KR20050084206A - Functional fluids - Google Patents

Abstract

This invention relates to base stocks and base oils that exhibit an unexpected combination of high viscosity index (130 or greater) and a ratio of measured-to-theoretical high-shear/low-temperature viscosity at - 30C or lower and the methods of making them. Specifically, the present invention relates to low-viscosity base stocks and base oils as used in functional fluids. More specifically, the present invention relates to automatic transmission fluids showing surprising low temperature Brookfield viscosities and methods to produce them.

Description

Hydraulic fluid {FUNCTIONAL FLUIDS}

The present invention relates to a base stock and base oil which shows an unexpected combination of high viscosity index (above 130) and measured high shear / cold viscosity at -30 ° C. or lower to theoretical high shear / cold viscosity. base oils), and methods for their preparation. In particular, the present invention relates to low viscosity base stocks and base oils used in hydraulic fluids. More specifically, the present invention relates to automatic transmission fluids and methods of making the same, which exhibit surprising low temperature Brookfield viscosity.

API 1509 Appendix E describes that a base stock (as opposed to a base oil and lubricant composition) is manufactured by a single manufacturer according to the same design specification (regardless of the raw material source or manufacturer's location) and only one chemical formula, product identification number, or It is defined as the hydrocarbon stream identified as both. Base stocks can be prepared using a variety of different processes including, but not limited to, distillation, solvent purification, hydrotreating, oligomerization, esterification, and refining. The refined raw material will be substantially free of substances introduced through manufacture, contamination or previous use. Base stock slates are a product line of base stocks having different viscosities but belonging to the same base stock family and made by the same manufacturer. Base oils are base stocks or blends of base stocks used in formulated lubricant compositions. The lubricant composition may be a base stock, base oil alone or a mixture of these and other raw materials, oils or functional additives.

Hydraulic fluids include a wide range of lubricants used in automotive and industrial hydraulic systems, automatic transmissions, power steering systems, shock absorbing fluids, and the like. These fluids must have carefully controlled viscosity characteristics as they transfer and regulate power in the mechanical system. In addition, these fluids can often be formulated to provide several grades of performance to ensure reliable operation throughout the year in varying climates.

Automatic Transmission Fluid (ATF) is one of the most common hydraulic fluids and an integral part of every automatic transmission. Automatic transmissions are used in about 80% to 90% of all vehicles in North America and Japan, and their use is becoming more common elsewhere in the world. These are the most complex and expensive subassemblies of vehicles, and major OEMs have strict design specifications to control all conditions of the components (including hydraulic fluid) used in their manufacture.

The ATF should have a suitable viscosity at ambient starting temperatures that can be on the order of -40 ° C while maintaining sufficient viscosity at higher operating temperatures of 100 ° C or higher. ATF should also be oxidatively stable as it is expected to be exposed to high temperatures and in some cases continue to be used up to 100,000 miles. Also, the friction characteristics are important for smoothly adjusting the movement to the clutch plate.

Significant advances have been made in ATF additive formulation science to meet these viscosity and oxidation conditions using solvent extracted mineral oils, commonly referred to as Group I base stocks. However, over the past few years, as the performance requirements for automatic transmission fluids have increased, the use of hydrogenated base stocks, commonly referred to as Group II or Group III base stocks, has become more widespread. These base stocks provide improved low temperature performance and longer oxidation life.

Existing OEM ATF conditions are usually only met by the use of Group I base stocks, or Group I base stocks mixed with small amounts of Group II or III base stocks. However, more recently, major automotive manufacturers have increased the need for ATF again by moving to smaller, higher power-density designs where the need for improved viscosity has increased. These new demands have resulted in the preparation of ATF from the Group III base stock, which is almost completely expensive in the related industry.

The tests used to describe the lubricant composition of the present invention are as follows:

(a) CCS viscosity measured by Cold Cranking Simulator Test (ASTM D5293);

(b) viscosity index (VI) measured by ASTM D2270;

(c) theoretical viscosity calculated by the Walter-MacCoull equation (ASTM D341 Appendix 1);

(d) kinematic viscosity measured by ASTM D445;

(e) pour point measured by ASTM D5950;

(f) Scanned Brookfield Viscosity as measured by ASTM D5133;

(g) Brookfield viscosity measured by ASTM D2983.

We note that while the Walter-Mcchol equation of ASTM D341 calculates the theoretical kinetic viscosity, CCS reports absolute viscosity. To calculate the ratios used herein, we converted the Walter-Mcchol viscosity into Equation I:

In the above formula, T ₁ is the desired temperature.

The well-known formula is used to estimate the density at -35 ° C from the density at 20 ° C. See, eg, A. Bondi, "Physical Chemistry of Lubricating Oils", 1951, p. 5].

1 is a graph comparing CCS viscosity measured at various temperatures to predicted Walter-Mcchol viscosity.

2 compares the kinematic viscosity versus CCS viscosity of various oils and comparative examples of the present invention.

It is a graph.

3 graphically depicts Brookfield viscosity versus pour point of various lubricants.

Summary of the Invention

The present invention relates to base stocks and base oils that achieve improved viscosity performance at low temperatures (up to about −25 ° C.). The present invention also includes base oils derived from waxy hydrocarbon feedstocks from natural or mineral sources or synthetic sources (e.g., a Fischer-Tropsch type of process) and contain a significant amount of Group II bases. It relates to a formulated hydraulic fluid that can still be used and can be used to prepare ATF that meets the new industrial Brookfield viscosity limits. The invention also relates to processes or methods for producing such base oils, base stocks and formulated hydraulic fluids and ATFs.

More specifically, the present invention relates to (a) a viscosity index (VI) of at least 130, (b) a pour point of -10 ° C. or less, (c) a measured low temperature viscosity of 1.2 or less at −30 ° C. or less versus a theoretical low temperature viscosity. Includes hydraulic fluid incorporating base stocks with surprising and unexpected simultaneous combinations of ratios, where the measured viscosity is cold crack simulator viscosity and the theoretical viscosity is calculated at the same temperature using the Walter-Mackol equation. .

Preferably, the base stocks and base oils of the present invention as used herein have a measured low temperature versus theoretical low temperature viscosity of about 0.8 to about 1.2 at −30 ° C. or lower. At this time, the measured viscosity is the cold crack simulator viscosity and the theoretical viscosity is calculated at the same temperature using Walter-Mcchol equation.

The base oil composition of the present invention can be used to prepare individual base stocks as prepared as well as mixtures or blends of two or more base stocks and / or base oils, where the resulting mixtures or blends meet the base stock conditions of the present invention. Include. The base oil composition of the present invention encompasses a range of useful viscosities, including base oil kinematic viscosity at 100 ° C. of about 1.5 to 8.5 cSt, preferably about 2 to 6 cSt, more preferably about 3 to 5 cSt. Base oils of the present invention encompass a range of useful pour points, including pour points of about -9 to -30 ° C, preferably about -12 to about -30 ° C, more preferably about -15 to -30 ° C. In some cases, the pour point can be -18 to -30 ° C, and can also be -20 to -30 ° C.

The working oil of the present invention (a) converts less than 5% by weight of the feedstock into a 650 ° F (343 ° C) minus product such that the VI increase results in a hydrogenated feedstock that is greater than 4 than the VI of the feedstock. Under effective hydrogenation conditions, the hydrogenation catalyst is used to hydroprocess a feedstock having a wax content of at least about 50% by weight based on the feedstock; (b) stripping or distilling the hydrotreated feedstock to separate the gaseous product from the liquid product; (c) Under effective hydrogen dewaxing conditions with a catalyst, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, ECR-42, ITQ-13, MCM Hydrogen dewaxes the liquid product using a dewaxing catalyst of at least one of -68, MCM-71, beta, fluoridated alumina, silica-alumina or fluorinated silica alumina (here, a dewaxing catalyst Contains at least one Group 9 or Group 10 precious metal; (d) a base stock or base, which may be prepared by subjecting the product from step (c) to a hydrogenation finishing, optionally using a medium mesoporous hydrogenation finishing catalyst from the M41S class under hydrogenation finishing conditions. Add oil.

In addition, the base stock and the base oil incorporated into the working oil of the present invention may have (a) a saturate content of 90% by weight or more and (b) a sulfur content of 0.03% by weight or less.

Another embodiment of the present invention provides a composition comprising (a) one or more base stocks having a kinematic viscosity of about 1.5 to about 8.5 mm ² / sec at 100 ° C., (b) a viscosity index of about 110 to 160, and (c) less than about −9 ° C. Pour point, (d) a working oil having a saturate content of about 92 to 100%.

The performance additives used in the present invention may, for example, include individual additives as components, one or more individual additives or combinations of components (eg additive systems), combinations of one or more additives with one or more suitable diluent oils (eg additive concentrates or packages). It may include. Additive concentrates include component concentrates and additive packages. Often, in the preparation or preparation of lubricant compositions or operating oils, viscosity modifiers or viscosity index improvers can be used individually as components or concentrates, regardless of the use of other performance additives in the form of components, concentrates or packages.

