JP2013512296A - Additive concentrate - Google Patents

Abstract

The invention relates to a Fischer-Tropsch derived base oil of at least 90% by weight, based on the total weight of the additive concentrate; a viscosity modifier of at least 3.0% by weight, based on the total weight of the additive concentrate; and additives An additive concentrate is provided that includes less than 5.0% by weight solubility promoter, based on the total weight of the concentrate.
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Description

  The present invention relates to an additive concentrate comprising a base oil and a viscosity modifier for incorporation into a lubricating oil composition.

  Lubricating oil compositions (especially for automotive crankcases and transmissions) are used to reduce wear in metal / metal contact between moving parts as well as to remove heat. In many applications, the lubricating oil composition requires the presence of polymeric viscosity modifier additives to obtain the desired viscosity characteristics over a wide range of shear forces and / or temperatures. These additives are usually high viscosity liquids or solids at room temperature. To ensure uniform distribution, avoid handling solids, and control the amount of additive added to the lubricating oil composition (thus ensuring uniform product quality). Additives are usually added as additive concentrates.

  Example 6 of US 2005/0133407 contains 86.30% by weight Fischer-Tropsch derived base oil, 0.3% by weight pour point depressant, and 13.4% by weight PCMO DI. A 0W-20 engine oil (ie, a fully formulated lubricating composition that is not an additive concentrate) containing an additive package is disclosed. As is apparent from paragraph [0147] of US 2005/0133407, the 0W-20 formulation of Example 6 does not contain a viscosity index improver.

  Example 3 of WO 02/064710 consists of 76.4% by weight of Fischer-Tropsch derived product, 14.6% by weight of a detergent inhibitor additive package, 0.25% by weight. 0W-30 engine oil (ie, a fully formulated lubricating composition that is not an additive concentrate) containing 1% corrosion inhibitor and 10.56% by weight viscosity modifier.

Example 2 of EP 1688476 has an 18% by weight additive package (see Example 1 of EP 1688476) and (90% × 82% by weight =) 73.8% by weight Fischer-Tropsch derived base oil and (10% × 82% by weight =) 8.2% by weight of Emery 2925 (triestered polyol ester derived from C ₈ -C ₁₀ acid, commercially available from Cognis ) In a blended state (ie not an additive concentrate). As can be seen from Table II of US 2007/0093396, Emery 2925 has an aniline point of 0 ° C. (according to ASTM D611) and is therefore a solubility booster according to the present invention. Can be considered.

  Example 7 of US Patent Application Publication No. 2009/0088352 includes 86.81 wt% Fischer-Tropsch derived base oil, 8.10 wt% additive package, 4.94 wt% viscosity modifier, A lubricating composition (ie, not an additive concentrate) prepared to meet the John Deere J20D standard containing 0.15% by weight pour point depressant and 0.07% by weight antifoaming agent. ) Is disclosed.

  As described in International Publication No. 2009/074572, Fischer-Tropsch derived base oils typically have low solubility, and as a base oil for making additive concentrates for additives such as polymer viscosity modifiers. Not appropriate. Thus, WO 2009/074572 proposes to include an alkylated aromatic compound (eg, “KR008” commercially available from King Industries) as a solubility promoter in the additive concentrate. According to WO 2009/074572, the solubility promoter is preferably present in an amount of 25% to 75% by weight, based on the weight of the additive concentrate.

US Patent Application Publication No. 2005/0133407 International Publication No. 02/064710 European Patent Application No. 1688476 US Patent Application Publication No. 2007/0093396 US Patent Application Publication No. 2009/0088352 International Publication No. 2009/074572

  Surprisingly, Fischer-Tropsch derived base oils can be used to produce additive concentrates containing viscosity modifiers, and these additive concentrates require the use of viscosity modifiers. Suitable for use in, for example, transmission oils, engine oils or other lubricating oils (including industrial lubricating oils such as hydraulic fluids) without the need to use significant amounts of solubility promoters Furthermore, the Applicant has found that no solubility promoter is required.

  To achieve this objective, the present invention provides at least 90% by weight Fischer-Tropsch derived base oil based on the total weight of the additive concentrate; at least 3.0% by weight based on the total weight of the additive concentrate. And a solubility enhancer of less than 5.0% by weight based on the total weight of the additive concentrate.

