl-2-butene, etc., and mixtures thereof.

Alkylation of hydroxyaromatic compounds with olefin mixtures is generally carried out in the presence of an alkylation catalyst. Useful alkylation catalysts include Lewis acids, solid acids, trifluoromethanesulfonic acid, and acidic molecular sieve catalysts. Suitable Lewis acids include aluminum trichloride, boron trifluoride, and boron trifluoride complexes (eg, boron trifluoride ether, boron trifluoride-phenol, and boron trifluoride-phosphate). Suitable solid acids include sulfonated acid ion exchange resin type catalysts such as Amberlyst 36 ^™ (available from Rohm and Haas, Philadelphia, PA).

The alkylation reaction conditions depend on the type of catalyst used. Appropriate combinations of reaction conditions can be employed that produce alkyl hydroxy aromatic products with high conversion efficiency without causing unacceptable amounts of cracking. In one preferred embodiment of the present invention, the alkyl hydroxyaromatic compound is a product of the alkylation, the alkyl hydroxyaromatic content of the alkyl group is C ₁₃ or less is not more than about 10%, preferably from about 5% Or less, more preferably 2% or less, and most preferably 1% or less. In another embodiment, the alkyl hydroxyaromatic compound is a product of the alkylation, the alkyl hydroxyaromatic content of the alkyl group is a C ₁₅ to C ₂₀ is at least about 20%, preferably at least about 30% More preferably at least about 40% and most preferably at least about 50%.

  In certain embodiments, the reaction temperature of the alkylation reaction is in the range of about 25 ° C to about 200 ° C. In another aspect, the reaction temperature for the alkylation reaction is in the range of about 85 ° C to about 135 ° C. The pressure during the reaction is generally atmospheric pressure, but higher or lower pressures can be employed. The alkylation treatment can be carried out batchwise, continuously or quasi-continuously. In some embodiments, the molar ratio of hydroxyaromatic compound to olefin mixture is typically in the range of about 10: 1 to about 0.5: 1. In some embodiments, the molar ratio of hydroxyaromatic compound to olefin mixture is usually in the range of about 5: 1 to about 3: 1.

  The alkylation reaction can be carried out under simple conditions or in the presence of a solvent inert to the reaction of the hydroxyaromatic compound with the olefin mixture. A typical solvent that can be used is hexane.

  After completion of the reaction, the necessary alkylhydroxy aromatic compound is separated by a conventionally known technique. In typical cases, the hydroxyaromatic compound is distilled from the reaction product.

  The alkyl group of the alkyl hydroxyaromatic compound is typically bonded preferentially to the ortho and para positions of the hydroxy aromatic compound.

  The alkyl hydroxy aromatic compound thus obtained is then contacted with a metal base under reaction conditions, preferably in an inert and compatible liquid hydrocarbon diluent, to form the alkyl hydroxy aromatic compound. A salt is formed. This reaction is preferably carried out in an inert gas, typically nitrogen. The metal base may be added once or multiple times at the midpoint of the reaction.

  Suitable metal basic compounds include metal hydroxides, oxides or alkoxides. Examples thereof are (1) an alkali or alkaline earth metal salt derived from a metal base selected from alkali hydroxide, alkali oxide or alkali alkoxide, or (2) alkaline earth metal hydroxide, alkaline earth. Alkaline earth metal salts derived from metal bases selected from metal oxides or alkoxides of alkaline earth metals. Representative examples of metal basic compounds that function as hydroxides are lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and aluminum hydroxide. Typical examples of the metal basic compound having a function as an oxide are lithium oxide, magnesium oxide, calcium oxide, and barium oxide. The metal base preferably used is, for example, calcium hydroxide in terms of ease of handling and cost when compared with calcium oxide.

  The neutralization reaction between the metal base and the alkylhydroxyaromatic compound is typically carried out at a temperature higher than room temperature (25 ° C.). The neutralization reaction is carried out in the presence of an accelerator such as ethylene glycol, formic acid, acetic acid, etc., and mixtures thereof.

  The salt of the alkyl hydroxy aromatic compound is then oligomerized to form a salt of the oligomerized alkyl hydroxy aromatic compound. Theoretically, neutralization can be performed as a separate step prior to oligomerization, but neutralization and oligomerization can also be performed simultaneously in a single process step. When the neutralization is performed as a separate step, the neutralization and the subsequent oligomerization step are performed under the same conditions as described above.

  In some embodiments, the oligomerization is carried out by contacting a salt of an alkyl hydroxyaromatic compound with a sulfur source, optionally in the presence of an oligomerization accelerator. Any suitable sulfur source can be used in the oligomerization step. Examples of sulfur sources include elemental sulfur, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate. Sulfur can be used as either molten sulfur, solid (eg, powder or fine particles), or a solid suspension in a compatible liquid hydrocarbon. Suitable as oligomerization accelerators are polyols, typically alkylene diols (eg, ethylene glycol). Typically from about 0.5 to about 4, preferably from about 2 to about 3 moles of sulfur are used per mole of alkyl hydroxyaromatic salt.

  In connection with the accelerator or mixture of accelerators, high molecular weight alkanols can be used as co-solvents. High molecular weight alkanols have straight or branched chain alkyls containing 8 to about 16 carbon atoms, preferably 9 to about 15 carbon atoms. Representative examples of suitable alkanols are 1-octanol, 1-decanol (decyl alcohol), 2-ethylhexanol, and others. Particularly preferred is 2-ethylhexanol. The use of high molecular weight alkanols in the reaction is beneficial. The reason is that the high molecular weight alkanol acts as a solvent and at the same time forms an azeotrope with water, so that the water generated by neutralization or other water generated in the system is reacted or (preferably) This is because it can be removed by a simple method by azeotropic distillation during the reaction. The high molecular weight alkanol has a certain role in the chemical reaction mechanism from the viewpoint of contributing to the removal of water, which is a byproduct during the reaction, and thereby promoting the reaction in the direction of progress of the reaction equilibrium.

