WO2011099195A1

WO2011099195A1 - Lubricant additive composition

Info

Publication number: WO2011099195A1
Application number: PCT/JP2010/067774
Authority: WO
Inventors: 八木下　和宏
Original assignee: Ｊｘ日鉱日石エネルギー株式会社
Priority date: 2010-02-12
Filing date: 2010-10-08
Publication date: 2011-08-18
Also published as: JP5537179B2; CN102753665A; SG183191A1; CN102753665B; EP2535397A1; US20120302475A1; EP2535397B1; EP2535397A4; JP2011162723A

Abstract

Disclosed is a lubricant additive composition that comprises a metal salt of a phosphorous-containing compound, is easy to prepare, does not have adverse effects such as causing rubber seals to swell, and moreover has excellent storage stability, wherein the lubricant additive composition is characterized by including 10 to 90 mass%, based on the total amount of the composition, of the metal salt of the phosphorous-containing compound, which is represented by formula (1), in a hydrocarbon solvent in which the kinematic viscosity at 100°C is 0.5 to 4.5 mm²/s, the %C_A is no more than 3, and the sulfur content is no more than 0.05 mass% that is selected from among a mineral oil, a synthetic hydrocarbon oil, and a mixture of both. (In formula (1), X¹ and X² represent an oxygen or sulfur atom, R¹, R², R³, and R⁴ each independently represent a C_3-12 linear alkyl group with an average carbon number of at least 5, and M represents a divalent metal atom.)

Description

Lubricating oil additive composition

The present invention relates to an additive composition for lubricating oil containing a metal salt of a phosphorus-containing compound.

Metal salts of phosphorus-containing compounds such as dialkylthiophosphates or dialkylphosphates that are solid or viscous liquids at room temperature have poor handling during production and transportation, or dissolve in base oils at room temperature in a short time. However, since it has problems such as poor storage stability after being dissolved, a technique for dissolving it in an amine compound or the like and liquefying it has been proposed (see Patent Document 1). However, when a metal salt of a phosphorus-containing compound dissolved in such an amine compound or the like is added to the lubricating oil, there is a possibility of adverse effects such as swelling of the rubber seal.

International Publication No. 2004/003118 Pamphlet

The present invention contains a dialkylthiophosphate ester or a metal salt of a dialkyl phosphate ester that is solid or viscous liquid at room temperature, without adverse effects such as swelling of the rubber seal, and excellent in storage stability. And a method for producing an additive composition for lubricating oil in which the above compound is dissolved in a base oil in a short time at a relatively low temperature of 60 ° C. or lower. It is.

As a result of intensive studies to solve the above problems, the inventors of the present invention have made it possible to shorten the metal salt of a phosphorus-containing compound at a high concentration and a relatively low temperature of 60 ° C. or less by using a specific hydrocarbon solvent. It has been found that it can be dissolved in time and the storage stability after dissolution is good, and the present invention has been completed.

That is, the present invention has a kinematic viscosity of 100 ° C. is ^{0.5 ~ 4.5mm 2 / s,%} C A of 3 or less, and mineral oil sulfur content is not more than 0.05 wt%, the hydrocarbon-based synthetic Lubricant comprising a hydrocarbon solvent selected from oil and a mixture thereof containing 10 to 90% by mass of a metal salt of a phosphorus-containing compound represented by the general formula (1) based on the total amount of the composition The present invention relates to an additive composition for oil.

(In the general formula (1), X ¹ and X ² are oxygen or sulfur atoms, R ¹ , R ² , R ³ and R ⁴ are each independently a straight-chain alkyl group having 3 to 12 carbon atoms and having an average carbon number 5 or more, M represents a divalent metal atom.)

Further, the present invention has a kinematic viscosity of 100 ° C. is ^{0.5 ~ 4.5mm 2 / s,%} C A of 3 or less, and mineral oil sulfur content is not more than 0.05 wt%, the hydrocarbon-based synthetic A lubricating oil characterized by dissolving 10 to 90% by mass of a metal salt of a phosphorus-containing compound represented by the general formula (1) in a hydrocarbon solvent selected from oil and a mixture thereof based on the total amount of the composition The present invention relates to a method for producing an additive composition.