  Fischer-Tropsch derived base oils are known in the art. In the context herein, the term “Fischer-Tropsch derived” means that a substance is a synthetic product of a Fischer-Tropsch condensation process or a derivative from the synthetic product, It means that. The term “non-Fischer-Tropsch derived” can be interpreted accordingly. Thus, a Fischer-Tropsch derived base oil is a hydrocarbon stream derived from a Fischer-Tropsch condensation process, either directly or indirectly, with a substantial portion (except for added hydrogen). A Fischer-Tropsch derived base oil can also be referred to as a GTL (Gas-To-Liquid) base oil. The term “base oil” may refer to a mixture comprising two or more base oils.

  To obtain further knowledge regarding the Fischer-Tropsch derived base oil and its production, reference is made to the above-mentioned International Publication No. 2009/074572, the disclosure of which is incorporated herein by reference.

  In general, the aromatics content of Fischer-Tropsch derived base oil (suitably measured according to ASTM D4629) is less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight It is more preferable that Suitably the base oil has a total paraffin content of at least 80% by weight, preferably a total paraffin content of at least 85% by weight, more preferably a total paraffin content of at least 90% by weight, It is more preferred to have a total paraffin content of 95% by weight and most preferred to have a total paraffin content of at least 99% by weight. Suitably the base oil has a saturated compound content (measured according to IP-368) of more than 98% by weight. The saturated compound content of the base oil is preferably greater than 99% by weight and more preferably greater than 99.5%. The base oil further preferably has an n-paraffin content of at most 0.5% by weight. The base oil further preferably has a naphthene compound content of 0 to less than 20% by weight, more preferably 0.5 to 10% by weight.

Fischer-Tropsch derived base oils generally have a kinematic viscosity (measured in accordance with ASTM D7042) at 100 ° C. of 1 to 25 mm ² / s (cSt), preferably a kinematic viscosity exceeding 2.5 mm ² / s. More preferably, it has a kinematic viscosity exceeding 3.0 mm ² / s. Fischer-Tropsch derived base oil preferably has a kinematic viscosity of less than 5.0 mm ² / s at 100 ° C., more preferably has a kinematic viscosity of less than 4.5mm ² / s, 4.2mm ² / More preferably, it has a kinematic viscosity of less than s.

Fischer-Tropsch derived base oils further generally have a kinematic viscosity (measured according to ASTM D7042) at 40 ° C. of 10-100 mm ² / s (cSt), preferably 15-50 mm ² / s. .

  The Fischer-Tropsch derived base oil further preferably has a pour point of less than −30 ° C. (measured according to ASTM D5950), more preferably has a pour point of less than −40 ° C., and a pour point of less than −45 ° C. Most preferably.

The flash point of Fischer-Tropsch derived base oil (measured according to ASTM D92) is preferably higher than 120 ° C, more preferably higher than 140 ° C.
The Fischer-Tropsch derived base oil preferably has a viscosity index (according to ASTM D2270) in the range of 100-200. The Fischer-Tropsch derived base oil preferably has a viscosity index of at least 125, and more preferably has a viscosity index of at least 130. Furthermore, the viscosity index is preferably less than 180, more preferably less than 150.

  Where a Fischer-Tropsch derived base oil contains a blend of two or more Fischer-Tropsch derived base oils, the above values apply to a blend of two or more Fischer-Tropsch derived base oils. .

  In addition to Fischer-Tropsch derived base oils, additive concentrates are so-called synthetic base oils (e.g. PAO) including mineral derived base oils and Group IV base oils in accordance with the definition of the American Petroleum Institute (API). One or more non-Fischer-Tropsch derived base oils may be included. These API categories are defined in “API Publication 1509, 15th Edition, Appendix E, July 2009”.

  The additive concentrate of the present invention preferably comprises at least 80% by weight Fischer-Tropsch derived base oil, based on the total weight of the additive concentrate, and comprises at least 90% by weight Fischer-Tropsch derived base oil. Is more preferable. The additive concentrate further preferably comprises less than 10.0% by weight non-FT derived base oil, based on the total weight of the additive concentrate, and comprises less than 5.0% by weight non-FT derived base oil. More preferably, it contains less than 2.0% by weight of non-FT derived base oil, more preferably less than 1.0% by weight of non-FT derived base oil. Most preferably, the additive concentrate does not contain any non-Fischer-Tropsch derived base oil.

