JP6939751B2 - Compounds and lubricating oil compositions - Google Patents

Description

The present specification discloses compounds and lubricating oil compositions.

Conventionally, as a lubricating oil composition, for example, a kinematic viscosity of 1 to 6 mm ² / s at 100 ° C.,% C _p is 70 or more, and the lubricating oil base oil is and% C _A is 2 or more, PSSI of 20 or less (For example, see Patent Document 1). In this lubricating oil composition, a styrene-isoprene hydrogenated copolymer, two types of dispersed polymethacrylate, an ethylene-propylene copolymer and the like are added to a group III base oil produced by hydrocracking to the above range. It is said to obtain the characteristics of.

Japanese Unexamined Patent Publication No. 2010-280821

However, the above-mentioned lubricating oil composition of Patent Document 1 is said to have sufficient fuel efficiency while maintaining practical performance such as durability, but it is not yet sufficient, for example, the viscosity characteristics are further improved. A new compound has been desired.

The present disclosure has been made in view of such a problem, and an object of the present disclosure is to provide a novel compound and a lubricating oil composition having a small change in viscosity with respect to a temperature change.

As a result of diligent research to achieve the above-mentioned object, the present inventors have found that a chain having a cyclic hydrocarbon group at the end of the main chain has a small change in viscosity with respect to a temperature change. The invention disclosed in the specification has been completed.

That is, the compounds disclosed herein are:
It has a carbon number in the range of 25 or more and 45 or less, may contain carbon and hydrogen, may contain oxygen, contains one or more unsaturated bonds, has a chain hydrocarbon group constituting the main chain, and is branched. It has a group in the range of 1 or more and 5 or less, has a cyclic hydrocarbon group at least at one end of the main chain, and has a cyclic hydrocarbon group as the branched group in the range of 1 or more and 2 or less. It is what you are doing.

The lubricating oil compositions disclosed herein include the compounds described above.

In the present disclosure, it is possible to provide a novel compound and a lubricating oil composition having a small change in viscosity with respect to a temperature change. The reason for this can be inferred as follows. For example, the compound of the present disclosure is composed of a chain hydrocarbon group and a plurality of cyclic hydrocarbon groups, and is less likely to be entangled and more entangled than a molecule composed of only chain hydrocarbons. It is thought that it is difficult to become strong. As a result, even if the temperature rises, the degree of disentanglement and the decrease in viscosity is low, so it is presumed that the change in viscosity is small with respect to the temperature change. As described above, in the present disclosure, it is possible to make the viscosity change small with respect to the temperature change.

(Compound)
The compound of the present disclosure (hereinafter, simply referred to as a compound) has a carbon number of 25 or more and 45 or less. This compound may contain carbon and hydrogen and may also contain oxygen. This compound contains one or more unsaturated bonds. In addition, this compound has a chain hydrocarbon group constituting the main chain, and has a branched group in the range of 1 or more and 5 or less. Further, this compound has a cyclic hydrocarbon group at at least one end of the main chain, and has a cyclic hydrocarbon group as a branched group in the range of 1 or more and 2 or less. This compound may have 30 or more carbon atoms, or may have 32 or more carbon atoms. Further, this compound may have 42 or less carbon atoms, or may have 40 or less carbon atoms. This compound may be oxygen-free or oxygen-containing. For example, this compound may be composed only of carbon and hydrogen, or may be composed only of carbon, hydrogen and oxygen. When oxygen is contained, it may be contained in the main chain of the compound or may be contained in a branched group. At this time, the main chain may be bonded to a group branched via oxygen. Further, one or more unsaturated bonds may be contained in, for example, a chain hydrocarbon group or a cyclic hydrocarbon group. Further, the chain hydrocarbon group may not contain an unsaturated bond, and at this time, the cyclic hydrocarbon group may contain an unsaturated bond. Further, both the chain hydrocarbon group and the cyclic hydrocarbon group may contain an unsaturated bond. Since the compound of the present disclosure has such a structure, it is presumed that the viscosity change is small with respect to the temperature change.