Surprisingly, the low measured to theoretical viscosity ratios that highlight the unexpected performance benefits of base stocks and base oils incorporated into the present invention can be expected to be observed even at temperatures below -35 ° C, such as below -40 ° C. have. Thus, at such low temperatures, the actual viscosity of the base stock and base oil of the present invention is expected to be close to the desired ideal and theoretical viscosity, while the control base stock and base oil deviate much more strongly from the theoretical viscosity. (Ie, higher measured viscosity to theoretical viscosity ratio).

The viscosity index of the base stocks and base oils of the present invention incorporated into the present invention may be at least 130, preferably at least 135 and in some cases at least 140. The desired pour point of the base stocks and base oils of the invention is about −9 ° C. or less, preferably −12 ° C. or less, and in some cases more preferably −15 ° C. or less. In some cases, the pour point may be -18 ° C or less, more preferably -20 ° C or less. For base stocks and base oils of the invention, the desired measured viscosity to theoretical viscosity ratio of cold crack simulator (CCS) viscosity is about 1.2 or less, preferably about 1.16 or less, more preferably about 1.12 or less. For the low temperature viscosity profiles of the base stocks and base oils of the invention, the desired base stocks and base oils have a CCS at −35 ° C. of less than 5500 cP, preferably less than 5200 cP, and in some cases more preferably less than 5000 cps. Has a viscosity.

The very advantageous low temperature (below -30 ° C) properties of these base stocks and base oils advantageously improve the performance of the finished oil at concentrations of at least 20% by weight of the total base stock and base oils contained in these compositions. Preferably, the hydraulic oils of the present invention incorporate these base stocks and base oils with other individual base stocks and base oils to achieve significant low temperature performance advantages in the finished finished lubricant composition or hydraulic fluid. More preferably, these base stocks and base oils can be used in at least 20% by weight of the total base stock and base oil contained in the formulated hydraulic oil without damaging the elements of the present invention. In certain cases, the base oil (s) may most preferably be used at least 40% by weight of the total base stock and base oil, or at least 60% by weight of the total base stock and base oil in the finished finished lubricant composition or working oil.

The inventors have unexpectedly discovered that the use of the base stocks and base oils described herein in hydraulic fluids can produce ATFs that exceed the new OEM Brookfield viscosity limit for ATF.

The present invention relates to hydraulic fluids and methods for optimizing the low temperature Brookfield viscosity of automatic transmission fluids. More specifically, the base oil incorporated into the hydraulic oil of the present invention may unexpectedly have a high viscosity index (130 or higher), which may advantageously be used to prepare low viscosity, final finished hydraulic fluid, in particular automatic transmission fluid (ATF), and- It has a ratio of measured high shear / cold viscosity to theoretical high shear / cold viscosity below 30 ° C.

Automatic Transmission Fluid (ATF) is one of the most common hydraulic fluids and an integral part of every automatic transmission. Automatic transmissions are used in about 80% to 90% of all vehicles in North America and Japan, and their use is becoming more common elsewhere in the world. These are the most complex and expensive subassemblies of vehicles, and major OEMs have strict design specifications to control all conditions of the components (including hydraulic fluid) used in their manufacture.

Automatic transmissions include torque converters or clutch assemblies, planetary gears, output travel and hydraulic systems. The ATF acts as a hydraulic fluid that drives complex adjustments to transfer power from the engine to the torque converter or clutch assembly and interlock the gears to provide the correct vehicle speed.

The ATF should have a suitable viscosity at ambient starting temperatures that can be on the order of -40 ° C while maintaining sufficient viscosity at higher operating temperatures of 100 ° C or higher. ATF should also be oxidatively stable as it is expected to be exposed to high temperatures and in some cases continue to be used up to 100,000 miles. Also, the friction characteristics are important for smoothly adjusting the movement to the clutch plate.

Significant advances have been made in ATF additive formulation science to meet these viscosity and oxidation conditions using solvent extracted mineral oils, commonly referred to as Group I base stocks. However, over the past few years, as the performance requirements for automatic transmission fluids have increased, manufacturers have relied on hydrolyzed base stocks, commonly referred to as Group II or Group III base stocks, to meet more stringent conditions.

Recently, major automotive manufacturers have again increased the performance specifications required for ATF as the need for improved viscosity shifts to larger, higher power-density designs (see Table 1). In particular, lower viscosities at lower operating temperatures are required to ensure proper hydraulic operation of the components.

Existing OEM ATF conditions have typically been met only by the use of Group I base stocks, or Group I base stocks blended with Group II or III base stocks. Only by formulating ATFs from the much more expensive Group III and Group IV base stocks can meet these new stringent performance requirements.

High viscosity index base stocks incorporated into the hydraulic fluids of the present invention have excellent low temperature performance when compared to other high viscosity index base stocks. The performance difference is most critical below -30 ° C, where conventional high viscosity index base stocks deviate significantly from theoretical viscosity. To illustrate, the measured low temperature CCS viscosity of comparable conventional high viscosity index base stocks is toward a higher viscosity index than predicted (Walter-Maccol equation) for the predicted theoretical viscosity at low temperature of the same base stock at low temperature. There is a tendency to deviate (see FIG. 1).

The base stocks, base oils of the present invention incorporated into the working oils of the present invention are surprisingly more ideal and highly desirable performance predicted by the theoretical viscosity behavior of the base stocks and base oils described according to the Walter-Mcchol equation (ASTM D341 Appendix). Indicates. In addition, the base stocks and base oils of the present invention surprisingly measure the ratio of the measured low temperature viscosity to the theoretical low temperature viscosity, where the actual viscosity is measured as Cold Crack Simulator (CCS) viscosity at -30 ° C or lower, It was found to be different from commercial Group III base oils in connection with the Walter-Mcchol equation (derived from ASTM D341, Appendix) at the same temperature as the measured CCS viscosity. CCS viscosity is measured under high shear conditions, while Brookfield viscosity is measured under low shear conditions.

Base stocks and base oils incorporated into the working oils of the present invention have a unique and very desirable feature of measured viscosity to theoretical viscosity ratios of up to 1.2, preferably up to 1.16, in many cases more preferably up to 1.12. Base stocks and base oils having a measured viscosity to theoretical viscosity ratio of less than about 1.2 and also close to about 1.0 are highly desirable because lower ratios represent a significant advantage in low temperature performance and operability. However, currently available Group III base stocks and base oils have a measured viscosity to theoretical viscosity ratio of at least 1.2, resulting in poorer base oil low temperature viscosity and operability. In some cases, it is desirable to have a measured viscosity to theoretical viscosity ratio of about 0.8 to about 1.2.

In one embodiment of the present invention, the working oil of the present invention comprises (a) a viscosity index (VI) of at least 130, (b) a pour point of -10 ° C or less, and (c) a measured low temperature viscosity of 1.2 or less at -30 ° C or less. Base stocks with surprising and unexpected simultaneous combinations of ratios of theoretical low temperature viscosity, where the measured viscosity is cold crack simulator viscosity and the theoretical viscosity is calculated at the same temperature using the Walter-Mcchol equation. Mix.

In addition, the base stock and the base oil incorporated into the working oil of the present invention may have (a) a saturate content of 90% by weight or more and (b) a sulfur content of 0.03% by weight or less.

The product incorporating the base stock or base oil of the present invention clearly has advantages over other similar products made from conventional Group II and III base stocks. One embodiment of the present invention is a formulated hydraulic fluid comprising the base stock and base oil of the present invention with one or more additional auxiliary base stocks and base oils. Another embodiment of the present invention is a formulated hydraulic fluid comprising the base stock and base oil of the present invention with one or more performance additives. The present invention is very advantageous for applications where low temperature properties are important for the performance of the finished oil. More specifically, the working oils of the present invention incorporating these base stocks or base oils have been found to produce ATFs with unexpectedly excellent Brookfield viscosity performance results.

Another embodiment of the present invention comprises (i) from about 1.5 to about 8.5 mm ² / sec at 100 ° C., preferably from about 2.0 to about 6.0 mm ² / sec at 100 ° C., more preferably from about 3.0 to about 100 ° C. A kinematic viscosity of 5.0 mm ² / sec, about 110 to about 160, preferably about 120 to about 150, more preferably about 130 to about 150, and a viscosity index of up to about -9 ° C, preferably about -12 ° C, More preferably one or more base stocks having a saturate content of about −15 ° C., a pour point, about 92 to about 100 mass%, more preferably about 96 to about 100 mass%; And (ii) optionally, one having a kinematic viscosity of about 1.5 to about 8.5 mm ² / sec at 100 ° C., a viscosity index of at least about 90, a pour point of up to about −15 ° C., and a saturate content of about 92 to about 100 mass% From about 0 to about 80 volume%, preferably from about 0 to about 50 volume%, of a hydrolyzed Group II or III base stock mixture comprising at least a hydrolyzed base stock; And (iii) optionally hydraulic fluid comprising one or more performance additives, wherein the base stock (i) of the present invention comprises from about 20 to about 100 volume percent, preferably from about 40 to about 100 volume percent of the base oil blend. Present in an amount, the hydrolyzed base stock (ii) is present in an amount from about 0 to about 80 volume percent, preferably from about 0 to about 60 volume percent, of the base oil blend, the mixture of base stocks being 100 A kinematic viscosity of from about 3 to about 6.5 mm ² / sec, preferably from about 3.5 to about 5.5 mm ² / sec at 100 ° C., a viscosity index of from about 100 to about 150, preferably from about 120 to about 150, up to about Having a pour point of −12 ° C., preferably up to about −15 ° C., and the working oil having a kinematic viscosity of from about 4.5 to about 9.5 mm ² / sec at 100 ° C., preferably from about 5.5 to about 8.5 mm ² / sec at 100 ° C., A viscosity index of about 150 to about 230, a pour point up to about -42 ° C, and It has a Brookfield viscosity of about 20,000 cP or less at −40 ° C. or less, preferably about 15,000 cP or less at −40 ° C. or less and about 10,000 cP or less at −40 ° C.

