KR20120093933A - Lubricating composition - Google Patents

Abstract

The present invention
-Base oils;
-Detergents; And
-The following general formula (I):
R ¹ NHR ² (I)
(Wherein R ¹ represents a hydrocarbyl group having 1 to 50 carbon atoms, R ² is selected from the group consisting of H and a hydrocarbyl group having 1 to 50 carbon atoms)
Amine compound having an amount of more than 0.3 wt% based on the weight of the lubricating composition
It provides a lubricating composition comprising a.

Description

Lubrication composition {LUBRICATING COMPOSITION}

The present invention relates to lubricating compositions, in particular lubricating compositions for use in internal combustion engines operating under constant high load conditions, such as marine diesel engines and power applications. More particularly, the present invention relates to marine cylinder oil.

Marine cylinder oils are known in the art. As an example, WO 2008/043901 A2 has a base number (according to ASTM D 2986) of at least 40 mg KOH / g, containing from 0.01 to 1.0 wt% of primary, secondary or tertiary mono-alcohol having 12 or more carbon atoms. And cylinder lubricating oil for two-stroke marine engines.

Lubrication compositions used in internal combustion engines are subject to high levels of stress. Lubricants provide good lubrication properties under a variety of conditions, among other things, providing good wear and corrosion protection, helping to keep the engine clean, thermally and oxidatively stable, and transferring heat from the engine. It is important.

Due to the fact that marine engines are typically operated continuously for a long time in almost full charge conditions, the lubricating composition used in marine diesel engines is subjected to particularly high levels of stress.

It will be appreciated in the art that the term "marine" engine is not limited to engines used in marine vessels. In other words, the term also includes engines used in power generating applications. These high grade, fuel efficient, low speed and medium speed marine and stationary diesel engines operate at high pressure, high temperature and long-stroke.

It is an object of the present invention to improve the corrosion wear protection and BN retention properties of lubricating compositions, especially for use in internal combustion engines such as marine diesel engines.

Another object of the present invention is to provide an alternative lubricating composition for use in an internal combustion engine.

One or more of the above or other objects

Base oils;

-Detergents; And

-The following general formula (I):

R ¹ NHR ² (I)

(Wherein, R ¹ represents a hydrocarbyl group of a carbon number of 1-50, R ² is selected from the group consisting of a hydrocarbyl group is a hydrogen atom (H) and having a carbon number of 1 to 50)

Amine compound having an amount of more than 0.3 wt% based on the weight of the lubricating composition

It can be achieved by providing a lubricating composition comprising a.

In this connection it is noted that WO 2008/095966 discloses industrial oil compositions, such as hydraulic oils, comprising base oils, aspartic acid derivatives and aliphatic amine compounds. As specified on page 12, line 9, the composition may comprise a detergent-dispersant. In addition to the fact that examples containing detergents are not disclosed in WO 2008/095966, it should be noted that the industrial oil composition (typically free of large amounts of detergent) is substantially different from the engine oil according to the invention. By way of example, the lubricating composition according to the invention preferably does not contain aspartic acid derivatives.

It has now been surprisingly found that the lubricating compositions according to the invention exhibit improved corrosion wear protection and / or BN retention and / or BN use properties.

There is no particular limitation regarding the base oil used in the lubricating composition according to the present invention, and various conventional mineral oils, synthetic oils, as well as natural derived esters such as vegetable oils may be conveniently used.

The base oil used in the present invention may conveniently comprise a mixture of one or more mineral oils and / or one or more synthetic oils; Thus, according to the invention, the term "base oil" may mean a mixture containing more than one base oil. Mineral oils include solvent-treated or acid-treated mineral oil-based lubricating oils and liquid petroleum of the paraffin, naphthenic, or mixed paraffin / naphthenic type, which can be further purified by hydrofinishing processes and / or dewaxing. do.

Suitable base oils for use in the lubricating oil compositions of the present invention are group I-III mineral oil base oils, group IV poly-alpha olefins (PAO), group I-III Fischer-Tropsch derived base oils and mixtures thereof. .