In the compounds of the present disclosure, the cyclic hydrocarbon group may have one or more unsaturated bonds or may not have an unsaturated bond. The cyclic hydrocarbon group may have either a phenyl group or a cyclohexyl group. The cyclic hydrocarbon group may be at the end of the main chain or at one end and not at the other end. This compound may have two of the same cyclic hydrocarbon groups, or may have two of the same cyclic hydrocarbon groups and one of the other cyclic hydrocarbon groups as a branched group. This cyclic hydrocarbon group may have a substituent. Moreover, it is preferable that this compound does not contain a heterocycle. This compound may contain any of a phenyl group, a cyclohexyl group, and the above-mentioned cyclic hydrocarbon group. This compound may contain the above-mentioned chain hydrocarbon group having a saturated or unsaturated hydrocarbon having 8 to 18 carbon atoms as a main chain. This chain hydrocarbon group may have a substituent as a branched group, or may contain an ether bond in which 1 or more and 3 or less methylene groups are substituted with oxygen atoms.

The compound of the present disclosure may be represented by the chemical formula (1). In this chemical formula (1), R ¹ and R ² are the above-mentioned cyclic hydrocarbon groups, and may be the same cyclic hydrocarbon group or different. The cyclic hydrocarbon group may have a substituent or may be a heterocycle. R ³ may be a hydrogen, a phenyl group, a cyclohexyl group, or any of ^{the above R 1} and R ^2. Of these, hydrogen, phenyl group, cyclohexyl group and the like are preferable. R ⁴ may be the above-mentioned chain hydrocarbon group having a saturated or unsaturated hydrocarbon having 8 to 18 carbon atoms as a main chain. This R ⁴ may have a substituent as a branched group, or may contain an ether bond in which 1 or more and 3 or less methylene groups are substituted with oxygen atoms.

The chemical formula (1) may have the following characteristics. For example, R ¹ and R ² may be represented by any of the chemical formulas (2) and (3). X in the chemical formula (2) is a linear group composed of saturated or unsaturated hydrocarbons having 1 or more carbon atoms and 4 or less carbon atoms, and may contain an ether bond in which one or two methylene groups are substituted with oxygen atoms. .. R ³ may be a group represented by any of the chemical formulas (2) to (5). R ⁴ may include a structure of any one or more of the chemical formulas (6) to (9). Further, R ⁴ may have one or more groups of any one or more of the chemical formulas (10) to (14) as branched groups in the range of 1 or more and 3 or less.

The compound of the present disclosure may be, for example, one or more of the chemical formulas (15) to (22). Alternatively, the compound of the present disclosure may be one or more of the chemical formulas (23) to (30).

In the compound of the present disclosure, the cyclic hydrocarbon group described above may be, for example, any one or more shown in the groups (1) to (56). Of these, as the cyclic hydrocarbon group, groups (2) to (4), groups (5), groups (41) and the like are preferable.

The compounds of the present disclosure preferably have a kinematic viscosity at 100 ° C. in ^{the range of 2.0 mm 2} / s or more and 10.0 mm ² / s or less, and 3.0 mm ² / s or more and 9.0 mm ² / s or less. More preferably, it is in the range. Further, the compound of the present disclosure preferably has a kinematic viscosity at 40 ° C. of 40.0 mm ² / s or less. The kinematic viscosity is preferably in such a range, and such a compound can be suitably used as a lubricating oil.

Further, the compound of the present disclosure preferably has a viscosity index VI (Viscosity Index) of higher, for example, preferably 215 or more, more preferably 235 or more, and further preferably 240 or more. .. When the viscosity index VI is 235 or more, it is higher than that of polyalphaolefin (PAO), which is preferable. The viscosity index VI is a value calculated based on JIS-K2284 from kinematic viscosities of 40 ° C. and 100 ° C.

(Compound manufacturing method)
A method for producing the compound of the present disclosure will be described. Here, a method for producing the compounds of the chemical formulas (15) to (17) will be described as an example. This production method may include a precursor production step of producing a precursor and a synthesis step of binding a main chain to the precursor. In the precursor generation step, a cyclic hydrocarbon compound in which a chain hydrocarbon group is bonded and MgBr is bonded to the end of the chain hydrocarbon and a chain hydrocarbon group are bonded to form a formyl group at the end of the chain hydrocarbon. It reacts with the bound cyclic hydrocarbon compound to produce a precursor alcohol having cyclic hydrocarbon groups at both ends. In this step, a raw material containing the structure and the bond described in the above-mentioned compound shall be appropriately used. For example, the cyclic hydrocarbon compound may have a structure of chemical formulas (2) and (3), particularly groups (1) to (56). Examples of the solvent used in this step include tetrahydrofuran (THF) and the like. The formation temperature of the precursor may be, for example, in the range of 20 ° C. or higher and 80 ° C. or lower. The obtained precursor alcohol may be extracted with dichloromethane or purified by chromatography, for example.