  In other embodiments, oligomerization can be carried out by contacting a salt of an alkyl hydroxy aromatic compound with an aldehyde to produce, for example, a salt of a methylene bridged alkyl hydroxy aromatic compound. Suitable aldehydes include aliphatic aldehydes, aromatic aldehydes, heterocyclic aldehydes, etc., and mixtures thereof. Representative examples of such aldehydes are formaldehyde, glyoxylic acid, acetaldehyde, propionaldehyde, butyraldehyde, glycoxal, furaldehyde, 2-methylpropionaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,3 -Including dimethylbutyraldehyde, 3,3-dimethylbutyraldehyde, pentanal, methyl substituted pentanal, benzaldehyde, furfural, etc., and mixtures thereof. The aldehyde may contain a substituent such as hydroxyl, halogen atom, nitrogen atom, etc., as long as the substituent does not greatly participate in the reaction. Preferred aldehydes are glyoxylic acid or formaldehyde components. Formaldehyde is available in many forms such as, for example, solid, liquid or gas. Particularly preferred is paraformaldehyde (a solid, typically a powder or flake product containing from about 91% to about 93% equivalent formaldehyde). Trioxane which is a crystalline solid (trioxane is a cyclic trimer of formaldehyde) can also be used. However, a formaldehyde solution (generally used is an aqueous formaldehyde solution, sometimes in methanol with a formaldehyde concentration of 37%, 44%, or 50%) or a liquid formaldehyde such as formaldehyde in an aqueous solution. Solutions can also be used. In addition, formaldehyde can be used as a gas.

  In another embodiment, the oligomerization can be carried out by contacting a salt of an alkyl hydroxyaromatic compound with an aldehyde and amine source in a well-known Mannich reaction. Suitable aldehydes include those described above. In some embodiments, the amine source contemplated in the present invention is an amine containing an amino group characterized by the presence of at least one active hydrogen atom. Such amines can contain only primary amino groups, only secondary amino groups, or both primary and secondary amino groups. The amine may be a monoamine or a polyamine. Representative examples of useful amine compounds are N-methylamine, N-ethylamine, Nn-propylamine, N-isopropylamine, Nn-butylamine, N-isobutylamine, N-sec-butylamine, N -Tert-butylamine, Nn-pentylamine, N-cyclopentylamine, Nn-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N- Benzylamine, N- (2-phenylethyl) amine, 2-aminoethanol, 3-amino-1-propanol, 2- (2-aminoethoxy) ethanol, N- (2-methoxyethyl) amine, N- (2 -Ethoxyethyl) amine, N, N-dimethylamine, N, N-diethylamine, N, N- -N-propylamine, N, N-diisopropylamine, N, N-di-n-butylamine, N, N-di-sec-butylamine, N, N-di-n-pentylamine, N, N-di- n-hexylamine, N, N-dicyclohexylamine, N, N-dioctylamine, N-ethyl-N-methylamine, N-methyl-Nn-propylamine, Nn-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N, N-di (2-hydroxyethyl) amine, N, N-di (3-hydroxypropyl) ) Amine, N, N-di (ethoxyethyl) amine, N, N-di (propoxyethyl) amine, ethylenediamine, diethylenetriamine, triethylenetetraamine, Traethylenepentamine, and pentaethylenehexamine, o-, m- and p-phenylenediamine, diaminonaphthalenes, N-acetyltetraethylenepentamine, and the corresponding formyl-, propionyl-, butyryl-, and other N -Substituted compounds, including morpholine, thiomorpholine, pyrrole, pyrroline, pyrrolidine, indole, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, piperidine, phenoxazine, phenothiazine, substituted analogs thereof and others.

  In a second aspect, the amine source is an amino acid or salt thereof. “Amino acid” means any organic acid having at least one primary, secondary, or tertiary amine (—N <) group and at least one acidic carboxyl (—COOH) group. Mixtures of various amino acids can also be used. Representative examples of amino acids are glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, tyrosine, methionine, 6-aminohexanoic acid, proline, hydroxyproline, tryptophan, histidine, lysine, hydroxy Includes lysine, arginine, aspartic acid, asparagine, glutamic acid, glutamine, cysteine, cystine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and other alpha amino acids containing 1 to 5 carboxyl groups. Particularly preferred amino acids are glycine, β-alanine, nitrilotriacetic acid and the like which can be easily and commercially available in large quantities.

  Typical Mannich reactions are well known in the art and are disclosed, for example, in U.S. Pat. Nos. 3,368,972, 3,649,229, 4,157,309, and 5,370,805, the contents of which are It is described in this specification for reference.

  The resulting salt of the oligomerized alkylhydroxy aromatic compound is then overbased by reaction with an acidic overbased compound such as carbon dioxide or boric acid. A particularly preferred overbasing method is carbonation, such as reaction with carbon dioxide. Such carbonation can be conveniently carried out by adding a polyol, particularly an alkylene diol (eg, ethylene glycol) and carbon dioxide to the oligomerized alkylhydroxy aromatic compound salt. The reaction can be carried out simply by simple means that bubbles of carbon dioxide gas pass through the reaction mixture. Excess diluent and any water formed in the overbasing reaction can be conveniently removed by distillation during or after the reaction.

  Another aspect of the present invention comprises at least (a) a major amount of oil having a lubricating viscosity and (b) an overbased salt of an oligomerized alkylhydroxy aromatic compound of the present invention useful as a lubricating oil additive. The present invention relates to a lubricating oil composition. Lubricating oil compositions can be prepared in a conventional manner by mixing an appropriate amount of the lubricating oil additive of the present invention with a base oil having a lubricating viscosity. The particular base oil is selected depending on the intended use of the lubricant and the presence of other additives. Generally, the overbased salt of the oligomerized alkylhydroxy aromatic compound of the present invention is about 0.01 to about 40% by weight, preferably about about 40% by weight, based on the total weight of the lubricating oil composition in the lubricating oil composition. It is present in an amount of 0.1 to about 20% by weight.