Way

Hydraulic oils derived from the incorporation of base stocks and base oils produced by this method exhibit not only a combination of unique physical properties, but also unique compositional characteristics that distinguish and differentiate them from commercially available products. Thus, the working oils incorporating the base stocks and base oils of the invention derived from the methods cited herein are expected to have unique chemical, compositional, molecular and structural characteristics that uniquely define the base stocks and base oils of the invention. It is expected.

According to a method comprising converting a waxy feedstock to produce an oil of lubricating viscosity having a high viscosity index, base stocks and base oils incorporated into the working oil of the present invention are produced in high yield. Thus, it is possible to obtain base stocks and base oils having VI of at least 130, preferably at least 135, more preferably at least 140 and having excellent low temperature properties. These base stocks can be produced with high yields while having excellent properties such as high VI and low pour point.

The waxy feedstock used in these methods can be derived from natural or mineral or synthetic sources. The feed of this process may have a waxy paraffin content of at least 50% by weight, preferably at least 70% by weight and more preferably at least 80% by weight. Preferred synthetic waxy feedstocks typically have a waxy paraffin content of at least 90% by weight, often at least 95% by weight and in some cases at least 97% by weight. In addition, the waxy feedstock used in these methods of making the base stocks and base oils of the present invention may comprise one or more individual natural, mineral or synthetic waxy feedstocks or any mixture thereof.

In addition, the feedstock to these methods may be taken from conventional mineral oils or may be taken by synthetic methods. For example, the synthesis method may include a gas-to-liquid (GTL) or fisher (Tropsch-Tropsch) hydrocarbon prepared by a method such as the Fischer-Tropsch method or the Kolbel-Englehardt method. have. Many of the preferred feedstocks are characterized by having the majority saturated (paraffinic) compositions.

More specifically, the feedstock used in the process of the present invention is typically a wax-containing feed boiling in a lubricating oil range with a 10% distillation point higher than 650 ° F. (343 ° C.) as measured by ASTM D 86 or ASTM 2887. And derived from mineral or synthetic sources. The wax content of the feedstock may be at least about 50 weight percent based on the feedstock and may amount to 100 weight percent wax. The wax content of the feed can be determined by nuclear magnetic resonance spectroscopy (ASTM D5292), correlated ndM method (ASTM D3238) or solvent means (ASTM D3235). Waxy feeds can be derived from a number of sources, such as natural or mineral or synthetic sources. In particular, waxy feeds can be, for example, raffinate, partially solvent dewaxed oil, deasphalted oil, distillate, vacuum gas oil, coker gas oil, slack wax, foot oil, and the like. Oils derived from the same solvent purification process, and Fischer-Tropsch wax. Preferred feeds are slack wax and Fischer-Tropsch wax. Slack wax is typically derived from the hydrocarbon feed by solvent or propane dewaxing. Slack wax contains some residual oil and typically no oil. Foot oil is derived from deoiled slack wax. The Fischer-Tropsch synthesis process produces Fischer-Tropsch wax. Non-limiting examples of suitable waxy feedstocks include Paraflint 80 (hydrogenated Fisher-Tropsch wax) and Shell MDS Wax Raffinate (hydrogenated and partially isomerized intermediate distillation synthesis). Waxy raffinate).

The feedstock may be high in nitrogen-contaminants and sulfur-contaminants. Feeds containing up to 0.2 wt% nitrogen and up to 3.0 wt% sulfur based on the feed can be processed in this process. Feeds with high wax content typically have a high viscosity index of at least 200. Sulfur content and nitrogen content can be determined by standard ASTM methods D5453 and D4629, respectively.

In the case of a feed derived from solvent extraction, the petroleum fraction with high boiling point from atmospheric distillation is sent to a vacuum distillation apparatus and the distillation fraction from this apparatus is solvent extracted. The residue from vacuum distillation can be deasphalted. The solvent extraction method selectively dissolves the aromatic components on the extract while leaving more paraffinic components on the raffinate. Naphthenes are distributed between the extract phase and the raffinate phase. Typical solvents for solvent extraction include phenol, furfural and N-methyl pyrrolidone. By controlling the solvent to oil ratio, the extraction temperature and the method of contacting the solvent with the distillate to be extracted, the degree of separation between the extract phase and the raffinate phase can be controlled.

Hydrogen Treatment

In the case of hydrogenation, the catalyst is an effective catalyst for hydrogenation such as catalysts containing Group 6 metals (based on the IUPAC Periodic Table with Groups 1-18), Group 8-10 Group metals and mixtures thereof. Preferred metals include nickel, tungsten, molybdenum, cobalt and mixtures thereof. These metals or mixtures of metals are typically present as oxides or sulfides on refractory metal oxide supports. The mixture of metals may also be present as a bulk metal catalyst, wherein the amount of metal is at least 30% by weight based on the catalyst. Suitable metal oxide supports include oxides such as silica, alumina, silica-alumina or titania, preferably alumina. Preferred aluminas are porous aluminas such as gamma or beta. The amount of metal in the individual metals or mixture is about 0.5 to 35% by weight based on the catalyst. For preferred mixtures of Group 9 and 10 metals and Group 6 metals, Group 9 and Group 10 metals are present in amounts of 0.5 to 5 percent by weight based on the catalyst and Group 6 metals in amounts of 5 to 30 percent by weight exist. The amount of metal can be measured by atomic absorption spectroscopy, inductively coupled plasma-atomic emission spectroscopy, or by other methods specified by ASTM for individual metals.

The acidity of the metal oxide support can be controlled by adding promoters and / or dopants, or by adjusting the properties of the metal oxide support, such as by controlling the amount of silica incorporated into the silica-alumina support. Examples of promoters and / or dopants include halogens, in particular fluorine, phosphorus, boron, yttria, rare earth oxides and magnesia. Accelerators, such as halogens, typically increase the acidity of the metal oxide support, while mild basic dopants, such as yttria or magnesia, tend to reduce the acidity of such supports.

Hydrogen treatment conditions are 150 to 400 ° C., preferably 200 to 350 ° C., 1480 to 20786 kPa (200 to 3000 psig), preferably 2859 to 13891 kPa (400 to 2000 psig), hydrogen partial pressure, 0.1 to 10 liquids per hour space velocity (LHSV), preferably from 0.1 to a space velocity of 5 LHSV, and 89 to 1780m ³ / m ³ (500 to 10000scf / B), preferably from 178 to hydrogen supply comprises a water ratio of 890m ³ / m ³ do.

Hydrogen treatment reduces the amount of nitrogen-containing and sulfur-containing contaminants to a level that does not unacceptably affect the dewaxing catalyst of the subsequent dewaxing step. In addition, multinuclear aromatic compounds may be present throughout this mild hydrogenation step. If present, these contaminants are removed at subsequent hydrogen finishing steps.

During the hydroprocessing, less than 5%, preferably less than 3%, more preferably less than 2% by weight of the feedstock is converted to a 650 ° F (343 ° C) minus product, so that the VI increase of the feedstock Hydrogenated feedstocks are produced that are less than 4, preferably less than 3, and more preferably less than 2.

The hydrotreated feedstock may be subjected directly to a dewaxing step, but preferably stripped to remove gaseous contaminants such as hydrogen sulfide and ammonia prior to dewaxing. Stripping may be by conventional means such as flash drums or fractionators.

Dewaxing catalyst

The dewaxing catalyst can be crystalline or amorphous. The crystalline material is a molecular sieve containing one or more 10 or 12 ring channels and may be based on aluminosilicate (zeolite) or silicoaluminophosphate (SAPO). The zeolites used for the oxygenation treatment may contain one or more 10 or 12 channels. Examples of such zeolites include ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Ferrierite, ITQ-13, MCM-68 and MCM-71. Examples of aluminophosphates containing one or more 10 ring channels include ECR-42. Examples of molecular sieves containing 12 ring channels include zeolite beta and MCM-68. Molecular sieves are described in US Pat. Nos. 5,246,566, 5,282,958, 4,975,177, 4,397,827, 4,585,747, 5,075,269 and 4,440,871. MCM-68 is described in US Pat. No. 6,310,265. MCM-71 and ITQ-13 are described in PCT publications WO 0242207 and WO 0078677. ECR-42 is disclosed in US Pat. No. 6,303,534. Preferred catalysts include ZSM-48, ZSM-22 and ZSM-23. Especially preferred is ZSM-48. The molecular sieve is preferably in hydrogen form. Reduction may be effected in situ during the dewaxing step or in a different vessel outside of the reaction system.