  There are no particular restrictions on the viscosity modifier used in the additive concentrate of the present invention. Those skilled in the art are familiar with the term “viscosity modifier” and will not be described in further detail. Viscosity modifiers (also known as VI improvers, viscosity index improvers, or viscosity improvers) provide high and low temperature operability to lubricating oils. The viscosity modifier preferably imparts acceptable viscosity at low temperatures and is shear stable. Generally, and as contemplated in accordance with the present invention, the viscosity modifier is a viscosity index (by incorporation into an additive concentrate (and / or a fully formulated lubricating oil composition in which the viscosity modifier is incorporated) ( (E.g., measured according to ASTM D2270) (e.g., at least about 5 units).

  According to the invention, the additive concentrate comprises at least 3.0% by weight of a viscosity modifier based on the total weight of the additive concentrate. The additive concentrate preferably includes at least 5.0 wt% (e.g., 5.0-10.0 wt%) viscosity modifier, based on the total weight of the additive concentrate, 6.0-10 It is more preferable to include 0.0% by weight of a viscosity modifier.

  Examples of viscosity modifiers include linear or star olefin copolymers, polyisobutylene, polymethacrylate, polymers of dienes (such as isobrene and butadiene), or copolymers with styrene that may be substituted with such dienes, etc. However, it is not limited to these. These copolymers are preferably hydrogenated to the extent that most of the olefinic unsaturation is saturated. Many other types of viscosity modifiers are known in the art and many of these are “Proceedings of Conference”, ““ Viscosity and flow properties of multigrade engine oils ”, Esslingen, Germany, December 1977”. It is described in. Further, the viscosity modifier may be functionalized to incorporate dispersibility (eg, dispersible viscosity index improvers based on block copolymers and polymethacrylates) and / or antioxidant functions and viscosity adjusting functions. It is also known in the art that pour point depressants can be mixed to provide a product that is easy to handle in cold climates.

  The viscosity modifier is preferably selected from the group consisting of olefin copolymers, polyisoprene polymers, and diene-styrene copolymers. The olefin copolymer is a product name of “PARATONE (registered trademark)” [“PARATONE (registered trademark) 8921”, “PARATONE (registered trademark) 8921” etc.] from Chevron Oronite Company LLC; ) "[" HiTEC (registered trademark) 5850B "etc.]; and commercially available from Lubrizol under the product name" Lublizol (registered trademark) 7067C ". Polyisoprene polymers are commercially available from Infineum International, for example under the name “SV200”; diene-styrene copolymers are commercially available from Infineum International, for example, under the name “SV260”.

  The additive concentrate of the present invention comprises less than 5.0% by weight solubility promoter based on the total weight of the additive concentrate. The additive concentrate preferably contains less than 2.0% by weight solubility promoter, more preferably less than 1.0% by weight, and less than 0.5% by weight, based on the total weight of the additive concentrate. It is more preferable to include. It is particularly preferred that the additive concentrate does not contain any solubility promoter.

  There are no specific restrictions regarding the solubility promoter contemplated according to the present invention. Those skilled in the art are familiar with the term “solubility enhancer” and will not be described in further detail. In general, and as contemplated according to the present invention, solubility promoters are compounds having an aniline point (according to ASTM D611) of less than 100 ° C.

  The solubility promoter is preferably an alkylated aromatic compound. Alkylated aromatic compounds include alkylated benzene, alkylated anthracene, alkylated phenanthrene, alkylated biphenyl, alkylated naphthalene, or any mixture thereof. The alkylated naphthalene is described in detail in WO 2009/074572.

  The additive concentrate may further contain a pour point depressant to improve pumpability. When a pour point depressant is present, the pour point depressant is preferably present in the range of 0.5 to 3% by weight, more preferably in the range of 1 to 2% by weight, Most preferably, it is present in the range of 1.4% by weight.

  The additive concentrate has a kinetic viscosity of less than 3000 cP at -30 ° C. (according to ASTM D5293) and at least 5.5 cSt at 100 ° C. when normalized to a 1.0 wt% viscosity modifier concentration. It has a kinematic viscosity (according to ASTM D7042). The kinetic viscosity at −30 ° C. is preferably less than 2000 cP, more preferably less than 1500 cP. Additive concentrates containing various amounts of viscosity modifiers can be obtained by diluting the concentrate with the appropriate amount of the same base oil (or base oil blend) used to make the additive concentrate. , And can be standardized to a concentration of 1.0% by weight.