  Base oils having a lubricating viscosity suitable for use in the lubricating oil composition of the present invention are generally present in large amounts relative to the total weight of the composition, specifically greater than 50% by weight, preferably about 70%. More than mass, more preferably from about 80 to about 99.5% by weight, most preferably from about 85 to about 98% by weight. The expression “base oil” as used herein should be understood to mean a base oil or a blend of base oils. This base oil is produced by a single manufacturer based on the same specification (regardless of where the raw material is supplied or where it is manufactured); conforms to the same manufacturer's specification, and also has a unique formulation, product identification number Or it is a lubricating component identified by both of them. The base oil used in the present invention may be a base oil discovered in the future in addition to those already known. This base oil is used in formulating lubricating oil compositions in some or all applications, such as engine oil, marine cylinder oil, functional liquids (eg, hydraulic oil, gear oil, transmission fluid), etc. Has a lubricating viscosity. In addition, the base oils used in the present invention are such as alkyl methacrylate polymers, olefin copolymers (eg, ethylene-propylene copolymers, styrene-butadiene copolymers), etc., and mixtures thereof. A viscosity index improver can optionally be included.

  The viscosity of the base oil depends on the application. This will be readily recognized by those skilled in the art. Thus, the viscosity of the base oil used in the present invention is typically in the range of about 2 to about 2000 centistokes (cSt) at 100 ° C. The individual base oils used as engine oils generally have a kinematic viscosity at 100 ° C. in the range of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt. Also, the base oil is selected and formulated according to the required end use and the additives ultimately included in the oil so as to give the required grade for the engine oil. The engine oil grade is, for example, that the lubricating oil composition has an SAE viscosity grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30. 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40. The oil used as the gear oil can have a viscosity of about 2 cSt to about 2000 cSt at 100 ° C.

  Base stocks can be manufactured using a variety of different methods. These methods include, but are not limited to, distillation methods, solvent purification methods, hydrotreating methods, oligomerization methods, esterification methods, and repurification methods. The re-purified stock should be substantially free of material added during manufacturing, contamination, or previous use. The base oil of the lubricating oil composition of the present invention is a natural or synthetic lubricating base oil. Suitable hydrocarbon synthetic oils include, but are not limited to, an ethylene polymerization reaction or a 1-olefin polymerization reaction, or carbon monoxide and hydrogen gas, which produces a polymer such as polyalphaolefin (PAO) oil. It includes oils synthesized by the hydrocarbon synthesis method used (eg, Fischer-Tropsch process). Examples of suitable base oils contain very little if a heavy fraction is present. For example, a lubricating oil fraction having a viscosity at 100 ° C. of 20 cSt or more is very small even if it exists.

  Base oils can be obtained from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. Suitable base oils are hydrogen produced by hydrocracking (rather than solvent extraction) aromatic and polar components in the crude product in addition to base oils obtained by isomerization of synthetic wax and slack wax. Contains chemical base oil. Suitable base stocks include those belonging to all of API categories I, II, III, IV, and V as defined in API publication 1509 (14th edition, Addendum I, December, 1998). The Type IV base stock is polyalphaolefin (PAO). Type V base stocks include all other base stocks not included in Type I, II, III, and IV. In this invention, type II, type III, and type IV base oils are preferably used, and the base oil belongs to one or more of type I, type II, type III, type IV, and type V. Oils or base oils can be combined for production.

  Useful natural oils include mineral lubricating oils (eg, liquid petroleum-derived oils, paraffinic, naphtha or paraffin-naphtha mixed or oil-treated mineral lubricating oils, oils obtained from coal or shale oil), Includes animal or vegetable oils (eg, rapeseed oil, castor oil, lard oil) and others.

  Useful synthetic lubricating oils include, but are not limited to, polymerized or copolymerized olefins (eg, polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly 1-hexenes). Hydrocarbon oils and halogen-substituted hydrocarbon oils such as poly 1-octenes and poly 1-decenes, and mixtures thereof; dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2- Alkyl benzenes such as ethylhexyl) benzenes: polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, etc .; alkylated diphenyl ethers, alkylated diphenyl sulfides and their derivatives, analogs, and Includes homologs and others.

  Other useful synthetic lubricating oils polymerize, but are not limited to, olefins having less than 5 carbon atoms (eg, ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof). The oil obtained by this is included. Methods for producing such polymer oils are well known to those skilled in the art.

Another useful synthetic hydrocarbon oil comprises a liquid polymer of alpha olefins with moderate viscosity. Particularly useful synthetic hydrocarbon oils are hydrogenated liquid oligomers (eg, 1-decent trimer) of C _{6 to} C ₁₂ alpha olefins.

Another class of useful synthetic lubricants includes, but is not limited to, alkylene oxide polymers, i.e., homopolymers, interpolymers, and derivatives thereof. These terminal hydroxyl groups may be modified, for example, by esterification or etherification. Examples of these oils are oils produced by polymerization of ethylene oxide or propylene oxide, alkyl or phenyl ethers of these polyoxyalkylene polymers (eg, methyl polypropylene glycol ether with an average molecular weight of 1000, polyethylene glycol with a molecular weight of 500 to 1000) Diphenyl ether, polypropylene glycol diethyl ether having a molecular weight of 1000 to 1500, or the like, or a mono- or polycarboxylic acid ester thereof (eg, acetate ester, mixed C _{3 to} C ₈ fatty acid ester), or C _{13 of} tetraethylene glycol. Contains oxo acid diesters.

  Yet another useful class of synthetic lubricating oils includes, but is not limited to, dicarboxylic acids (eg, phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid , Sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene) Glycol, diethylene glycol monoether, propylene glycol and the like). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, sebacin It includes dieicosyl acid, 2-ethylhexyl diester of linoleic acid dimer, complex ester formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid, and others.

  Other esters useful as synthetic oils include, but are not limited to, carboxylic acids and alcohols having from about 5 to about 12 carbon atoms (eg, methanol, ethanol, etc.), polyols and polyol ethers (eg, Neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol), and others.

  Silicone-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils constitute another useful class of synthetic lubricants. Specific examples of these include, but are not limited to, tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethylhexyl) silicate, tetra (4-methylhexyl) silicate, tetra (p-tert-butylphenyl) silicate. Hexyl (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, and the like. Still other useful synthetic lubricating oils include, but are not limited to, polymers of tetrahydrofuran, such as liquid esters of acids containing phosphorus (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanophosphinic acid, Including others.