In the present invention, "Group I", "Group II", "Group III" and "Group IV" base oils mean lubricant base oils according to the definition of category I-IV of the American Petroleum Institute (API). These API categories are defined in the API Publication 1509, 15th Edition, Appendix E, April 2002.

Fischer-Tropsch derived base oils are known in the art. The term "Fischer-Tropsch derived" means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. Fischer-Tropsch derived base oils may also be referred to as Gas-To-Liquid (GTL) base oils. Suitable Fischer-Tropsch derived base oils which can conveniently be used as base oils in the lubricating compositions of the invention are for example EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.

Synthetic oils include hydrocarbon oils such as olefin oligomers (such as polyalphaolefin base oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols (PAG), alkyl naphthalenes, and dewaxing waxy isomerates. Synthetic hydrocarbon base oils sold under the name "Shell XHVI" by the Shell Group may be conveniently used.

Poly-alpha olefin base oils (PAO) and their preparation are known in the art. Preferred poly-alpha olefin base oils that can be used in the lubricating composition of the invention can be derived from linear C ₂ to C ₃₂ , preferably C ₆ to C ₁₆ alpha olefins. Particularly preferred feedstocks of the poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.

The total amount of base oil included in the lubricating composition of the present invention is preferably in an amount in the range of 60 to 99 wt%, more preferably in an amount in the range of 65 to 98 wt%, most preferably based on the total weight of the lubricating composition. It is present in an amount ranging from 70 to 95 wt%.

There is no particular limitation with regard to the detergents used in the lubricating composition according to the present invention, and various conventional detergents or mixtures thereof can be conveniently used. Examples of cleaning agents that can be used are oil-soluble neutral and over-based sulfonates, phenates, sulfides of metals, in particular alkali or alkaline earth metals, for example sodium, potassium, lithium, especially calcium and magnesium. , Thiophosphonates, salicylates and naphthenates and other oil-soluble carboxylates. Preferred metal detergents are neutral and over-based detergents having a total base number (TBN; according to ASTM D2896) of 20 to 450. Detergents can be used in over-based or neutral or a combination of both.

The amount of detergent in the composition of the present invention is typically from 0.01 wt% to 35.0 wt% with respect to the total weight of the lubricating composition. According to a preferred embodiment of the invention, the composition comprises at least 4 wt% of a detergent relative to the total weight of the composition. Preferably the composition comprises at least 6 wt%, more preferably at least 8 wt%, even more preferably at least 10 wt%, most preferably at least 15 wt% of the detergent relative to the total weight of the composition.

Also preferably the detergent is selected from sulfonate-type detergents, phenate detergents, or mixtures thereof. Sulfonate-type and phenate-type detergents are known in the art.

The amine compound of formula (I) as defined above may include a wide variety of compounds. As mentioned above, R ¹ represents a hydrocarbyl group having 1 to 50 carbon atoms, and R ² represents H or a hydrocarbyl group having 8 to 30 carbon atoms.

The hydrocarbyl groups of R ¹ and R ² may be saturated or unsaturated and linear or branched, but are preferably saturated carbon chains and are preferably linear (and therefore unbranched). Preferably, R ¹ and R ² (when R ² does not represent H) are both independently from 4 to 40 carbon atoms, more preferably from 8 to 30 carbon atoms, even more preferably from 10 to 24 carbon atoms. Phosphorus, most preferably a hydrocarbyl group having 12 to 18 carbon atoms.

Preferably, in General Formula (I), R ² represents H. In the latter case, the amine compound is a primary amine having the general formula (II)

R ¹ NH ₂ (II).

Further, preferably, R ¹ in General Formula (I) or (II) represents a hydrocarbyl group having 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, more preferably 12 to 18 carbon atoms. Particularly preferred primary amines are n-dodecylamine (laurylamine), n-tridecylamine, n-tetradecylamine (myristolamine), n-pentadecylamine, n-hexadecylamine (n-palmitylamine ), n-heptadecylamine and n-octadecylamine (n-stearylamine).