Amorphous dewaxing catalysts include alumina, fluorinated alumina, silica-alumina, fluorinated silica-alumina and silica-alumina doped with Group 3 metals. Such catalysts are described, for example, in US Pat. Nos. 4,900,707 and 6,383,366.

Dewaxing catalysts are difunctional. That is, metal hydrogenation components that are one or more Group 6 metals, one or more Group 8 to 10 metals, or mixtures thereof may be added. Preferred metals are Group 9 and Group 10 metals. Especially preferred are Group 9 and Group 10 precious metals, such as Pt, Pd or mixtures thereof (based on the IUPAC Periodic Table having Groups 1-18). These metals are added at a ratio of 0.1 to 30% by weight based on the catalyst. Catalyst preparation and metal addition methods are described, for example, in US Pat. No. 6,294,077 and include, for example, impregnation with ion exchange and degradable metal salts. Metal dispersion techniques and catalyst particle size control are described in US Pat. No. 5,282,958. Catalysts having a small particle size and well dispersed metal are preferred.

Molecular sieves may typically be complexed with or contain no binder (self-bonding) with high temperature resistant binder materials that can be used under dewaxing conditions to produce a final finished dewaxing catalyst. The binder material is typically a binary combination of silica, alumina, silica-alumina, silica and other metal oxides (e.g. titania, magnesia, toria, zirconia, etc.) and ternary combinations of these oxides (e.g. silica-alumina-toria and silica). Inorganic oxides such as alumina and magnesia. The amount of molecular sieve in the finished dewaxing catalyst is 10 to 100, preferably 35 to 100% by weight, based on the catalyst. Such catalysts are prepared by methods such as spray drying, extrusion and the like. The dewaxing catalyst can be used in sulfided or unsulfated form, preferably in sulfided form.

Dewaxing conditions are temperatures of 250 to 400 ° C., preferably 275 to 350 ° C., 791 to 20786 kPa (100 to 3000 psig), preferably 1480 to 17339 kPa (200 to 2500 psig), 0.1 to 10 hours ⁻¹ , preferably Preferably a liquid hourly space velocity of 0.1 to 5 hours ⁻¹ , and hydrogen treatment of 45 to 1780 m ³ / m ³ (250 to 10000 scf / B), preferably 89 to 890 m ³ / m ³ (500 to 5000 scf / B) Gas velocity.

Hydrogen finish

At least some of the product from the dewaxing is sent directly to the hydrogenation stage without leaving. It is desirable to hydrogenate the product resulting from dewaxing to adjust product quality to the desired design specification. Hydrogen finish is a form of mild hydrogenation to saturate olefins and residual aromatics in any lubricating oil range as well as to remove any residual heteroatoms and color bodies. Hydrogen finishing after dewaxing is usually carried out in series with the dewaxing step. In general, the hydrogenation finish is performed at about 150 to 350 ° C, preferably 180 to 250 ° C. The total pressure is typically 2859 to 20786 kPa (about 400 to 3000 psig). A liquid hourly space velocity is typically from 0.1 to 5LHSV (hour ^-1), preferably from 0.5 to 3 hr ^-1, and a hydrogen gas processing rate is 44.5 to 1780m ³ / m ³ (250 to 10,000scf / B).

Hydrogen finish catalysts are those containing Group 6 metals (based on the IUPAC Periodic Table having Groups 1-18), Group 8-10 Metals, and mixtures thereof. Preferred metals include one or more precious metals having a strong hydrogenation action, in particular platinum, palladium and mixtures thereof. The metal mixture may also be present as a bulk metal catalyst in which the amount of metal is at least 30% by weight based on the catalyst. Suitable metal oxide supports include low acid oxides, preferably alumina, such as silica, alumina, silica-alumina or titania. Preferred hydrogenation catalysts for aromatic compound saturation include one or more metals having relatively strong hydrogenation on the porous support. Typical support materials include amorphous or crystalline oxide materials such as alumina, silica and silica-alumina. The metal content of the catalyst is often as high as about 20% by weight for non-noble metals. Precious metals are usually present in amounts up to about 1% by weight.

Hydrogen finishing catalysts are preferably intermediate porous materials belonging to the M41S class or population of catalysts. The M41S population of catalysts is described in J. Amer. Chem. Soc., 1992, 114, 10834, which is an intermediate porous material having a high silica content. Examples include MCM-41, MCM-48 and MCM-50. Medium porosity refers to a catalyst having a pore size of 15 to 100 GPa. A preferred member of this class is MCM-41, the method of preparation of which is described in US Pat. No. 5,098,684. MCM-41 is an inorganic porous non-laminar phase with uniformly sized pores arranged in a hexagon. The physical structure of the MCM-41 resembles a bundle of straws with a straw inlet (pore cell diameter) of 15 to 100 mm 3. MCM-48 is cubic symmetric and is described, for example, in US Pat. No. 5,198,203, while MCM-50 has a layered structure. MCM-41 can be made to have different sized pore inlets in the medium porosity range. The mesoporous material can include metal hydrogenation components that are one or more of Group 8, Group 9, or Group 10 metals. Preferred are noble metals, in particular Group 10 noble metals, most preferably Pt, Pd or mixtures thereof.

In general, the hydrogenation finish is performed at about 150 to about 350 ° C, preferably at 180 to 250 ° C. The total pressure is typically 2859 to 20786 kPa (about 400 to 3000 psig). A liquid hourly space velocity is typically from 0.1 to 5LHSV (hour ^-1), preferably from 0.5 to 3 hr ^-1 and a hydrogen gas processing rate is 44.5 to 1780m ³ / m ³ (250 to 10,000scf / B).

In one embodiment, the present invention is directed to (1) converting less than 5% by weight of the feedstock into a 650 ° F. (343 ° C.) minus product so that its VI increase is less than 4 greater than the VI of the feedstock. Under effective hydrogenation conditions to produce hydrogen, a hydrogenation catalyst is used to hydrotreat the feedstock having a wax content of at least about 60% by weight based on the feedstock; (2) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (3) Under hydrogenodewax conditions effective in terms of catalyst, ZSM-48, ZSM-57, ZSM-23, ZSM-22, ZSM-35, Ferrilite, ECR-42, ITQ-13, MCM-71, Dehydrogenation of the liquid product using a dewaxing catalyst, which contains at least one of MCM-68, beta, fluorinated alumina, silica-alumina or fluorinated silica alumina, which contains one or more Group 9 or Group 10 precious metals A hydraulic oil comprising at least one base stock having at least 130 VIs, prepared by a method comprising waxing.

Another embodiment of the present invention (1) converts less than 5% by weight of the feedstock into a 650 ° F. (343 ° C.) minus product to produce a hydrogenated feedstock whose VI increase is less than 4 greater than the VI of the feedstock. Under effective hydrogenation conditions to produce, hydroprocessing a lubricating oil feedstock having a wax content of at least about 50% by weight based on the feedstock using a hydrogenation catalyst; (2) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (3) Under the conditions of effective hydrogen dewaxing in terms of catalyst, ZSM-22, ZSM-23, ZSM-35, Ferrierite, ZSM-48, ZSM-57, ECR-42, ITQ-13, MCM-68, The liquid product was hydrogenated using a dewaxing catalyst (which contains at least one Group 9 or Group 10 precious metal) of at least one of MCM-71, beta, fluorinated alumina, silica-alumina or fluorinated silica-alumina. Dewaxed; (4) at least one base with at least 130 VI, prepared by a process comprising finishing the product from step (3) using a mesoporous hydrogenated finishing catalyst from the M41S class under hydrogen finishing conditions. It relates to a working oil containing a stock.

Another embodiment of the present invention (1) converts less than 5% by weight of the feedstock into a 650 ° F. (343 ° C.) minus product to produce a hydrogenated feedstock whose VI increase is less than 4 greater than the VI of the feedstock. Under effective hydrogenation conditions to produce, hydroprocessing a lubricating oil feedstock having a wax content of at least about 60% by weight based on the feedstock using a hydrogenation catalyst; (2) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (3) hydrogenowax the liquid product using a dewaxing catalyst, ZSM-48, which contains one or more Group 9 or Group 10 precious metals, under hydrogenodewaxing conditions effective in terms of catalyst; (a) optionally comprising one or more base stocks with at least 130 VIs, prepared by a method comprising hydrogenating the product from step (3) using MCM-41 under hydrogen finishing conditions It relates to the working oil.

Further details regarding the methods of constructing the present invention can be found in co-pending US patent application Ser. No. 60 / 416,865, incorporated herein by reference.