  Lubricating oils can be obtained from unrefined, refined and rerefined oils. These oils may be natural, synthetic or a mixture of those belonging to two or more classes disclosed above. Unrefined oil is obtained from natural or synthetic raw materials (eg, coal, shale, or tar sand bitumen) without refining or processing. Examples of unrefined oils include, but are not limited to, shale oil obtained directly by a dry distillation operation, petroleum oil obtained directly by distillation, or ester oil obtained directly by an esterification process. Both of these examples are used without further processing. Refined oils are similar to unrefined oils, except that they have been treated with one or more refining steps to further improve one or more properties. Such purification techniques are known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or alkali extraction, filtration, percolation, hydrotreatment, dewaxing, and the like. Rerefined oil is obtained by treating spent oil in a manner similar to that used to obtain refined oil. Such rerefined oils, also known as reclaimed or reprocessed oils, are often further processed by techniques to remove spent additives and oil breakdown products.

  A lubricating base oil obtained by hydroisomerization of wax may be used alone or in combination with the above natural and / or synthetic base oils. Such wax isomerate oil is produced by hydroisomerizing a natural or synthetic wax or a mixture thereof in the presence of a hydroisomerization catalyst.

  A typical natural wax is slack wax recovered by solvent dewaxing of mineral oil. A typical synthetic wax is a wax produced by the Fischer-Tropsch process.

  The lubricating oil composition of the present invention can further contain well-known additives to add ancillary functions, so that the final lubricating oil composition in which these additives are dispersed or dissolved is added. can get. For example, lubricating oil compositions are antioxidants, antiwear agents, detergents (eg, metal-containing detergents), rust inhibitors, antifogging agents, demulsifiers, metal deactivators, friction modifiers, pour point depressants. Can be mixed with agents, antifoaming agents, co-solvents, package compatibilizers, corrosion inhibitors, ashless dispersants, dyes, extreme pressure agents, etc., and mixtures thereof. Various additives are known and are commercially available. Additives and their analogous compounds can be used in the production of the lubricating oil composition of the present invention by common mixing methods.

  Examples of antioxidants include, but are not limited to, amine type (eg, diphenylamine, phenyl-α-naphthylamine, N, N-di (alkylphenyl) amines; alkylated phenylenediamines); phenol Type (eg BHT, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4- (2-octyl-3-propane) Acid) sterically hindered alkylphenols such as phenol); and mixtures thereof.

  Examples of ashless dispersants include, but are not limited to, polyalkylene succinic anhydrides; derivatives of polyalkylene succinic anhydrides that do not contain nitrogen atoms; succinimides, carboxylic acid amides, hydrocarbyl monoamines , Hydrocarbyl polyamines, Mannich bases, phosphonoamides, and phosphoramides, basic nitrogen compounds; triazoles (eg, alkyltriazoles and benzotriazoles); one or more other carboxylic acid esters Copolymers (eg, acrylic acid or methacrylic acid long-chain alkyls) with a polar functional group (eg, amine, amide, imine, imide, hydroxyl, carboxyl, etc.) Product); other, and it Comprising a mixture of. Derivatives of these dispersants (eg, boronated dispersants such as boronated succinimides) can also be used.

  Examples of the rust inhibitor include, but are not limited to, nonionic polyoxyalkylene agents (eg, polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl). Ethers, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate); stearic acid and other fatty acids; dicarboxylic acids; Metal soap; fatty acid amine salt; metal salt of strong sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphate ester; (short chain) alkenyl succinic acid; Ester and their nitrogenous derivatives, synthetic alkaryl sulfonic acids (e.g., dinonyl naphthalene sulfonic acid metal salts) and the like; and mixtures thereof.

Examples of friction modifiers include, but are not limited to, alkoxylated aliphatic amines; boronated aliphatic epoxides; aliphatic phosphorous acid, aliphatic epoxides, aliphatic amines, boronated alkoxylated aliphatic amines , Fatty acid metal salts, fatty acid amides, glycerol esters, boronated glycerol esters; and aliphatic imidazolines disclosed in US Pat. No. 6,372,696, the contents of which are incorporated herein by reference. A reaction product of a fatty acid ester of C _{4 to} C ₇₅ , preferably C _{6 to} C ₂₄ , most preferably C _{6 to} C ₂₀ and a nitrogen-containing compound selected from the group consisting of ammonia and alkanolamine Friction modifiers obtained from: others, and mixtures thereof.

  Examples of antifoaming agents include, but are not limited to, polymers of alkyl methacrylates; polymers of dimethyl silicone; others, and mixtures thereof.

  When using the additives described above, a functionally effective amount is used to impart the required properties to the lubricant. Therefore, for example, if the additive is a friction modifier, the functional effective amount of the friction modifier is an amount sufficient to impart the friction adjustment performance required for the lubricant. The individual concentrations in the use of these additives are generally from about 0.001% to about 20% by weight, and in some embodiments from about 0.01% to about 10%, based on the total weight of the lubricating oil composition. % By mass.

  The final application fields of the lubricating oil composition of the present invention include, for example, marine cylinder lubricating oil, trunk piston engine oil, automobile and railway crankcase lubricating oil used in crosshead diesel engines, functional fluids, heavy machinery Lubricating oil etc. (for example steelworks) or bearing grease etc. are possible. Whether the lubricating oil composition is liquid or solid generally depends on the presence or absence of a thickener. Exemplary thickeners include polyurea acetate, lithium stearate, and others.

  In another form of the invention, the propylene oligomer described above is an alkylating agent in addition to being an alkylating agent to produce an alkyl hydroxy aromatic intermediate used in the manufacture of the overbased salts of the invention. It can also be used to produce reaction products other than hydroxy aromatic compounds. For example, using the propylene oligomer described above, oxo alcohols, alkoxylated alkylhydroxy aromatics such as ethoxylated alkylphenol, alkylaromatics such as alkylbenzene and alkyltoluene, alkylated diphenylamines, and alkyl mercaptans, etc. Can also be generated. The methods for forming these reaction products are within the scope of those skilled in the art. The propylene oligomer of the present invention can also be used directly as a high boiling point organic solvent, for example.