Furthermore, the present invention relates to a lubricating oil composition comprising the above lubricating oil additive composition.

The additive composition for lubricating oil of the present invention can be produced in a short time at a relatively low temperature of 60 ° C. or less, has no adverse effect such as swelling of the rubber seal, and is excellent in storage stability.

Hereinafter, the present invention will be described in detail.
Hydrocarbon solvents employed in the lubricating oil additive composition of the present invention has a kinematic viscosity of 100 ° C. is ^{0.5 ~ 4.5mm 2 / s,%} C A of 3 or less, and sulfur content of 0. It is a solvent selected from mineral oil, hydrocarbon-based synthetic oil, and a mixture thereof of not more than 05% by mass.

Specifically, as mineral oil, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, hydrocracked, and solvent dewaxed. , Oil refined by one or more treatments such as hydrorefining, or lubricating oil produced by isomerizing GTL WAX (Gas Liquid Wax) produced by wax isomerized mineral oil, Fischer-Tropsch process, etc. A base oil can be illustrated.

Examples of hydrocarbon synthetic oils include polybutene or hydrides thereof; poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; aromatic synthetic oils such as alkylnaphthalenes and alkylbenzenes, or two of these. The above mixture can be illustrated.

As the hydrocarbon solvent used in the present invention, mineral oil, hydrocarbon synthetic oil, or an arbitrary mixture of two or more hydrocarbon solvents selected from these can be used. For example, one or more mineral oils, one or more hydrocarbon-based synthetic oils, a mixed oil of one or more mineral oils and one or more hydrocarbon-based synthetic oils can be used.

The kinematic viscosity at 100 ° C. of the hydrocarbon solvent used in the present invention needs to be 0.5 to 4.5 mm ² / s, preferably 1.0 to 4.3 mm ² / s, more preferably 1 0.5 to 4.2 mm ² / s, and most preferably 2.0 to 4.1 mm ² / s. When the kinematic viscosity at 100 ° C. of the hydrocarbon solvent is less than 0.5 mm ² / s, it is not preferable in terms of evaporation loss, and when it exceeds 4.5 mm ² / s, the phosphorus-containing compound dissolves in the metal salt. It is not preferable because the force is insufficient.

% C _A of hydrocarbon solvent used in the present invention it is necessary that is 3 or less, preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less. If the% C _A value of the hydrocarbon solvent is more than 3 tend to dissolving power for metal salts of phosphorus-containing compound is undesirably reduced. Incidentally,% C _A of hydrocarbon solvent used in the present invention may be zero.
And says% _{C A} in the present invention, obtained by a method in accordance with ASTM D 3238-85 (n-d- M ring analysis), it means a percentage of the total number of carbon atoms of the aromatic carbon atoms.

The sulfur content of the hydrocarbon solvent used in the present invention must be 0.05% by mass or less, preferably 0.04% by mass or less, more preferably 0.03% by mass or less, particularly preferably. It is 0.02 mass% or less. When the sulfur content of the hydrocarbon solvent exceeds 0.05% by mass, the solubility of the phosphorus-containing compound in the metal salt may be reduced, which is not preferable.

Usually, the sulfur content of the hydrocarbon solvent depends on the sulfur content of the raw material. For example, when a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like is used, a hydrocarbon solvent that does not substantially contain sulfur can be obtained. Moreover, when using raw materials containing sulfur such as slack wax obtained in the purification process of hydrocarbon solvents and microwax obtained in the refinement process, the sulfur content in the obtained hydrocarbon solvent is usually 0.01. It becomes mass% or more. In the present invention, the sulfur content needs to be 0.05% by mass or less.
In addition, the sulfur content as used in the field of this invention means the sulfur content measured based on JISK2541-1996.

The viscosity index of the hydrocarbon solvent used in the present invention is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, and most preferably 120 or more so that excellent viscosity characteristics from low temperature to high temperature can be obtained. preferable. The upper limit of the viscosity index is not particularly limited, and those having about 135 to 180 such as normal paraffin, slack wax, GTL wax, etc., or isoparaffinic mineral oil obtained by isomerizing these can also be used. If the viscosity index of the hydrocarbon solvent is less than 80, the solubility of the phosphorus-containing compound in the metal salt may be deteriorated.