Base Stocks and Base Oils

A wide range of base stocks and base oils are known in the art. Base stocks and base oils that can be used as auxiliary base stocks or auxiliary base oils that are incorporated together into the working oils of the present invention together with the unique base stocks and base oils described herein are natural, mineral and synthetic oils. These lubricant base stocks and base oils can be used individually or in any combination with the mixtures of the present invention. Natural, mineral and synthetic oils (or mixtures thereof) may be used in the form of crude, refined or refined (also known as recycled or reprocessed oils). Crude oils are obtained directly from natural, mineral or synthetic sources and are used without purification. These include shale oil obtained directly from the rectification process, petroleum directly obtained from the primary distillation, and ester oils obtained directly from the ester process. Refined oils are similar to the oils discussed for crude oil, except that refined oils have been improved in one or more refining steps to improve one or more lubricant properties. One skilled in the art is familiar with many purification methods. These methods include, for example, solvent extraction, distillation, secondary distillation, acid extraction, base extraction, filtration, infiltration, dewaxing, hydrogen isomerization, hydrogenolysis, hydrogenation, and the like. Rerefined oils are obtained by methods similar to refined oils using oils already used.

Groups I, II, III, IV, and V were developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to make guidelines for lubricant base stocks and base oils. Wide range of base oil stocks. Group I base stocks typically have a viscosity index of about 80 to 120 and contain more than about 0.03% sulfur and / or less than about 90% saturates. Group II base stocks generally have a viscosity index of about 80 to 120 and contain up to about 0.03% sulfur and at least about 90% saturates. Group III base stocks generally have a viscosity index of greater than about 120 and contain up to about 0.03% sulfur and more than about 90% saturates. Group IV includes polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I-IV. Table 2 below summarizes the characteristics of each of these five groups.

Base stocks and base oils can be derived from a number of sources. Natural oils include animal oils, vegetable oils (eg castor oil and lard oil) and mineral oils. With regard to animal oils and vegetable oils, oils with desirable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely in relation to raw material sources such as, for example, paraffinic, naphthenic or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils also vary in relation to the methods used for their preparation and purification (eg, their distillation range and whether they are direct current or decomposed, hydrogen purified or solvent extracted).

Synthetic oils include hydrocarbon oils. Hydrocarbon oils are polymerized olefins and copolymerized olefins (polybutylene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers and ethylene-alphaolefin copolymers, polymers or copolymers of hydrocarbyl-substituted olefins ( At this time, the hydrocarbyl contains an oil, such as optionally containing O, N or S). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. By way of example, PAO derived from C8, C10, C12, C14 olefins or mixtures thereof can be used. See US Pat. Nos. 4,956,122, 4,827,064 and 4,827,073, which are incorporated herein by reference.

Group III and PAO base stocks and base oils typically exhibit a plurality of viscosity grades (eg, 4cSt, 5cSt, 6cSt, 8cSt, 10cSt, 12cSt, 40cSt, 100cSt or greater, and any number of intermediate viscosity grades at 100 ° C). Viscosity). In addition, PAO base stocks and base oils with high viscosity index characteristics are typically available at higher viscosity grades, such as kinematic viscosity at 100 ° C. of 100 cSt to 3000 cSt or higher. PAO's are known materials and are usually available on a large commercial scale from suppliers such as ExxonMobil Chemical Company, Chevron-Phillips, BP-Amoco, etc. The number average molecular weight typically varies from about 250 to about 3000. PAOs typically include, but are not limited to, C2 to about C32 alphaolefins (preferably C8 to C16 alphaolefins such as 1-octene, 1-decene, 1-dodecene and the like). It consists of a hydrogenated polymer or oligomer. Preferred polyalphaolefins are poly-1-octenes, poly-1-decenes and poly-1-dodecenes, and mixtures thereof, and mixed olefin-derived polyolefins. However, dimers of higher olefins in the range of C14 to C18 can be used to provide a low viscosity base stock of an acceptable low volatility. Depending on the viscosity grade and the starting oligomer, the PAO may be trimers and tetramers of the starting olefins having a viscosity of about 1.5-12 cSt and having trace amounts of higher olefins. PAO base stocks and base oils may be used in lubricant compositions or hydraulic fluids formulated individually or in any combination of two or more.

Friedel-Krafts, including, for example, a complex of aluminum trichloride, boron trifluoride or boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate PAO fluids can be conveniently prepared by polymerizing alphaolefins in the presence of a polymerization catalyst such as Friedel-Crafts catalyst. For example, the methods disclosed in US Pat. No. 4,149,178 or US Pat. No. 3,382,291 can be conveniently used herein. Other information on PAO synthesis can be found in US Pat. Nos. 3,742,082, 3,769,363, 3,876,720, 4,239,930, 4,367,352, 4,413,156, 4,434,408, 4,910,355, 4,956,122 and 5,068,487. It is. Dimers of C14 to C18 olefins are described in US Pat. No. 4,218,330. All of the foregoing patents are incorporated herein by reference.

Other types of synthetic PAO base stocks and base oils include the high viscosity index lubricating oils described in US Pat. Nos. 4,827,064 and 4,827,073, which, together with the base stocks and base oils of the present invention, are also formulated in the present invention. It can be used very advantageously in formulated lubricant compositions or hydraulic fluids. Other useful synthetic lubricants, such as, for example, "Synthetic Lubricants", Gunderson and Hart, Reinhold Publ. Corp., New York, 1962] can also be used.

Other synthetic base stocks and base oils are optionally added in high molecular weight compounds of low molecular weight compounds in which the reactor is not olefinic (e.g., iso dewaxing, alkylation, esterification, hydrogen isomerization, dewaxing, etc.). Hydrocarbon oils derived from oligomerization or polymerization to a base oil of lubricating viscosity.

Hydrocarbyl aromatic base stocks and base oils are also widely used in lubricating oils and hydraulic oils. In alkylated aromatic compound stocks (eg, hydrocarbyl aromatic compounds), ACS Petroleum Chemistry Preprint 1053-1058, "Poly n-Alkylbenzene Compounds: A Class of Thermally Stable and Wide Liquid Range Fluids", Yfen et al., Phila. As described for alkyl benzene in 1984, alkyl substituents are typically alkyl groups having about 8 to 25 carbon atoms, typically about 10 to 18 carbon atoms, and these alkyl substituents may be up to three. Trialkyl benzenes can be prepared by cyclodimerizing 1-alkaine having 8 to 12 carbon atoms as described in US Pat. No. 5,055,626. Other alkylbenzenes are described in EP 168534 and US Pat. No. 4,658,072. Alkylbenzenes are used as lubricant base stocks, in particular in low temperature applications (Arctic vehicle service and refrigeration oil) and papermaking oil. These are linear alkylbenzenes such as Vista Chem. Co., Huntsman Chemical Co., Chevron Chemical Co., and Nippon Oil Co. (LAB) can be purchased from the manufacturer. Linear alkylbenzenes typically have good low pour point and low temperature viscosity, and VI values greater than 100, with good solubility in additives. Other alkylated aromatic compounds that can be used if desired are described, for example, in "Synthetic Lubricants and High Performance Functional Fluids", Dressler, Chapter 5, (Schkin edit), Marcel Dekker, New York 1993. Aromatic base stocks and base oils are, for example, benzene, naphthalene, biphenyl, diaryl ether, di-aryl sulfides, di-aryl sulfones, di-aryl sulfoxides, di-aryl methanes or ethane or propane or higher homologues. , Hydrocarbyl alkylated derivatives of mono- or di- or tri-aryl heterocyclic compounds containing one or more O, N, S or P.

Hydrocarbyl aromatic compounds that may be used may be any hydrocarbyl molecule containing at least about 5% of the weight derived from aromatic residues such as benzenoid residues or naphthenoid residues or derivatives thereof. These hydrocarbyl aromatic compounds include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenols, and the like. The aromatic compound may be mono-alkylated, dialkylated, polyalkylated and the like. Aromatic compounds can be monofunctional or polyfunctionalized. Hydrocarbyl groups may also consist of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups. Hydrocarbyl groups can range from about C6 to about C60, with the range of about C8 to about C40 often being preferred. Mixtures of hydrocarbyl groups are sometimes preferred. Hydrocarbyl groups may optionally contain sulfur, oxygen and / or nitrogen containing substituents. Aromatic groups may also be derived from natural (petroleum) sources when at least about 5% of the molecules consist of aromatic moieties of this type. A viscosity at 100 ° C. of about 3 cSt to about 50 cSt is preferred, and a viscosity of about 3.4 cSt to about 20 cSt is often more preferred for the hydrocarbyl aromatic component. In one embodiment, alkyl naphthalene is used in which the alkyl group consists mainly of 1-hexadecene. Other alkylates of aromatic compounds can be advantageously used. Naphthalene can be alkylated with, for example, olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like. Useful concentrations of the hydrocarbyl aromatic compound in the lubricating oil composition may be from about 2 to about 25%, preferably from about 4 to about 20%, more preferably from about 4 to about 15%, depending on the application.