  The additive concentrate preferably further comprises 5 to 500 ppm of antioxidant (preferably selected from phenolic antioxidants, amine antioxidants, or mixtures thereof).

In a further aspect, the present invention provides a lubricating oil composition comprising a base oil, one or more additives other than a viscosity modifier, and an additive concentrate of the present invention.
There are no specific restrictions regarding the base oil used in the lubricating oil composition of the present invention. The base oil may be a Fischer-Tropsch derived base oil, a non-Fischer-Tropsch derived base oil, or a mixture thereof.

  One or more additives other than viscosity modifiers are a wide range of additives (eg, antioxidants, antiwear additives, dispersants, detergents, overbased detergents, extreme pressure additives, friction modifiers, Pour point depressants, metal passivators, corrosion inhibitors, demulsifiers, antifoaming agents, seal compatibilizers, additive diluent base oils and the like. Those skilled in the art are familiar with these and other additives and will not be described in further detail. Specific examples of such additives are described, for example, in “Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pp. 477-526”.

  EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited by these examples.

Additive concentrates Various additive concentrates were formulated. Table 1 shows the characteristics of the base oil used in the additive concentrate. Tables 2-5 show the composition and properties of the tested compounded additive concentrates. The amounts of the components are expressed in weight percent based on the total weight of the additive concentrate. Table 6 shows the storage stability of the additive concentrate of the present invention. In addition, Table 7 shows a fully formulated lubricating composition (ie, SAE 5W-30 engine oil) comprising the additive concentrate of the present invention.

  All viscosities and viscosity indices measured for the additive concentrate are at the viscosity modifier concentration normalized to 1.0 wt% by dilution with the same base oil used to blend the additive concentrate. Measured (because neat concentrate is too viscous and falls outside the test range of the indicated test method).

  All additive concentrates tested contained a combination of base oil, viscosity modifier and optional antioxidant.

“Base oil 1” is a Fischer-Tropsch derived base oil (“GTL4”) having a kinematic viscosity (ASTM D7042) of about 4 cSt (mm ² / s) at 100 ° C. This GTL4 base oil can be appropriately produced by, for example, the method described in International Publication No. WO 02/070631 (the disclosure of the publication is included in the present specification by reference).

  “Base oil 2” is a commercially available Group I base oil having a kinematic viscosity (ASTM D7042) of about 4 cSt at 100 ° C. Base oil 2 is commercially available from ExxonMobil under the trade name “Americas SN115”.

  “Base oil 3” is a commercially available Group II base oil having a kinematic viscosity (ASTM D7042) of about 4.7 cSt at 100 ° C. Base oil 3 is commercially available from Motiva Enterprises LLC under the trade name “Star5 +”.

  “Base oil 4” is a commercially available Group II base oil having a kinematic viscosity (ASTM D7042) of about 6.5 cSt at 100 ° C. Base oil 4 is commercially available from Motiva Enterprises LLC under the trade name "Star6".

  “VM1” is an olefin copolymer viscosity modifier commercially available from Chevron Oronite Company LLC (Richmond, Calif., USA) under the trade name “PARATONE® 8921”.

  “VM2” is an olefin copolymer viscosity modifier commercially available from Afton Chemical Co. (Richmond, Virginia, USA) under the trade name “HiTEC® 5850B”.

  “VM3” is an olefin copolymer viscosity modifier commercially available from Lubrizol (Wicklife, Ohio, USA) under the trade name “Lublizol® 7067C”.

  “VM4” is a polyisoprene polymer viscosity modifier commercially available from Infineum International (Linden, New Jersey, USA) under the trade designation “SV200”.

  “VM5” is a diene-styrene copolymer viscosity modifier commercially available from Infineum International under the trade designation “SV260”.

  “Antioxidant” is an amine-based antioxidant commercially available from Ciba (Houston, Texas, USA) under the trade name “Ciba® IRGANOX® L57”.

  The compositions of Examples 1-8 and Comparative Examples 1-8 were mixed by mixing the base oil and viscosity modifier using a Silverson high shear mixer and then following the blending procedure recommended by the viscosity modifier supplier. Obtained.