  In another aspect of the present invention, the lubricating oil additive of the present invention can be provided as a package or concentrate of the additive. In additive concentrates, the additive is added to an organic diluent (eg, mineral oil, naphtha, benzene, toluene, or xylene) that is substantially inert and normally liquid to form the additive concentrate. To do. These concentrates usually contain from about 20% to about 80% by weight of the diluent. Generally, neutral oils having a viscosity of from about 4 to about 8.5 cSt at 100 ° C., preferably from about 4 to about 6 cSt at 100 ° C. are used as diluents, but for additives and finally produced lubricating oils. Synthetic oils and other organic liquids that are compatible can also be used. The additive package can also include various other additives as described above in a ratio that is easy to combine directly with the required amount of oil having the required amount and having a lubricating viscosity.

  The invention will be further described in the following examples, which are not intended to limit the invention.

[Example 1]
(Production of propylene oligomer)
Propylene oligomers are feedstocks rich in propylene (on average containing 81.4% by weight propylene, 17.4% by weight propane, 0.8% by weight ethane, and 0.4% by weight isobutane) and It was obtained by oligomerization using a large amount of liquid phosphoric acid catalyst. Feed rate was 7.1 KBPD (1000 barrels / day), pressure was 670 psig, and temperature was 245 ° F. (118 ° C.). In the oligomerization reaction, the acid strength of the phosphoric acid catalyst was 114% to 115%. The propylene oligomer was distilled as the bottom fraction. The propylene oligomer had an initial boiling point of at least 248.5 ° C. and an end boiling point of 342.9 ° C. as measured by ASTM D86, and had a carbon atom number distribution as shown in Table 1 below. .

Table 1 ────────────────
mass%
────────────────
C ₁₃ 0
C ₁₄ 3.1
C ₁₅ 21.3
C ₁₆ 15.1
C ₁₇ 12.8
C ₁₈ 13.6
C ₁₉ 7.3
C ₂₀ 6.6
C ₂₁ 7.1
C ₂₂ 3.2
C ₂₃ 2.8
C ₂₄ 2.7
C ₂₅ 1.5
C ₂₆ 1.2
C ₂₇₊ 1.7
────────────────

[Examples 2 to 5]
(Production of propylene oligomer)
Each propylene oligomer was prepared using propylene oligomers distilled at different points in the oligomerization reaction using the same ingredients, amounts and conditions as in Example 1. Each initial boiling point, final boiling point, and carbon atom number distribution are shown in Table 2 below.

Table 2 ──────────────────────────────────
Example 2 Example 3 Example 4 Example 5
──────────────────────────────────
IBP (° C.) 221 228 229 249
FBP (° C) 338 327 336 336
C _12-0 0 0 0
C ₁₂ 9.7 0.9 0.6 0.6
C ₁₃ 0 4.4 6.4 6.4
C ₁₄ 13.6 13.7 14.0 14.0
C ₁₅ 19.5 20.7 20.6 20.6
C ₁₆ 10.1 10.9 11.1 11.1
C ₁₇ 9.4 10.3 9.7 9.7
C ₁₈ 10.5 11.4 10.7 10.7
C ₁₉ 5.5 6.0 5.6 5.6
C ₂₀ 5.0 5.2 4.9 4.9
C ₂₁ 5.2 5.2 5.3 5.3
C ₂₂ 2.5 2.9 2.4 2.4
C ₂₃ 2.2 2.2 2.2 2.2
C ₂₄ 2.3 2.2 2.2 2.2
C ₂₅ 1.2 1.3 1.3 1.3
C ₂₆ 1.0 1.2 1.0 1.0 1.0
C ₂₇₊ 2.3 1.5 1.2 1.2
──────────────────────────────────

[Example 6]
(Production of alkyl hydroxy aromatic compounds)
An alkylphenol was produced by alkylating phenol with the propylene oligomer of Example 1. To a 4 liter round bottom flask was added 744 g (3.03 mol) of the propylene oligomer of Example 1 and 1128 g (12 mol) of phenol. Each reactant was mixed and heated to 80 ° C. At this temperature, 89.3 g of Amberlyst ^™ 36 catalyst (Rohm and Haas) was added and the temperature of the reaction mixture was raised to 110 ° C. The reaction was allowed to proceed for 4 hours under nitrogen at this temperature and under atmospheric pressure. The reaction mixture was cooled to 100 ° C. and the catalyst was removed by filtration. The reaction mixture was then heated to 230 ° C. under 30 mm Hg vacuum and this condition was maintained for 15 minutes to distill excess phenol. The analysis result of the obtained alkylphenol is as follows.
Monoalkylphenol: 92.85%
Paraalkylphenol: 87.76%
Orthoalkylphenol: 5.09%
Dialkylphenol: 1.34%
Unreacted olefin: 4.39%
Ether: 1.29%
Phenol: 0.13%

[Example 7]
(Production of oligomerized alkylphenol overbased salts)
802 g of the alkylated phenol of Example 6 is combined with 747 g of 130N oil, 44.1 g of alkyl aryl sulfonic acid, and 0.2 g of antifoam SI200 (available from Dow Corning) into a 4 liter flask. Put at ambient temperature. The mixture was warmed to 110 ° C. over 25 minutes, and 380 g of slaked lime warmed at that time was added. After adding slaked lime in the warmed state, 112.7 g of sulfur was added and the reaction temperature was raised to 150 ° C. over 20 minutes. After the sulfur was added, the reactor pressure was reduced to 680 mmHg. H ₂ S gas generated in the sulfiding process was captured by two caustic soda bubblers. At 150 ° C., 58.2 g of ethylene glycol was added over 45 minutes. At 150 ° C., 328 g of 2-ethylhexanol was added over 15 minutes. The reaction was then heated to 170 ° C. over 1 hour and 95.5 g ethylene glycol was added in this step.