Other useful base stocks include, but are not limited to, hydrogen isomerized waxy stocks (e.g. gas oils, slack waxes, fuel hydrogen cracker bottom products, etc.), hydrogen isomerized Fischer-Tropsch waxes, GTL base stocks and base oils, And wax isomer base stocks and base oils, including other wax isomerized hydrogen isomerized base stocks and base oils, or mixtures thereof. Fischer-Tropsch wax, the high boiling residue of Fischer-Tropsch synthesis, is a highly paraffinic hydrocarbon with very low sulfur content. In the hydrogen processing used to prepare such base stocks, amorphous hydrogen decomposition / hydrogen isomerization, such as a special lubricating oil hydrolysis (LHDC) catalyst or a crystalline hydrogen decomposition / hydrogen isomerization catalyst, preferably one of zeolite catalysts Catalysts can be used. For example, one useful catalyst is ZSM-48 described in US Pat. No. 5,075,269. Processes for producing hydrocracked / hydrogen isomerized distillates and hydrocracked / hydrogen isomerized waxes are described, for example, in US Pat. Nos. 2,817,693, 4,975,177, 4,921,594 and 4,897,178, and the United Kingdom. Patents 1,429,494, 1,350,257, 1,440,230 and 1,390,359. Particularly preferred methods are described in EP 464546 and 464547. Methods of using Fischer-Tropsch wax feeds are described in US Pat. Nos. 4,594,172 and 4,943,672. GTL base stocks and base oils, Fischer-Tropsch wax-derived base stocks and base oils, and other wax isomerized hydrogen isomerization (wax isomers) base stocks and base oils can be advantageously used in the present invention, and Useful kinematic viscosity at 100 ° C. of 3 to about 50 cSt, preferably about 3 to about 30 cSt, more preferably about 3.5 to about 25 cSt (eg, for GTL4, kinematic viscosity at 100 ° C. of about 3.8 cSt and about Having a viscosity index of 138). GTL base stocks and base oils, Fischer-Tropsch wax-derived base stocks and base oils, and other wax isomerized hydrogen isomerized base stocks and base oils may have useful pour points up to about -20 ° C., and some conditions Under it can have an advantageous pour point of about -25 ° C or less and a useful pour point of about -30 ° C to about -40 ° C or less. Useful compositions of GTL base stocks and base oils, Fischer-Tropsch wax derived base stocks and base oils, and wax isomerized hydrogen isomerized base stocks and base oils are described, for example, in US Pat. No. 6,080,301, incorporated herein by reference, 6,090,989 and 6,165,949.

GTL base stocks and base oils, Fischer-Tropsch wax derived base stocks and base oils are conventional Group II and III group base stocks and bases that can be used as co-base stocks or co-base oils with the present invention. Advantageous kinematic viscosity over oil has the advantage. GTL base stocks and base oils may have a significantly higher kinematic viscosity of about 20 to 50 cSt at 100 ° C., while by comparison, commercial Group II base stocks and base oils have kinematic viscosities of about 15 cSt or less at 100 ° C. Commercially available Group III base stocks and base oils may have a kinematic viscosity of about 10 cSt or less at 100 ° C. Compared with the more defined kinematic viscosities of Group II and III base stocks and base oils, in combination with the present invention, the higher kinematic viscosity ranges of GTL base stocks and base oils are further advantageous in formulating lubricant compositions. This can provide an advantage. In addition, GTL base stocks and base oils and other wax isomerized hydrogen isomerized base stocks and base oils, combined with low sulfur contents of suitable olefin oligomer and / or alkyl aromatic compound base stocks and base oils, and in combination with the present invention The very low sulfur content of may provide additional advantages in lubricant compositions where very low total sulfur content can advantageously affect lubricant performance.

Alkylene oxide polymers and copolymers, and derivatives thereof containing modified terminal hydroxyl groups obtained by, for example, esterification or etherification, are useful synthetic lubricants. By way of example, ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol having an average molecular weight of about 1000, polyethylene having a molecular weight of about 500 to 1000 Diphenyl ether of glycol and diethyl ether of polypropylene glycol having a molecular weight of about 1000 to 1500) or mono- and polycarboxylic acid esters thereof (eg, acidic acid esters of tetraethylene glycol, mixed These oils can be obtained by polymerization of C3-8 fatty acid esters, or C13 oxo acid diesters).

The ester constitutes a useful base stock. By using esters such as esters of monoalkanols and dibasic acids and polyol esters of monocarboxylic acids, additive solubility and sealing compatibility characteristics can be ensured. Esters of the former type include, for example, various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and the like, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, schubertic acid, Esters of dicarboxylic acids such as sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid and the like. Specific examples of this type of ester are dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl Phthalate, diedecyl phthalate, diicosyl sebacate and the like.

Particularly useful synthetic esters are one or more polyhydric alcohols, preferably hindered polyols such as neopentyl polyols such as neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol , Trimethylol propane, pentaerythritol and dipentaerythritol) containing alkanes containing at least about 4 carbon atoms, such as C5 to C30 acids (e.g. caprylic acid, capric acid, lauric acid, myristic) Obtained by reacting with saturated straight chain fatty acids, including acid, palmitic acid, stearic acid, arachic acid and behen, or with corresponding branched or unsaturated fatty acids such as oleic acid or mixtures thereof.

Suitable synthetic ester components include esters of one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms with trimethylol propane, frymethylol butane, trimethylol ethane, pentaerythritol and / or dipentaerythritol Include. Such esters are widely commercially available, for example, as Mobil P-41 and P-51 esters (ExxonMobil Chemical Company).

Other esters can include natural esters and derivatives thereof, optionally fully esterified or partially esterified with free hydroxyl or carboxyl groups. Such esters may include glycerides, derivatives of natural and / or modified vegetable oils, fatty acids or fatty alcohols.

Silicon-based oils are another class of useful synthetic lubricants. These oils include polyalkyl-, polyaryl-, polyalkoxy- and polyaryloxy-siloxane oils and silicate oils. Examples of suitable silicon-based oils include 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) siloxane and poly- (methyl-2-methylphenyl) siloxane.

Another class of synthetic lubricants is esters of phosphorus-containing acids. These include, for example, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid.

Other types of base stocks and base oils are polymer tetrahydrofuran and the like, and derivatives thereof that are partially or fully derivatized or capped with a suitable hydrocarbyl group in which the reactive pendant group or terminal group may optionally contain O, N or S. It includes.

A very advantageous viscosity advantage of the base stocks and base oils of the present invention with one or more performance additives can be realized and the desired measured below -25 ° C, preferably below -30 ° C, in the resulting formulated lubricant composition or hydraulic oil. Viscosity to theoretical viscosity ratios are realized. These lubricant compositions or hydraulic oils are also characterized by unique and very preferred measured viscosity to theoretical viscosity ratios of up to 1.2, preferably up to 1.16, in many cases more preferably up to 1.12. Thus, the effect of the measured viscosity of the base stock and base oil versus the theoretical viscosity feature of the present invention is preserved even in the presence of a performance additive, thereby improving the formulation comprising the base stock and base oil and one or more performance additives of the present invention. Produced lubricant composition or hydraulic fluid.

Performance additives

Additional lubricant components in effective amounts of lubricant composition, such as, for example, polar and / or nonpolar lubricant base oils, and for example metal and ashless oxidation inhibitors, metal and ashless dispersants, metal and ashless detergents, corrosion and rust inhibitors, metal deactivation Agents, antiwear agents (metals and non-metals, low ash, phosphorus-containing and non-phosphorus, sulfur-containing and non-sulfur types), extreme pressure additives (metals and non-metals, phosphorus-containing and non-phosphorus, sulfur- Containing and non-sulfur types), anti-seizure agents, pour point depressants, wax modifiers, viscosity index improvers, viscosity modifiers, sealing compatibilizers, friction modifiers, lubricants, antifouling agents, colorants, antifoams, demulsifiers, etc. The present invention can be used together. For an overview of many commonly used additives, see Klamann, Lubricants and Related Products , Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0, which also describes many of the lubricant additives discussed below. See also “ Lubricant Additives ”, M. Ranney, Noyes Data Corporation, N. Park Ridge, NJ (1973). In particular, the base oils of the present invention may exhibit significant performance benefits with modern additives and / or additive systems and additive packages that impart low sulfur, low phosphorus and / or low ash characteristics to the formulated lubricant compositions or hydraulic fluids. .

Abrasion Resistant and Extreme Pressure Additives

Additional antiwear additives may be used with the present invention. While many different types of antiwear additives exist, for decades the major antiwear additives for internal combustion engine crankcase oils are metal alkylthiophosphates, more specifically metal dialkyldithiophosphates whose main metal component is zinc or Zinc dialkyldithiophosphate (ZDDP). ZDDP compounds are usually of the formula Zn [SP (S) (OR ¹ ) (OR ² )] ₂ , wherein R ¹ and R ² are C ₁ -C ₁₈ alkyl groups, preferably C ₂ -C ₁₂ alkyl groups Compound. These alkyl groups can be straight chain or branched. For example, suitable alkyl groups include isopropyl, 4-methyl-2-pentyl and isooctyl. ZDDP is commonly used in amounts of about 0.4 to about 1.4 weight percent of the total lubricating oil composition, but can often be advantageously used in more or less amounts.