The additive composition for lubricating oil of the present invention is a metal salt of a phosphorus-containing compound represented by the following general formula (1) (hereinafter simply referred to as a metal salt of a phosphorus-containing compound) in the above-described specific hydrocarbon solvent. 10) to 90% by mass based on the total amount of the composition.

In the general formula (1), X ¹ and X ² are oxygen or sulfur atoms. R ¹ , R ² , R ³ and R ⁴ are each independently a linear alkyl group having 3 to 12 carbon atoms, preferably a linear alkyl group having 4 to 11 carbon atoms, more preferably a straight chain group having 4 to 10 carbon atoms. A chain alkyl group, most preferably a linear alkyl group having 4 to 8 carbon atoms. When the number of carbon atoms of the hydrocarbon group is less than 3, the solubility may be inferior. On the other hand, when it exceeds 12, the production may be difficult. Further, the average carbon number of R ¹ , R ² , R ³ and R ⁴ needs to be 5 or more. M is a divalent metal atom, and specific examples include zinc, copper, nickel, cobalt, calcium, magnesium and the like, with zinc being most preferred.

Linear alkyl groups include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl Group, n-dodecyl group and the like.

Specific examples of phosphorus-containing compounds include di-n-butyl phosphate, di-n-hexyl phosphate, di-n-octyl phosphate, di-n-decyl phosphate, di-n-dodecyl phosphate, n-butyl-n-hexyl phosphate, n-butyl-n-octyl phosphate, di-n-butyl thiophosphate, di-n-hexyl thiophosphate, di-n-octyl thiophosphate, n- Mention may be made of butyl-n-hexylthiophosphate, n-butyl-n-octylthiophosphate, or mixtures thereof.
Specific examples of the general formula (1) include metal salts such as zinc, copper, nickel, cobalt, calcium, and magnesium of the phosphorus-containing compound.

The mixing ratio of the metal salt of the phosphorus-containing compound with respect to the hydrocarbon solvent is 10 to 90% by mass, preferably 30 to 85% by mass, more preferably 35 to 80% by mass, and most preferably 40 to 40% by mass based on the total amount of the composition. 75% by mass. When the mixing ratio is less than 10% by mass, the blending amount at the time of producing the lubricating oil increases, and there is a possibility that the evaporability of the lubricating oil may increase. When the mixing ratio is more than 90% by mass, May cause separation.

Kinematic viscosity at 100 ° C. of the lubricating oil additive composition of the present invention is preferably a 0.5 ~ 4.5mm ² / s, more preferably 1.0 ~ 4.3mm ² / s, more preferably Is 1.5 to 4.2 mm ² / s.

The additive composition for lubricating oil of the present invention is, for example, added with a metal salt of a finely pulverized phosphorus-containing compound in a hydrocarbon solvent heated to 30 to 60 ° C., and stirred at a rotational speed of about 300 rpm. Or by dissolving a metal salt of a phosphorus-containing compound in an organic solvent such as hexane and mixing with a hydrocarbon solvent and distilling off the organic solvent.

The additive composition for lubricating oil of the present invention thus obtained is used as an additive for various lubricating oils.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 8, Comparative Examples 1 to 16]
Lubricating oil additive compositions having the compositions shown in Tables 1 and 2 were prepared by blending the following hydrocarbon solvents with metal salts of phosphorus-containing compounds (Examples 1 to 8, Comparative Examples 1 to 16). ). The metal salts of hydrocarbon solvents and phosphorus-containing compounds in the table are as follows.