In the synthesis step, the chain hydrocarbon compound having a chain hydrocarbon group constituting the main chain and having Br at the end is reacted with the precursor alcohol prepared above, and the chain hydrocarbon group is added to the oxygen of the precursor alcohol. To synthesize the above compound. The chain hydrocarbon compound may contain, for example, one or more structures of any one or more of the chemical formulas (6) to (9). Examples of the solvent used in this step include tetrahydrofuran (THF) and the like. In this step, an alkali hydride may be added to carry out the synthesis reaction. The reaction temperature may be in the range of 20 ° C. or higher and 50 ° C. or lower. After the synthesis reaction, the solvent may be removed and purified by chromatography. In this way, the compounds of the chemical formulas (15) to (17) can be produced.

(Lubricating oil composition)
The lubricating oil composition of the present disclosure contains the above-mentioned compounds. This lubricating oil composition may contain one kind of the above-mentioned compound, or may contain two or more kinds of the above-mentioned compounds. Further, this lubricating oil composition may contain one or more of solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil and solvent dewaxed base oil in addition to the above-mentioned compounds. The lubricating oil composition preferably contains more of the above-mentioned compounds, preferably 80% by mass, more preferably 85% by mass or more, and further preferably 90% by mass or more.

This lubricating oil composition may contain various additives in addition to the above-mentioned compounds. Examples of the additive include a hydrocarbon-based viscosity index improver and a poly (meth) acrylate-based viscosity index improver. In addition, "poly (meth) acrylate" is a general term for polymethacrylate and polyacrylate. Examples of the hydrocarbon-based viscosity index improver include one or more of a styrene-diene hydrogenated copolymer, an ethylene-α-olefin copolymer or a hydride thereof, polyisobutylene or a hydride thereof, and polyalkylstyrene. It may be a mixture of one or more of these. Examples of the diene include butadiene and isoprene. Examples of the α-olefin include propylene, isobutylene, 1-butene, 1-hexene, 1-octene, 1-decene and 1-dodecene.
Examples of the poly (meth) acrylate-based viscosity index improver include dimethylaminomethylmethacrylate, dimethylaminoethylmethacrylate, diethylaminomethylmethacrylate, 2-methyl-5-vinylpyridinemorpholinomethylmethacrylate, morpholinoethylmethacrylate, and N-vinyl as monomers. Examples thereof include those containing one or more of pyrrolidone methacrylate and the like.

Further, the lubricating oil composition of the present disclosure may contain a wear modifier as an additive. Examples of the wear adjusting agent include organic molybdenum and ashless wear adjusting agent. Examples of the organic molybdenum include molybdenum dithiophosphate and molybdenum dithiocarbite.

In the present embodiment described in detail above, it is possible to provide a novel compound and a lubricating oil composition having a small change in viscosity with respect to a temperature change. The reason for this is that, for example, the above-mentioned compound is composed of a chain hydrocarbon group and a plurality of cyclic hydrocarbon groups, and is less likely to be entangled and entangled than a molecule composed of only chain hydrocarbons. It is thought that the match is stronger and less likely to occur. As a result, even if the temperature rises, the degree of disentanglement and the decrease in viscosity is low, so it is presumed that the change in viscosity is small with respect to the temperature change. As described above, in the above-mentioned compound, it is possible to make the viscosity change small with respect to the temperature change.

It goes without saying that the present disclosure is not limited to the above-described embodiment, and can be implemented in various embodiments as long as it belongs to the technical scope of the present disclosure.

Hereinafter, an example in which the compound of the present disclosure is specifically prepared will be described as an experimental example. Experimental Examples 17 to 19 correspond to Comparative Examples, and Experimental Examples 1 to 16 correspond to Examples.

(Experimental Example 1)
50 mL of dehydrated tetrahydrofuran (THF) is placed in a flask, 0.432 g of magnesium and 2.1 mL of (2-bromoethyl) benzene are added, and 2-phenylethyl magnesium bromide is stirred at 50 ° C. for 2 hours under a nitrogen atmosphere. Was adjusted (Scheme 1). While maintaining 50 ° C., 2.22 mL of 3-phenylpropanal was added dropwise to this solution, and the mixture was refluxed overnight. After cooling to 0 ° C., 10 mL of saturated aqueous ammonium chloride solution was added, and the mixture was extracted with dichloromethane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solution was filtered. After distilling off the solvent, the residue was purified by silica gel chromatograph to obtain 3.3 g of the precursor 1,5-diphenylpentane-3-ol (Scheme 2). 50 mL of dehydrated THF and 2.7 g of 1,5-diphenylpentane-3-ol were placed in a flask, 0.27 g of sodium hydride was added little by little, and the mixture was stirred under a nitrogen atmosphere for 30 minutes (Scheme 3). 3.2 g of farnesyl bromide was added and refluxed overnight. After distilling off the solvent, the residue was purified by silica gel chromatograph to obtain 1.5 g of the compound of the formula (15). The structure was confirmed by GC-MS, ^{1 1} H-NMR.