Storage Stability To demonstrate the storage stability of the additive concentrate of the present invention, separate samples of the additive concentrate of Example 1 were each 70 ° C., ambient temperature (20 ° C.), 0 ° C., and − Stored at 20 ° C. for 30 days. The measured viscosity after storage for 30 days is shown in Table 6 below. Similar good storage stability was obtained for the additive concentrates of Examples 2-8.

SAE 5W30 engine oil Two SAE 5W-30 engine oil formulations meeting the so-called SAE J300 standard (revised January 2009) using the additive concentrates of Examples 2 and 4 and conventional additive packages (Examples 9 and 10) were produced. SAE stands for “Society of Automotive Engineers”.

The amount of each component and the characteristics of SAE 5W-30 engine oil are shown in Table 7 below.
The additive package contained pour point depressants and other typical additives for use in SAE 5W-30 engine oil.

As can be seen from the discussion tables 2-5, surprisingly, the present invention uses a Fischer-Tropsch derived base oil, but without the use of a significant amount of solubility promoter, and even a solubility promoter. Offers the possibility of producing additive concentrates containing viscosity modifiers without the use of any. Furthermore, the additive concentrates of the present invention exhibit significantly better low temperature properties compared to conventional additive concentrates using mineral derived Group I (ie, non-Fischer-Tropsch derived) base oils (this This is highly desirable in blending multigrade lubricating oils).

Furthermore, as can be seen from Table 6, the additive concentrate of the present invention has excellent storage stability over a long period of time at various temperatures.
The additive concentrate of the present invention is suitable for use in a wide range of lubricants (eg, in engine oils, transmission fluids, and other lubricants where viscosity modifiers are required). As shown in Table 7, SAE 5W-30 formulations can be formulated when using the additive concentrates of the present invention.

Claims (12)

At least 90 wt.% Fischer-Tropsch derived base oil based on the total weight of the additive concentrate; at least 3.0 wt.% Viscosity modifier based on the total weight of the additive concentrate; and the total additive concentrate An additive concentrate comprising less than 5.0% by weight solubility promoter, based on weight. The additive concentrate is less than 10.0% by weight, preferably less than 5.0% by weight, more preferably less than 2.0% by weight, and even more preferably, based on the total weight of the additive concentrate. The additive concentrate of claim 1 comprising less than 0 wt% non-Fischer-Tropsch derived base oil. Fischer-Tropsch derived base oil, of less than 5.0 mm ² / s at 100 ° C., preferably less than 4.5 mm ² / s, more preferably (according to ASTM D7042) kinematic viscosity of less than 4.2 mm ² / s The additive concentrate according to claim 1 or 2, wherein 4. The additive concentrate according to any one of claims 1 to 3, wherein the Fischer-Tropsch derived base oil has a viscosity index (according to ASTM D2270) of at least 125, preferably at least 130. The additive concentrate according to any one of claims 1 to 4, wherein the additive concentrate comprises 5.0 to 10 wt% of a viscosity modifier based on the total weight of the additive concentrate. The additive concentrate comprises less than 2.0 wt.%, Preferably less than 1.0 wt.%, More preferably less than 0.5 wt.% Solubility promoter based on the total weight of the additive concentrate. The additive concentrate according to any one of claims 1 to 5. The additive concentrate according to any one of claims 1 to 6, wherein the solubility promoter has an aniline point (according to ASTM D611) of less than 100C. The additive concentrate according to any one of claims 1 to 7, wherein the solubility promoter is an alkylated aromatic component. The additive concentrate according to claim 8, wherein the alkylated aromatic component is selected from alkylated benzene, alkylated anthracene, alkylated phenanthrene, alkylated biphenyl, alkylated naphthalene or any mixture thereof. When the additive concentrate is standardized to a viscosity modifier concentration of 1.0% by weight, a kinetic viscosity of less than 3000 cP at -30 ° C. (according to ASTM D5293) and at least 5.5 cSt at 100 ° C. The additive concentrate according to any one of claims 1 to 9, having a kinematic viscosity (according to ASTM D7042). The additive concentration according to any one of claims 1 to 10, further comprising 5 to 500 ppm of antioxidant, preferably selected from phenolic antioxidants, amine antioxidants, or mixtures thereof. object. A lubricating oil composition comprising a base oil, one or more additives other than a viscosity modifier, and the additive concentrate according to any one of claims 1 to 11.