The amount of amine compound in the composition of the present invention is greater than 0.3 wt%, preferably less than 2.5 wt%, preferably 0.4 wt% to 2.4 wt%, more preferably 0.5 to 2.0 wt%, based on the total weight of the lubricating composition. In the range from%, in particular from 1.0 wt% to 2.0 wt%.

The lubricating composition according to the present invention is composed of antioxidants, antiwear agents, dispersants, other detergents, extreme pressure additives, other friction modifiers, viscosity modifiers, pour point depressants, metal deactivators, corrosion inhibitors, demulsifiers, antifoam agents, seal compatibility agents And one or more other additives such as additional dilution base oils and the like. Preferably, however, the lubricating composition according to the invention is less than 5.0 wt%, more preferably 4.0 wt% in addition to at least one detergent, at least one dispersant and at least one amine compound (s) of general formula (I). It contains less than or even less than 3.0 wt% of any additives. Preferably, the composition contains no additives other than at least one detergent, at least one dispersant and at least one amine compound (s) of general formula (I).

Those skilled in the art are familiar with these and other additives and will not be discussed in further detail herein. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 14, pages 477-526.

The additives mentioned above are typically present in amounts ranging from 0.01 to 35.0 wt% with respect to the total weight of the lubricating composition, preferably in amounts ranging from 5.0 to 30.0 wt% with respect to the total weight of the lubricating composition.

Preferably, the composition has a total salt (TBN) value (particularly according to ASTM D 2896) of 75 mg KOH / g or less, preferably 70 mg KOH / g or less, more preferably 65 mg KOH / g, Even more preferably 60 mg KOH / g or less. Typically, the composition has an infectious agent (TBN) value (according to ASTM D 2896) of greater than 20.0 mg KOH / g.

Also preferably according to the invention the composition has a kinematic viscosity at 100 ° C. (particularly according to ASTM D 445) of more than 5.6 mm 2 / s and less than 21.9 mm 2 / s, preferably more than 12.5 mm 2 / s, more preferably It is more than 14.3 mm <2> / s.

The lubricating composition of the present invention can be conveniently prepared by mixing one or more additives with the base oil (s).

In another aspect, the present invention is directed to improving one or more of the corrosion wear protection properties (especially according to the procedure described below based on ASTM G181) and the BN retention properties (especially measured according to ASTM D 2896). It provides a use of a lubricating composition according to. The present invention also provides the use of a lubricating composition according to the invention for improving BN retention properties while maintaining corrosion wear protection properties.

The lubricating composition according to the invention is generally useful for lubrication equipment, in particular for use as engine oil for internal combustion engines. These engine oils include passenger car engines, diesel engines, marine diesel engines, gas engines, 2- and 4-cycle engines and the like, in particular marine diesel engines.

The invention is described below with reference to the following examples, which do not in any way limit the scope of the invention.

Example

Lubricant composition

Various lubricating compositions have been formulated for use as marine cylinder oil in marine diesel engines.

Table 1 shows the composition and properties of the formulations tested; The amount of ingredients is given in wt% relative to the total weight of the fully formulated formulation.

All marine diesel engine oil formulations tested are the so-called SAE J300 specification [revised January 2009; SAE was formulated as a SAE 40 or SAE 50 formulation that satisfies the Society of Automotive Engineers.

All marine cylinder oil formulations tested contained a combination of base oils, detergent additive packages and-if present-fatty amines or fatty alcohols. The detergent additive package contained a combination of neutral and over-based detergents.

"Base oil 1" was a commercially available Group I base oil blend having a kinematic viscosity at 100 ° C. (ASTM D445) of approximately 16 cSt (mm 2 s ⁻¹ ). This base oil blend is for example manufactured by Shell Chemicals Ltd. (London, UK) commercially available under the trade name "Catenex".