However, phosphorus from these additives has a detrimental effect on the catalyst in the converter with the catalyst and also on the oxygen sensor in the motor vehicle. One way to minimize this effect is to replace some or all of the ZDDP with a phosphorus-free antiwear additive.

Various non-phosphorus additives are also used as antiwear additives. Sulfurized olefins are useful as antiwear and EP additives. Sulfur-containing olefins can be prepared by sulfiding various organic materials including aliphatic, arylaliphatic or cycloaliphatic olefinic hydrocarbons containing about 3 to 30, preferably 3 to 20, carbon atoms. The olefinic compound contains one or more non-aromatic double bonds. Such compounds are defined by the formula R ³ R ⁴ C═CR ⁵ R ⁶ , wherein R ³ to R ⁶ are each independently hydrogen or a hydrocarbon radical. Preferred hydrocarbon radicals are alkyl or alkenyl radicals. Any two of R ³ to R ⁶ may be linked to form a cyclic ring. Additional information regarding sulfurized olefins and methods for their preparation can be found in US Pat. No. 4,941,984, which is incorporated herein by reference.

Use of thiophosphoric acid and thiophosphoric acid esters as lubricant additives for polysulfides is disclosed in US Pat. Nos. 2,443,264, 2,471,115, 2,526,497 and 2,591,577. Wear protection, oxidation prevention and addition as EP additives of phosphorothionyl disulfide is disclosed in US Pat. No. 3,770,854. Alkylthiocarbamoyl compounds such as bis (dibutyl) thioca together with molybdenum compounds such as oxymolybdenum diisopropylphosphorodithioate sulfide and phosphorus esters such as dibutyl hydrogen phosphite The use of night oils) as antiwear additives in lubricants is disclosed in US Pat. No. 4,501,678. US Patent 4,758,362 discloses the use of carbamate additives to provide improved wear protection and extreme pressure properties. The use of thiocarbamate as an antiwear additive is disclosed in US Pat. No. 5,693,598. Thiocarbamate / molybdenum complexes such as moly-sulfur alkyl dithiocarbamate trimer complexes (R═C ₈ -C ₁₈ alkyl) are also useful antiwear agents. The aforementioned patents are each incorporated herein by reference.

Esters of glycerol can be used as antiwear agents. For example, mono-, di- and tri-oleate, mono-palmitate and mono-myristate can be used.

ZDDP is combined with other compositions that provide antiwear properties. U.S. Patent No. 5,034,141 discloses that a combination of a thiodixanthogen compound (e.g. octylthiodiixanthogen) and a metal thiophosphate (e.g. ZDDP) can improve the wear protection properties. U.S. Patent No. 5,034,142 discloses the use of metal alkoxyalkyl xanthates (eg nickel ethoxyethyl xanthate) and dizantogens (eg diethoxyethyl diszantogen) in conjunction with ZDDP to improve wear protection properties. Doing.

The antiwear additive may be used in an amount of about 0.01 to 6 weight percent, preferably about 0.01 to 4 weight percent.

Viscosity Index Improver

Viscosity index improvers (also known as VI improvers, viscosity modifiers or viscosity improvers) provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and impart acceptable viscosity at low temperatures.

Suitable viscosity index improvers include low molecular weight and high molecular weight hydrocarbons, polyesters and viscosity index improvers and dispersants that act as dispersants. Typical molecular weights of these polymers are about 10,000 to 1,000,000, more typically about 20,000 to 500,000, even more typically about 50,000 to 200,000.

Examples of suitable viscosity index improvers are polymers and copolymers of methacrylate, butadiene, olefins or alkylated styrenes. Polyisobutylene is a commonly used viscosity index improver. Other suitable viscosity index improvers are polymethacrylates, such as copolymers of alkyl methacrylates of various chain lengths, and some formulations also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates, such as copolymers of acrylates of various chain lengths. Specific examples include styrene-isoprene or styrene-butadiene based polymers having a molecular weight of about 50,000 to 200,000.

Viscosity index improvers may be used in amounts of about 0.01 to 15 weight percent, preferably about 0.01 to 10 weight percent, and in some cases more preferably about 0.01 to 5 weight percent.

Antioxidant

Antioxidants delay degradation by oxidation of the base oil during use. This deterioration results in deposits on the metal surface, the presence of sludge or an increase in the viscosity of the lubricant. One skilled in the art knows a wide variety of oxidation inhibitors useful in lubricating oil compositions. See, eg, Lubricants and Related Products, cited above, and US Pat. Nos. 4,798,684 and 5,084,197, which are incorporated herein by reference. Useful antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds, or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, which include derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position relative to each other. Typical phenolic antioxidants include the alkylene coupled derivatives of these hindered phenol and hindered phenol substituted with C ₆ + alkyl group. Examples of this type of phenolic material are 2-3-butyl-4-heptyl phenol, 2-3-butyl-4-octyl phenol, 2-3-butyl-4-dodecyl phenol, 2,6-di Tert-butyl-4-heptyl phenol, 2,6-di-tert-butyl-4-dodecyl phenol, 2-methyl-6-tert-butyl-4-heptyl phenol and 2-methyl-6- Tert-butyl-4-dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenol propionic ester derivatives. Bis-phenolic antioxidants can also be advantageously used in the present invention. Examples of ortho bonded phenols include 2,2'-bis (6-tert-butyl-4-heptyl phenol), 2,2'-bis (6-tert-butyl-4-octyl phenol) and 2,2 '-Bis (6-tert-butyl-4-dodecyl phenol). Para-bonded bisphenols are for example 4,4'-bis (2,6-di-tert-butyl phenol) and 4,4'-methylene-bis (2,6-di-tert-butyl phenol) Include.

Non-phenolic antioxidants that can be used include aromatic amine antioxidants and can be used on their own or in combination with phenols. Typical examples of non-phenolic antioxidants are of the formula R ⁸ R ⁹ R ¹⁰ N, wherein R ⁸ is an aliphatic, aromatic or substituted aromatic group, R ⁹ is an aromatic or substituted aromatic group, and R ¹⁰ is H, Alkyl, aryl or R ¹¹ S (O) _x R ¹² , R ¹¹ is an alkylene, alkenylene or aralkylene group, R ¹² is a higher alkyl or alkenyl, aryl or alkaryl group, x is 0, 1 Or 2) alkylated and non-alkylated aromatic amines, such as aromatic monoamines. Aliphatic groups R ⁸ may contain from 1 to about 20 carbon atoms and preferably contain 6 to 12 carbon atoms. Aliphatic groups are saturated aliphatic groups. Preferably, R ⁸ and R ⁹ are both aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. The aromatic groups R ⁸ and R ⁹ can be linked together with other groups such as S.

Typical aromatic amine antioxidants have alkyl substituents having about 6 or more carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Generally, aliphatic groups do not contain more than about 14 carbon atoms. Common types of amine antioxidants useful in the present compositions include diphenylamine, phenyl naphthylamine, phenothiazine, imidodibenzyl and diphenyl phenylene diamine. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants may also be used. Specific examples of aromatic amine antioxidants useful in the present invention include p, p'-dioctyldiphenylamine, tert-octylphenyl-alpha-naphthylamine, phenyl-alphanaphthylamine and p-octylphenyl-alpha-naphthyl Amines.

Sulfurized alkyl phenols and their alkali or alkaline earth metal salts are also useful antioxidants. Low sulfur peroxide decomposers are also useful as antioxidants.

Another class of antioxidants used in lubricating oil compositions are oil soluble copper compounds. Suitable copper compounds of any oiliness can be blended into the lubricant. Examples of suitable copper antioxidants include copper dihydrocarbyl thio or dithio-phosphate and copper salts (naturally occurring or synthesized) of carboxylic acids. Other suitable copper salts include copper dithiacarbamate, sulfonate, phenate and acetylacetoneate. Basic, neutral or acidic copper Cu (I) and / or CU (II) salts derived from alkenyl succinic acids or anhydrides are known to be particularly useful.

Preferred antioxidants include hindered phenols, arylamines, low sulfur peroxide decomposers and other related ingredients. These antioxidants can be used individually by type or in combination with each other. These additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 2% by weight.

Detergent

Detergents are commonly used in lubricant compositions. Typical detergents are anionic materials containing long chain lipophilic sites of the molecule and smaller anionic or oleophobic sites of the molecule. Anionic sites of detergents are typically derived from organic acids such as sulfuric acid, carboxylic acids, phosphoric acid, phenols or mixtures thereof. Counter ions are typically alkaline earth metals or alkali metals.

Salts containing substantially stoichiometric amounts of metal are described as neutral salts and have a total base number of 0 to 80 (measured according to TBN, ASTM D2896). Many compositions containing large amounts of metal bases obtained by reacting excess metal compounds (such as metal hydroxides or oxides) with acidic gases (such as carbon dioxide) are overbased. Useful detergents may be neutral, weakly overbased or very overbased.