Following the addition of ethylene glycol, the pressure was increased slightly to 720 mmHg and the reaction conditions were maintained for 20 minutes. The temperature was maintained at 170 ° C. and the pressure was increased to 760 mmHg. At atmospheric pressure, 9 g of carbon dioxide was added over 30 minutes. Following the addition of carbon dioxide, 79.2 g of ethylene glycol was added over 1 hour and the CO ₂ addition rate was increased to 0.8 g / min. About 120 g of CO ₂ was added to stop the carbonation process.

  The solvent was distilled over 1 hour at 215 ° C. and 30 mmHg. While purging with nitrogen at 80 mmHg, the temperature was further increased to 220 ° C. over 1 hour. The product was filtered through celite at 165 ° C. The filtered overbased salt of alkylphenol was degassed in air at 150 ° C. for 4 hours under the condition of 5 liters / hour / kg (product mass). The product had Ca: 9.46%, S: 3.2%, kinematic viscosity at 100 ° C: 235.2 cSt, and TBN: 260 mg / KOH / g.

[Comparative Example 1]
(Production of propylene tetramer)
A propylene tetramer was produced in the same manner as the propylene oligomer of Example 1 except that the acid strength of phosphoric acid was 111% to 112%. The resulting propylene oligomer had an initial boiling point of 180 ° C. and an end point of 219 ° C. as measured by ASTM D86. Table 3 below shows the carbon atom distribution of the propylene tetramer.

Table 3────────────────
mass%
────────────────
C ₉ 2.1
C ₁₀ 3.5
C ₁₁ 6.3
C ₁₂ 59.5
C ₁₃ 8.2
C ₁₄ 7.0
C ₁₅ 12.0
C ₁₆₊ 1.3
────────────────

[Comparative Example 2]
(Production of alkylphenols)
Alkylphenol was produced in the same manner as in Example 3 except that the propylene tetramer of Comparative Example 1 was used in place of the propylene oligomer of Example 1. The analysis results of the produced alkylphenol are as follows.
Monoalkylphenol: 95.84%
Paraalkylphenol: 87.97%
Orthoalkylphenol: 7.87%
Dialkylphenol: 1.73%
Light alkylphenol: 1.54%
Unreacted olefin: 4.39%
Ether: 0.59%
Phenol: 1.03%.

[Comparative Example 3]
(Production of overbased sulfurized alkylphenols from propylene tetramer alkylphenols)
Using the alkylphenol described in Comparative Example 2, an overbased sulfurized alkylphenol was produced in the same manner as in Example 4. The analysis results of the overbased sulfurized alkylphenol produced are as follows. Ca: 9.68%, S: 3.37%, kinematic viscosity at 100 ° C .: 406.3 cSt, and TBN: 271 mg / KOH / g.

[Comparative Example 4]
(Manufacturing additive packages)
An additive package containing the following (a) to (h) was produced: (a) 24.1% by weight of overbased sulfurized alkylphenol of Comparative Example 3; (b) bissuccinimide dispersant treated with ethylene carbonate ( MW 2300 polybutene derived) oily concentrate 35.2% by weight; (c) low overbased calcium sulfonate oily concentrate 10.6% by weight; (d) secondary zinc dithiophosphate antiwear agent 13.4% by weight of oily concentrate; (e) 1.7% by weight of oily concentrate of molybdate sulfide complex of succinimide dispersant (derived from polybutene of MW 1000); (f) Borated glycerol mono Oleic acid friction modifier 3.11% by weight; (g) 0.05% by weight of antifoaming agent; and (h) remaining exon 150N (class I base oil, Exxon Mobil Commercially available from).

[Comparative Example 5]
(Manufacture of lubricating oil composition)
91.1% by weight of a mixture of 74% by weight of Exon 150N (Class I base stock) and 26% by weight of Exon 600N (Class I base stock, commercially available from Exxon Mobil), and viscosity index A lubricating oil composition was produced by adding the additive package of Comparative Example 4 to a mixture of 8.9% by weight of improver (Paratone 8004). The final concentration of the additive package in the lubricating oil composition was 9.65% by weight.

[Example 8]
(Manufacturing additive packages)
An additive package containing the same components as in Comparative Example 4 in the same amount except that 23.6% by mass of the overbased salt of the alkylated oligomer of Example 7 was used instead of the overbased sulfurized alkylphenol of Comparative Example 3 Manufactured.

[Example 9]
(Manufacture of lubricating oil composition)
A mixture of 74% by mass of exon 150N (type I base oil) and 26% by mass of exon 600N (type I base oil) and 8.9% by mass of a viscosity index improver (Paratone 8004) A lubricating oil composition was prepared by adding the additive package of Example 8. The final concentration of the additive package in the lubricating oil composition was 9.65% by weight.

[test]
(Compatibility test 1)
In the compatibility test 1, the additive package of Example 8 and the additive package of Comparative Example 4 were compared. In this test, the tendency of the additive package to form precipitates, aggregates, or gels over time was evaluated. The additive package was poured into a glass flask and stored at 20 ° C. In order to test the compatibility of the package at 80 ° C., the package was subjected to a heating cycle (8 hours at 80 ° C., then 14 hours at 20 ° C.) daily. The test was conducted for 28 days and evaluated at the end of this period. Evaluation was based on the following criteria.
0 = no sediment.
1 = Muddy but no precipitate.
2 = There is a precipitate.
3 = gelled.
Table 4 below shows the results of the test.

  The compatibility test 1 was applied under the same time and temperature conditions, and the lubricating oil compositions of Example 9 and Comparative Example 5 were also evaluated. Table 4 below shows the results of the test.

(Compatibility test 2)
In order to further demonstrate the compatibility of the oligomerized alkylphenol overbased salt of the present invention, each of the oligomerized alkylphenol overbased salt of Example 7 and the overbased sulfurized alkylphenol of Comparative Example 3 was treated with high excess. Combined with an additive package containing basic calcium sulfonate on an equivalent calcium basis. That is, each package was derived from the overbased salt of the oligomerized alkylphenol of Example 7 or the overbased sulfurized alkylphenol of Comparative Example 3 and 100 millimoles of calcium per kg of additive package and the remaining sulfonate of the base oil. From 100 milligrams of calcium per kg of additive package. These additive packages were poured into glass flasks and stored at 20 ° C. In order to test the compatibility of the package at 80 ° C., the package was subjected to a daily heating cycle (8 hours at 80 ° C., then 14 hours at 20 ° C.). The test was conducted for 28 days and evaluated at the end of this period. Evaluation was carried out in the same manner as compatibility test 1. Table 4 below shows the results of this test.