(Experimental Examples 1 to 16)
The molecular structure was designed by calculation by combining Monte Carlo tree search and molecular dynamics method to improve the structure of the molecule. A candidate compound is designed by the search algorithm of the Monte Carlo tree search method, and the viscosity index VI of the candidate compound is evaluated by the calculation of the molecular dynamics method. The process of designing a candidate compound in which the above was changed was repeated to obtain some compounds having a viscosity index VI of 250 or more. Using this compound as a base material, a synthetic molecular structure was designed, and its kinematic viscosity and viscosity index VI were derived by calculation of the molecular dynamics method. Compounds having a viscosity index VI in a good range were designated as Experimental Examples 1 to 16. The compounds of the above chemical formulas (15) to (30) were designated as Experimental Examples 1 to 16, respectively.

(Experimental Examples 17-19)
The PAOs decene, decene, and dodecene were designated as Experimental Examples 17 to 19, respectively.

(Examination of viscosity index VI and kinematic viscosity)
^{The kinematic viscosity (mm 2} / s) and viscosity index VI of Experimental Examples 1 to 19 at 40 ° C. and 100 ° C. were calculated by the molecular dynamics method.

(Results and discussion)
Table 1 shows the structures of Experimental Examples 1 to 19, the viscosity index VI, and the kinematic viscosity (mm ² / s) at 40 ° C. and 100 ° C. Table 1 shows the error between the calculation results of Experimental Examples 17 to 19 and the literature values (Ind.Eng.Chem.Prod.Res.Dev., (1980), 10, 2). It was evaluated that the calculation results for the kinematic viscosities at each temperature showed values close to those in the literature. Further, regarding the viscosity index VI, the calculation result tends to overestimate the viscosity index VI compared to the literature value, but it can be evaluated that the order of the viscosity index VI can be reproduced. Incidentally, literature values of Example 17, a kinematic viscosity of 40 ° C. is 15.6mm ² / s, 100 ℃ was 3.7 mm ² / s, viscosity index VI is 122. The literature values of Experimental Example 18 were that the kinematic viscosity at 40 ° C. was 20.2 mm ² / s, the viscosity at 100 ° C. was 4.4 mm ² / s, and the viscosity index VI was 131. Literature values of Example 19, a kinematic viscosity of 40 ° C. is 24.3mm ² / s, 100 ℃ was 5.1 mm ² / s, viscosity index VI of 144. As shown in Table 1, in Experimental Examples 1 to 16, the compound has a novel structure, and the kinematic viscosity at 100 ° C. is in ^{the range of 2.0 mm 2} / s or more and 10.0 mm ² / s or less. It was found that the kinematic viscosity at 40 ° C. was 40.0 mm ² / s or less and had preferable kinematic viscosity characteristics. Further, it was found that in Experimental Examples 1 to 16, the viscosity index VI was 215 or more, and the characteristics were equal to or higher than those of Experimental Examples 17 to 19 which are general lubricating oils. In particular, Experimental Examples 1 to 5, 9 to 12, 15 and 16 had a viscosity index VI of 235 or more, and were found to have particularly preferable characteristics.

It should be noted that the present disclosure is not limited to the above-described examples, and it goes without saying that the present disclosure can be carried out in various aspects as long as it belongs to the technical scope of the present disclosure.

The compounds and lubricating oil compositions disclosed herein are available in the technical field of lubricating oils.

Claims (6)

A compound represented by the chemical formulas (1) to (16).

The compound according to claim 1, wherein the kinematic viscosity at 100 ° C. is in ^{the range of 2.0 mm 2} / s or more and 10.0 mm ² / s or less. The compound according to claim 1 or 2 , wherein the kinematic viscosity at 100 ° C. is in ^{the range of 3.0 mm 2} / s or more and 9.0 mm ² / s or less. The compound according to any one of claims 1 to 3 , wherein the kinematic viscosity at 40 ° C. is 40.0 mm ² / s or less. A lubricating oil composition containing the compound according to any one of claims 1 to 4. The lubricating oil composition according to claim 5, which contains 80% by mass or more of the compound.