“Base oil 2” was a base oil blend containing a thickener and 75 wt% of a Group II base oil; This formulation is commercially available from Chevron Products Company (San Ramon, Calif., USA) under the trade name "Chevron 600 R".

"Cleaner Package 1" was a salicylate-type freshener package. Freshener package 1 is for example Infineum UK Ltd. (Abingdon, UK) commercially available under the trade name "Infineum M".

"Cleaner Package 2", "Cleaner Package 3" and "Cleaner Package 4" were combinations of phenate-type and sulfonate-type detergents. The detergent package 2, 3 and 4 components are commercially available, for example, under the trade names "OLOA 219C", "OLOA 249SX" and "OLOA 246S" from Chevron Oronite (Windsor, UK), respectively.

"Amine 1" was n-hexadecylamine. Amine 1 is commercially available, for example, under the trade name "445312 (Aldrich)" from Sigma-Aldrich (St. Louis, USA).

"Amine 2" was n-dodecylamine. Amine 2 is commercially available, for example, under the name "D3629 (Sigma)" from Sigma-Aldrich (St. Louis, USA).

"Alcohol 1" was n-octadecanol. Alcohol 1 is commercially available, for example, under the trade name "807680 Stearyl alcohol" from Merck KGaA (Darmstadt, Germany).

"Alcohol 2" was n-hexadecanol. Alcohol 2 is commercially available, for example, under the trade name "818704 Cetyl alcohol" from Merck KGaA (Darmstadt, Germany).

The compositions of Examples 1-10 and Comparative Examples 1-10 were obtained by mixing base oils with detergents, amines and / or alcohols using conventional lubricating oil blending procedures.

Table 1

^{1 according to} ASTM D 2896; ^{2 per} ASTM D 445

Table 1 (continued)

^{1 according to} ASTM D 2896; ^{2 per} ASTM D 445

Table 1 (continued)

^{1 according to} ASTM D 2896; ^{2 per} ASTM D 445

Corrosion abrasion test

To demonstrate the corrosion wear protection properties of the present invention, a corrosion procedure based on the standard ASTM G181 test ("Standard practice for conducting friction tests of piston ring and cylinder liner materials under lubricated conditions") is used. Measurements were carried out using a known Plint TE-77 Reciprocating Test Rig (available from Phoenix Tribology Ltd, Newbury, UK) by reciprocating a moving specimen under contact control with a stationary plate simulating the piston upper position. . As test specimens, finely cut pins were used from steel plates (Steel 20 RC, annealed) and two-stroke engine piston rings (Bolnes DNL 190/600).

A lubricant feed rate of 0.05 ml / min was used during the test; Also, use an acid (acid strength: H ₂ S0 ₄ 6N) feed rate of 0.05 ml / min over the contact surface on the plate for 5 minutes every 10 minutes (ie 5 minutes off, 5 minutes on, 5 minutes off, etc.) did. In the test, the following test conditions were used:

Load: 200 N

Temperature: 180 ℃

Round trip frequency: 10 Hz

Stroke length: 15 mm

-Time: 60 minutes.

The measured corrosion wear properties are shown in Table 2 below.

Table 2

^{1 according to} ASTM D 2896, after the test; ² reduction in BN compared to pre-test TBN values (see Table 1); For Example 1 this is [(71.28-58.08) /71.28] * 100% = 18.52; ³ Total corrosion wear is the sum of wear trace depth and pin height reduction on the plate. Wear trace depth on the plate was measured with a depth gauge (Digimatic Indicator ID-H, manufactured by Mitutoyo Corporation), and pin height reduction was measured with an Absolute Digimatic Micrometer, manufactured by Mitutoyo Corporation; ⁴ Normalized corrosion wear is the total wear measured [μm] divided by the wear measured for the selected comparative example (based on the same detergent formulation). Examples 1 and 2 and Comparative Examples 5 and 6 are compared with Comparative Example 1 (hence the normalized wear for Comparative Example 1 is 1.00); Examples 3 and 4 and Comparative Example 7 are compared with Comparative Example 2; Examples 5 and 6 are compared with Comparative Example 3; Examples 7 and 8 are compared with Comparative Example 4. Examples 9 and 10 are compared with Comparative Examples 8, 9 and 10.