Table 4 ───────────────────────────────────
Performance Test Example 7 Example 7 Comparative Example 3 Comparative Example 3
───────────────────────────────────
Compatibility test 1 20 ° C 80 ° C 20 ° C 80 ° C
-Additive package 2 2 2 2
-Additive package + oil 2 2 2 2
Compatibility test 2 20 ° C 80 ° C 20 ° C 80 ° C
-Additive package 2 2 2 2
───────────────────────────────────
0 = no precipitate 1 = cloudy 2 = precipitate 3 = gelled

(Komatsu Hot Tube (KHT) test)
The lubricating oil compositions of Example 9 and Comparative Example 5 were evaluated by the Komatsu Hot Tube (KHT) test. The lubricating oil composition was passed through a glass tube that was temperature controlled over a period of time using an appropriate air flow. The test was conducted for 16 hours at a test temperature of 290 ° C. Next, the glass tube was cooled and washed, and the color of the lacquer deposits remaining on the inner surface of the glass tube was determined using the color merit to evaluate in the range of 0-10 (0 = black, 10 = clean). If the glass tube is completely blocked by deposits, the test result is recorded as “blocked”. Table 5 below shows the results of the Komatsu heat tube test.

(Dispersibility test)
The lubricating oil compositions of Example 9 and Comparative Example 5 were evaluated by a dispersibility test. In this test, the ability of oil to retain asphaltenic and carbonaceous materials was evaluated by measuring the dispersibility of the oil and black material on filter paper. Dispersibility was measured for both fresh and aged oils with different treatments under heating conditions and those with and without water added.

  Fresh samples consisted mainly of a lubricating oil composition and carbon black. Aged samples consisted of a mixture of fresh lubricating oil compositions that were aged by heating at high temperatures under oxidizing conditions. Carbon black was added to the aged sample following the aging process.

  Both the fresh oil sample and the aged oil sample were subjected to 3 different heat treatments (6 different treatments in total) with and without water added. The treated sample was then dripped onto the filter paper and allowed to develop for 48 hours in an incubator. After color development, the droplet formed a small dark sludge area surrounded by light oil. The oil and sludge area diameters were measured and the oil: sludge diameter ratio was calculated. Test results were recorded as 6X (sum of oil: sludge diameter ratio from 6 different treatments). Table 5 below shows the results of the dispersibility test.

Table 5 ──────────────────────────────
Performance Test Example 9 Comparative Example 5
──────────────────────────────
Komatsu Heat Tube Test 8 8
Dispersibility test 489/600 492/600
──────────────────────────────

(Low temperature viscosity performance of lubricating oil)
The low temperature viscosity performance of the overbased salt of the oligomerized alkylphenol of Example 7 and the overbased sulfurized alkylphenol of Comparative Example 3 was compared in 5W30 oil and 5W40 oil.

  5W30 oil contains the following (a) to (j): (a) 3% by weight of oily concentrate of boronated bissuccinimide dispersant; (b) oily concentration of bissuccinimide dispersant treated with ethylene carbonate (C) low overbased calcium sulfonate oily concentrate 1.36% by weight; (d) terephthalic acid and bissuccinimide dispersant salt oily concentrate 0.4% by weight; (e) Oil concentrate of secondary zinc dithiophosphate antiwear agent 1.08% by weight; (f) Oil concentrate of molybdate sulfide complex of monosuccinimide dispersant 0.4% by weight; (g) alkylated diphenylamine Antioxidant 0.5% by weight; (h) phenolic (phenolic) antioxidant 0.5% by weight; (i) antifoaming agent 30 ppm; and (j) the balance of the base type III base oil. The overbased salt of the oligomerized alkylphenol of Example 7 and the overbased sulfurized alkylphenol of Comparative Example 3 were added to 5W30 oil on an equivalent calcium basis. The overbased salt of the oligomerized alkylphenol of Example 7 added to 5W30 oil was 2.32% by mass. The overbased sulfurized alkylphenol of Comparative Example 3 added to 5W30 oil was 2.37% by mass.

  The 5W40 oil contains the following (a) to (j): (a) 3% by weight of an oily concentrate of a boronated bissuccinimide dispersant; (b) an oily concentrate of a bissuccinimide dispersant treated with ethylene carbonate (C) low overbased calcium sulfonate oily concentrate 1.36% by weight; (d) terephthalic acid and bissuccinimide dispersant salt oily concentrate 0.4% by weight; (e) Oil concentrate of secondary zinc dithiophosphate antiwear agent 1.08% by weight; (f) Oil concentrate of molybdate sulfide complex of monosuccinimide dispersant 0.4% by weight; (g) alkylated diphenylamine Antioxidant 0.5% by weight; (h) phenolic (phenolic) antioxidant 0.5% by weight; (i) antifoaming agent 30 ppm; and (j) the balance of the base type III base oil. The overbased salt of the oligomerized alkylphenol of Example 7 and the overbased sulfurized alkylphenol of Comparative Example 3 were added to 5W40 oil on an equivalent calcium basis. The overbased salt of the oligomerized alkylphenol of Example 7 added to 5W40 oil was 2.32% by mass. The overbased sulfurized alkylphenol of Comparative Example 3 added to 5W40 oil was 2.37% by mass.

  The low temperature viscosity performance of the final 5W30 and 5W40 oils was evaluated using the ASTM D 4684 Mini-Rotary Viscometer (MRV) test.

(ASTM D4684 small rotational viscometer (MRV) test)
In this test, the test oil was first heated in a small rotational viscometer cell and then cooled to the test temperature (in this case -35 ° C). Each cell contains a tuned rotor-stator set. A string with a weight attached is wound around the rotor shaft, and the rotor is rotated by the string. Test results were recorded in yield stress as “<” for force applied in Pascal units. A 150 g weight is then applied to determine the apparent viscosity of the oil. The higher the apparent viscosity, the less oil will be supplied to the oil pump supply port sufficiently and continuously. Test results were recorded as viscosities in centipoise.