(1) Hydrocarbon solvent Solvent 1: Paraffinic solvent refined mineral oil (kinematic viscosity at 100 ° C .: 2.1 mm ² / s,% C _A : 5, sulfur content: 800 mass ppm)
Solvent 2: hydrorefined mineral oil (kinematic viscosity at 100 ° C .: 2.7 mm ² / s,% C _A : 0, sulfur content: 0 mass ppm)
Solvent 3: Poly-α-olefin (PAO) (kinematic viscosity at 100 ° C .: 4.0 mm ² / s,% C _A : 0, sulfur content: 0 mass ppm)

(2) Metal salt of phosphorus-containing compound Phosphorus compound A: n-butyl-n-hexyl phosphate zinc salt (average carbon number: 5, phosphorus content: 11.5% by mass, zinc content: 11.9% by mass) )
Phosphorus compound B: di-n-hexyl phosphate zinc salt (average carbon number: 6, phosphorus content: 10.4% by mass, zinc content: 10.7% by mass)
Phosphorus compound C: n-butyl-n-octyl phosphate zinc salt (average carbon number: 6, phosphorus content: 10.4% by mass, zinc content: 10.7% by mass)
Phosphorus compound D: n-butyl-n-octylthiophosphate ester zinc salt (average carbon number: 6, phosphorus content: 9.8% by mass, zinc content: 10.1% by mass, sulfur content: 10.1 mass%)
Phosphorus compound E: di-n-butyl phosphate zinc salt (average carbon number: 4, phosphorus content: 12.8% by mass, zinc content: 13.1% by mass)
Phosphorus compound F: di-n-butylthiophosphate ester zinc salt (average carbon number: 4, phosphorus content: 11.9% by mass, zinc content: 12.3% by mass, sulfur content: 12.3% by mass)
Phosphorus compound G: n-butyl-n-hexyl phosphate zinc salt (average carbon number: 4.5, phosphorus content: 12.2% by mass, zinc content: 12.6% by mass)
Phosphorus compound H: zinc salt of di-2-ethylhexyl phosphate (phosphorus content: 8.8% by mass, zinc content: 9.1% by mass)
Phosphorus compound I: di-2-ethylhexylthiophosphate ester zinc salt (phosphorus content: 8.4 mass%, zinc content: 8.7 mass%, sulfur content: 8.7 mass%)

The lubricating oil additive compositions of Examples 1 to 8 and Comparative Examples 1 to 16 were subjected to a storage test at room temperature, liquefiability at 60 ° C., and after 1 week, 2 weeks, 3 weeks and The presence or absence of insoluble analysis after 4 weeks was observed. The obtained results are shown in Tables 1 and 2. When the solvent 1 that does not have the properties defined in the present invention is used, and when the phosphorus-containing compound having a branched alkyl group is used, a stable lubricating oil additive composition cannot be prepared.

The additive composition for lubricating oil of the present invention can be produced in a short time at a relatively low temperature of 60 ° C. or less, has no adverse effect such as swelling of a rubber seal, and is excellent in storage stability. The above utility value is extremely large.

Claims

100 ° C. kinematic viscosity of 0.5 ~ 4.5mm 2 / s,% C A of 3 or less, and mineral oil sulfur content is not more than 0.05 wt%, the hydrocarbon-based synthetic oils and mixtures thereof An additive composition for lubricating oil, characterized in that the selected hydrocarbon solvent contains a metal salt of a phosphorus-containing compound represented by the general formula (1) in an amount of 10 to 90% by mass based on the total amount of the composition. .

(In the general formula (1), X 1 and X 2 are oxygen or sulfur atoms, R 1 , R 2 , R 3 and R 4 are each independently a straight-chain alkyl group having 3 to 12 carbon atoms and having an average carbon number 5 or more, M represents a divalent metal atom.)
100 ° C. kinematic viscosity of 0.5 ~ 4.5mm 2 / s,% C A of 3 or less, and mineral oil sulfur content is not more than 0.05 wt%, the hydrocarbon-based synthetic oils and mixtures thereof Production of an additive composition for lubricating oil, wherein a metal salt of a phosphorus-containing compound represented by the general formula (1) is dissolved in a selected hydrocarbon solvent in an amount of 10 to 90% by mass based on the total amount of the composition. Method.

(In the general formula (1), X 1 and X 2 are oxygen or sulfur atoms, R 1 , R 2 , R 3 and R 4 are each independently a straight-chain alkyl group having 3 to 12 carbon atoms and having an average carbon number 5 or more, M represents a divalent metal atom.)
A lubricating oil composition comprising the lubricating oil additive composition according to claim 1.