Table 2 (continued)

^{1 according to} ASTM D 2896, after the test; ² reduction in BN compared to pre-test TBN values (see Table 1); For Example 1 this is [(71.28-58.08) /71.28] * 100% = 18.52; ³ Total corrosion wear is the sum of wear trace depth and pin height reduction on the plate. Wear trace depth on the plate was measured with a depth gauge (Digimatic Indicator ID-H, manufactured by Mitutoyo Corporation), and pin height reduction was measured with an Absolute Digimatic Micrometer, manufactured by Mitutoyo Corporation; ⁴ Normalized corrosion wear is the total wear measured [μm] divided by the wear measured for the selected comparative example (based on the same detergent formulation). Examples 1 and 2 and Comparative Examples 5 and 6 are compared with Comparative Example 1 (hence the normalized wear for Comparative Example 1 is 1.00); Examples 3 and 4 and Comparative Example 7 are compared with Comparative Example 2; Examples 5 and 6 are compared with Comparative Example 3; Examples 7 and 8 are compared with Comparative Example 4. Examples 9 and 10 are compared with Comparative Examples 8, 9 and 10.

Table 2 (continued)

^{1 according to} ASTM D 2896, after the test; ² reduction in BN compared to pre-test TBN values (see Table 1); For Example 1 this is [(71.28-58.08) /71.28] * 100% = 18.52; ³ Total corrosion wear is the sum of wear trace depth and pin height reduction on the plate. Wear trace depth on the plate was measured with a depth gauge (Digimatic Indicator ID-H, manufactured by Mitutoyo Corporation), and pin height reduction was measured with an Absolute Digimatic Micrometer, manufactured by Mitutoyo Corporation; ⁴ Normalized corrosion wear is the total wear measured [μm] divided by the wear measured for the selected comparative example (based on the same detergent formulation). Examples 1 and 2 and Comparative Examples 5 and 6 are compared with Comparative Example 1 (hence the normalized wear for Comparative Example 1 is 1.00); Examples 3 and 4 and Comparative Example 7 are compared with Comparative Example 2; Examples 5 and 6 are compared with Comparative Example 3; Examples 7 and 8 are compared with Comparative Example 4. Examples 9 and 10 are compared with Comparative Examples 8, 9 and 10.

Review

As can be seen from Table 2, the corrosion wear protection and BN retention properties for the compositions according to the invention are significantly compared to Comparative Examples 1-4 and 8, which contain base oils and one or more detergents but no amine compounds. Improved; More specifically, the presence of amine compounds in the examples according to the invention is characterized by lower consumption of BN (and thus better BN retention), optimal use of spent BN fraction (ie improved use of BN) and lower total corrosion. Resulted in wear and normalized corrosion wear. It is noted in this regard that Comparative Examples 3 and 4 exhibited desirable consumed BN values, but with much poorer corrosion wear data (reference, eg total corrosion wear).

It can also be seen that the corrosion wear protection properties for the compositions according to the invention are significantly improved compared to Comparative Examples 5-7 containing base oils, one or more detergents and primary fatty alcohols. In this connection it is noted that the primary fatty alcohols have recently been proposed for the purpose of optimizing BN use, which means improved acid neutralization properties and thus improved corrosion wear protection (cf. WO 2008/043901).

According to the invention from the comparison of the BN retention values of Examples 1 to 3, a mixture of sulfonate-type and phenate-type detergents (rather than salicylate-type detergents) is given, as in Examples 3 and 4, Lower consumption of BN and thus better BN retention for BN levels).