  Tables 6 and 7 below show the MRV test results for 5W30 and 5W40 oils, respectively.

Table 6
5W30 oil ───────────────────────────────
Performance Test Example 7 Comparative Example 3
──────────────────────────────
MRV
Yield stress 0 <Y <= 35 0 <Y <= 35
Viscosity 18512 18224
──────────────────────────────

Table 7
5W40 oil ───────────────────────────────
Performance Test Example 7 Comparative Example 3
──────────────────────────────
MRV
Yield stress 0 <Y <= 35 0 <Y <= 35
Viscosity 33946 36225
──────────────────────────────

(Corrosion test)
The corrosivity of the oil containing the oligomerized alkylphenol overbased salt of Example 7 and the oil containing the overbased sulfurized alkylphenol of Comparative Example 3 was evaluated by ASTM D6594-06 corrosion test. In this test, a metal test tube formed from lead (Pb), tin (Sn) or copper (Cu) was placed in high temperature (135 ° C.) oil for 168 hours with a constant amount of air flowing. The amount of corrosion is shown as parts per million (ppm) of the amount of metal in the oil. The lubricating oil composition used is the same as that for 5W30 in the lubricating oil low temperature performance test described above. Table 8 below shows the results of the corrosion test.

Table 8────────────────────────────
Performance Test Example 7 Comparative Example 3
────────────────────────────
Corrosion test Pb (ppm) 78 106
Cu (ppm) 9 9
Sn (ppm) 1 1
────────────────────────────

Various modifications can be made to the aspects disclosed herein. Accordingly, the above description should not be construed as limiting, but merely exemplary of preferred embodiments. For example, the functions described or suggested above and as the best mode for carrying out the invention are for illustrative purposes only. Other modifications and schemes may be implemented by those skilled in the art without departing from the scope and spirit of the present invention. Further, those skilled in the art will be able to make other modifications within the scope and spirit of the claims appended hereto.

Claims (15)

  An overbased salt of an oligomerized alkylhydroxy aromatic compound, wherein the alkyl group of the alkylhydroxyaromatic compound has an initial boiling point of at least 195 ° C. and a temperature exceeding 325 ° C. and not more than 400 ° C., as measured by ASTM D86 An overbased salt of an oligomerized alkylhydroxyaromatic compound which is derived from an olefin mixture comprising a propylene oligomer having an end point of   The overbased salt of claim 1, wherein the propylene oligomer has an initial boiling point of at least 220 ° C as measured by ASTM D86.   The overbased salt according to claim 1 or 2, wherein the propylene oligomer has an end point of 330 ° C to 375 ° C as measured by ASTM D86. Propylene oligomers, overbased salt according to any one of claims 1 to 3 carbon atoms distribution including at least 50% by weight of those having carbon atoms of C ₁₄ to C _20. The overbased salt according to any one of claims 1 to 4, wherein the propylene oligomer contains 1% by mass to 5% by mass of C ₂₇₊ carbon atoms.   The overbased salt according to any one of claims 1 to 5, wherein the salt is an alkali metal salt or an alkaline earth metal salt.   The overbased salt according to any one of claims 1 to 6, wherein the oligomerized alkylhydroxy aromatic compound is a sulfurized alkylhydroxy aromatic compound.   8. The hydroxy aromatic compound is phenol and the olefin mixture comprises propylene pentamer, hexamer, heptamer, octamer, nonamer, or mixtures thereof. The overbased salt according to item. A process for producing an overbased salt of an oligomerized alkylhydroxyaromatic compound comprising the following steps:
(A) alkylating a hydroxy aromatic compound with an olefin mixture comprising a propylene oligomer having an initial boiling point of at least 195 ° C. and an end point of greater than 325 ° C. and less than or equal to 400 ° C., as measured by ASTM D86 Obtaining a hydroxy aromatic compound;
(B) a step of neutralizing the alkylhydroxy aromatic compound of step (a) to obtain a salt of the alkylhydroxyaromatic compound;
(C) oligomerizing the salt of the alkylhydroxyaromatic compound of step (b) to obtain an oligomerized alkylhydroxyaromatic salt; and (d) the oligomerized alkylhydroxyaromatic of step (c) A step of overbasing a salt of a compound to obtain an overbased salt of an oligomerized alkylhydroxy aromatic compound.   The method of claim 9, wherein the propylene oligomer has an initial boiling point of at least 220 ° C and an end point of 330 ° C to 375 ° C as measured by ASTM D86. Propylene oligomers, those having a carbon atom of the C ₁₄ to C ₂₀ comprises at least 50 wt%, and according to those having carbon atoms of C _27Tasu to claim 9 or 10 carbon atoms distribution including at least 1 wt% Method.   A lubricating oil composition comprising (a) a major amount of oil having a lubricating viscosity and (b) an overbased salt of an oligomerized alkylhydroxyaromatic compound according to any one of claims 1-9.   A method for reducing endocrine disruption as an effect of a lubricating oil composition on mammals, comprising the overbased salt of an oligomerized alkylhydroxyaromatic compound according to any one of claims 1 to 9, Adding to a lubricating oil composition comprising a major amount of oil having a lubricating viscosity. Propylene oligomer having an initial boiling point of at least 195 ° C. measured by ASTM D86 and an end boiling point of more than 325 ° C. and not more than 400 ° C., and having at least 50 masses of C _{14 to} C ₂₀ carbon atoms % Propylene oligomer having a carbon atom distribution. (A) contacting a feedstock containing at least 50% by weight of propylene with respect to the total weight of a liquid phosphoric acid catalyst having an acid strength of 114% to 122% in a reaction zone under oligomerization conditions; and (b ) Propylene oligomer having an initial boiling point of at least 195 ° C. measured by ASTM D86 and an end boiling point of more than 325 ° C. and not more than 400 ° C., having at least 50 carbon atoms of C _{14 to} C ₂₀ Separating a propylene oligomer having a carbon atom distribution comprising mass%.