In addition, TBN levels 40 (Examples 7 and 8) and 55 (Examples 5 and 6) from Examples 5 to 8, in combination with the amine, were similar to or lower (ie, improved) total wear values than Comparative Examples 1 and 2. It can be seen that it caused. This is surprisingly a composition with relatively low TBN (eg 40 or 55) but amines that are equal or better in corrosion wear protection when compared to compositions that contain relatively high TBN (eg 70) but no amines. Performance, which would provide a route to formulate lower BN products as an alternative to existing commercial 70 BN marine cylinder lubricants.

It can also be seen from Comparative Examples 8-10 and Examples 9 and 10 that amine compound levels of greater than 0.3 wt% provide significantly lower corrosion wear. Comparative Examples 9 and 10 (containing only 0.2 wt% and 0.3 wt% amine, respectively) had total corrosion wear of 232 μm and 239 μm, respectively, while Examples 9 and 10 (0.5 wt% and 1.0 wt%, respectively) of Amine) had a total corrosion wear of 195 μm and 180 μm, respectively.

Claims (14)

-Base oils;
-Detergents; And
-The following general formula (I):
R ¹ NHR ² (I)
(Wherein R ¹ represents a hydrocarbyl group having 1 to 50 carbon atoms, R ² is selected from the group consisting of H and a hydrocarbyl group having 1 to 50 carbon atoms)
Amine compounds having an amount greater than 0.3 wt% and less than 2.5 wt% by weight of the lubricating composition
Lubricating composition comprising a. The lubricating composition of claim 1, wherein the amine compound is present at a level ranging from 0.4 wt% to 2.4 wt% by weight of the lubricating composition. The lubricating composition of claim 1 or 2 wherein the amine compound is present at a level in the range of 0.5 wt% to 2.0 wt%, based on the weight of the lubricating composition. The lubricating composition according to any one of claims 1 to 3, wherein R ² represents H. The lubricating composition according to any one of claims 1 to 4, wherein R ¹ represents a hydrocarbyl group having 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, more preferably 12 to 18 carbon atoms. The lubricating composition of claim 1 comprising from 0.01 wt% to 2.0 wt% of the amine compound of formula (I), relative to the total weight of the composition. The lubricating composition according to claim 1 comprising at least 4 wt%, preferably at least 10 wt%, more preferably at least 15 wt% of a detergent relative to the total weight of the composition. 8. The lubricating composition of claim 1, wherein the detergent is selected from sulfonate-type detergents, phenate-type detergents, or mixtures thereof. 9. The infectious agent according to claim 1, wherein the infectious group has a (TBN) value (particularly in accordance with ASTM D 2896) of 75 mg KOH / g or less, preferably 70 mg KOH / g or less, more preferably A lubricating composition that is at most 65 mg KOH / g, even more preferably at most 60 mg KOH / g. The kinematic viscosity at 100 ° C. according to claim 1, which is higher than 5.6 mm 2 / s and less than 21.9 mm 2 / s, preferably higher than 12.5 mm 2 / s, more preferably 14.3 mm 2 / s. Phosphorus lubricating composition. The lubricating composition according to any one of claims 1 to 10, which contains no additives other than at least one detergent, at least one dispersant and at least one amine compound (s) of general formula (I). The lubricating composition according to any one of claims 1 to 11, which is marine diesel engine oil, preferably marine cylinder oil. -Base oils;
-Detergents; And
-The following general formula (I):
R ¹ NHR ² (I)
(Wherein R ¹ represents a hydrocarbyl group having 1 to 50 carbon atoms, R ² is selected from the group consisting of H and a hydrocarbyl group having 1 to 50 carbon atoms)
Amine compound having an amount of more than 0.3 wt% based on the weight of the lubricating composition
/ RTI &gt;
A lubricating composition having a total salt (TBN) value (particularly according to ASTM D 2896) of 65 mg KOH / g or less, even more preferably 60 mg KOH / g or less. Lubrication according to any one of claims 1 to 13 for improving one or more of the corrosion wear protection properties (particularly in accordance with ASTM G181), the BN retention and the BN usage properties (in particular measured according to ASTM D 2896). Use of the composition.