It is desirable that at least some detergents be overbased. Overbased detergents are produced by the combustion process to help neutralize the acidic impurities contained in the oil. Typically, overbased materials have a ratio of metal ions to anionic sites of the detergent on an equivalent basis of about 1.05: 1 to 50: 1. More preferably, the ratio is about 4: 1 to about 25: 1. The resulting detergent is typically an overbased detergent having a TBN of at least about 150, often at least about 250 to 450. Preferably, the overbased cation is sodium, calcium or magnesium. Mixtures of detergents with different TBNs can be used in the present invention. Preferred detergents include alkali metal salts or alkaline earth metal salts of sulfates, phenates, carboxylates, phosphates and salicylates.

Sulfonates can be prepared from sulfonic acids typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (eg, chlorobenzene, chlorotoluene and chloronaphthalene). Alkylating agents typically have about 3 to 70 carbon atoms. Alkaryl sulfonates typically contain about 9 to about 80 or more carbon atoms, more typically about 16 to 60 carbon atoms.

Klaman, cited above, discloses a number of overbased metal salts of various sulfonic acids that are useful as detergents and dispersants in lubricants. CV Smallheer and RK Smith, " Lubricant Additives ", Lezius-Hiles Co., Cleveland, Ohio. (1967) discloses a number of overbased sulfonates that are similarly useful as dispersants / detergents.

Alkaline earth metal phenates are another useful class of detergent. These detergents can be prepared by reacting alkaline earth metal hydroxides or oxides such as CaO, Ca (OH) ₂ , BaO, Ba (OH) ₂ , MgO, Mg (OH) ₂ with alkyl phenols or sulfided alkylphenols. . Useful alkyl groups include straight or branched C ₁ -C ₃₀ alkyl groups, preferably C ₄ -C ₂₀ alkyl groups. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, 1-ethyldecylphenol, and the like. It should be noted that the starting alkylphenols may each contain more than one alkyl substituent, either straight or branched. In the case of using non-sulfurized alkylphenols, sulfided products can be obtained by methods well known in the art. These methods include heating a mixture of alkylphenols and sulfiding agents (including elemental sulfur, sulfur halides such as sulfur dichloride, etc.) and then reacting the sulfided phenols with alkaline earth metal bases.

Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents can be prepared by reacting a basic metal compound with one or more carboxylic acids and removing free water from the reaction product. These compounds can be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long-chain alkyl salicylates, wherein the alkyl group has 1 to about 30 carbon atoms, and there are 1 to 4 alkyl groups per benzenoid nucleus, and the metals of the compounds include alkaline earth metals. Preferred R groups are alkyl chains of at least about C ₁₁ , preferably at least C ₁₃ . R may be optionally substituted with substituents that do not interfere with the action of the detergent. M is preferably calcium, magnesium or barium. More preferably, M is calcium.

Hydrocarbyl-substituted salicylic acid can be prepared from phenol by the Kolbe reaction. See US Pat. No. 3,595,791 for additional information on the synthesis of these compounds. Metal salts of hydrocarbyl-substituted salicylic acid can be prepared by double decomposition of metal salts in polar solvents such as water or alcohols. Alkaline earth metal phosphates are also used as detergents.

Detergents may be known as simple detergents or hybrid or complex detergents. Complex detergents can provide the properties of both detergents without the need to blend separate materials. See, eg, US Pat. No. 6,034,039.

Preferred detergents include calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate and other related ingredients, including borated detergents. Typically, the total detergent concentration is about 0.01 to about 6 weight percent, preferably about 0.1 to 4 weight percent.

In addition, nonionic detergents can be preferably used in the lubricating composition. These nonionic detergents may be ashless or low ash compounds and may include separate molecular compounds and oligomeric and / or polymeric compounds.

Dispersant

During engine operation, insoluble oxidative by-products are produced. Dispersants help keep these by-products in solution to reduce their deposition on metal surfaces. Dispersants may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not substantially produce ash upon combustion. For example, it is believed that the non-metal- or boron metal-free dispersant is ashless. In contrast, the metal-containing detergents discussed above produce ash upon combustion.

Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain about 50 to 400 carbon atoms.

Dispersants include phenates, sulfonates, sulfated fenates, salicylates, naphthenates, stearates, carbamates, thiocabamates and phosphorus derivatives. Particularly useful dispersant classes are typically alkenylsuccinic acid derivatives prepared by reacting long-chain substituted alkenyl succinic acid compounds, usually substituted succinic anhydrides with polyhydroxy or polyamino compounds. The long chain group constituting the lipophilic moiety of the molecule that imparts solubility in oil is usually a polyisobutylene group. Many examples of these types of dispersants are well known. Exemplary US patents describing such dispersants include US Pat. Nos. 3,172,892, 3,2145,707, 3,219,666, 3,316,177, 3,341,542, 3,444,170, 3,454,607, 3,541,012, 3,630,904 3,632,511, 3,787,374 and 4,234,435. Other types of dispersants include U.S. Pat. 3,726,882, 4,454,059, 3,329,658, 3,449,250, 3,519,565, 3,666,730, 3,687,849, 3,702,300, 4,100,082, 5,705,458. Further description of the dispersant may also be found in EP 471 071. The above mentioned patents and patent applications are each incorporated herein by reference.

Hydrocarbyl-substituted succinic acid compounds are well known dispersants. In particular, succinimides, succinate esters or succinate ester amides prepared by reacting a hydrocarbon-substituted succinic acid having preferably at least 50 carbon atoms in a hydrocarbon substituent with at least one equivalent of alkylene amine are particularly useful.

Succinimides are prepared by the condensation reaction between alkenyl succinic anhydrides and amines. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA may vary from about 1: 1 to about 5: 1. Representative examples are described in US Pat. Nos. 3,087,936, 3,172,892, 3,219,666, 3,272,746, 3,322,670, 3,652,616, 3,948,800 and Canadian Patent 1,094,044, each of which is incorporated herein by reference. It is.

Succinate esters are prepared by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, condensation products of alkenyl succinic anhydrides and pentaerythritol are useful dispersants.

Succinate ester amides are prepared by the condensation reaction between alkenyl succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are described in US Pat. No. 4,426,305, which is incorporated herein by reference.

The molecular weight of the alkenyl succinic anhydride used in the above paragraph is about 800 to 2,500. The product may be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids (eg oleic acid) and boron compounds (eg borate esters or highly borated dispersants). Boronizing the dispersant using about 0.1 to about 5 moles of boron per mole of dispersant reaction product, including those derived from mono-succinimide, bis-succinimide (also known as disuccinimide), and mixtures thereof You can.

Mannich base dispersants are prepared from the reaction of alkylphenols, formaldehyde and amines. See US Pat. No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts such as oleic acid and sulfonic acid may also be part of the reaction mixture. The molecular weight of alkylphenols is 800 to 2,500. Representative examples are described in US Pat. Nos. 3,697,574, 3,703,536, 3,704,308, 3,751,365, 3,756,953, 3,798,165, and 3,803,039, which are incorporated herein by reference.

Typical high molecular weight fatty acid modified Mannich condensation products useful in the present invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatic compounds or HN (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenols, polybutylphenols and other polyalkylphenols. These polys are alkylated with high molecular weight polypropylene, polybutylene and other polyalkylene compounds in the presence of alkylating agents such as BF ₃ to provide alkyl substituents on the benzene ring of phenols having an average molecular weight of 600 to 100,000. Alkylphenols can be obtained.

Examples of HN (R) ₂ group-containing reactants are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing one or more HN (R) ₂ groups, suitable for use in the preparation of Mannich condensation products, are well known and are mono- and di-amino alkanes and substituted analogs thereof such as ethylamine and Diethanol amines; Aromatic diamines such as phenylene diamine, diamino naphthalene; Heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine; Melamine and substituted analogs thereof.

Examples of alkylene polyamide reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexaamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene deca Amines, decaethylene undecaamine and mixtures of these amines. Some preferred compositions correspond to the formula H ₂ N— (Z—NH—) _n H where Z is divalent ethylene and n is 1 to 10. Propylene diamines and corresponding propylene polyamines such as di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants. Alkylene polyamines are typically obtained by reaction of ammonia with dihalo alkanes such as dichloro alkanes. Accordingly, alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloro alkanes having 2 to 6 carbon atoms and chlorine on different carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of high molecular weight products useful in the present invention include aliphatic aldehydes such as formaldehyde (eg, paraformaldehyde and formallyne), acetaldehyde and aldol (eg, b-hydroxybutyraldehyde). Formaldehyde or formaldehyde-producing reactants are preferred.

Hydrocarbyl substituted amine ashless dispersant additives are well known to those skilled in the art. See, for example, US Pat. Nos. 3,275,554, 3,438,757, 3,565,804, 3,755,433, 3,822,209 and 5,084,197, which are incorporated herein by reference.

Preferred dispersants include borated and non-borated succinimides, including mono-succinimides, bis-succinimides and / or derivatives from mixtures of mono-succinimides and bis-succinimides, Carbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of about 500 to about 5000 or a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine bound Mannich adducts, capped derivatives thereof and other related compounds. Such additives may be used in amounts of about 0.1 to 20% by weight, preferably about 0.1 to 8% by weight.

Other dispersants may include oxygen-containing compounds such as polyether compounds, polycarbonate compounds, and / or polycarbonyl compounds as low molecular weight to high molecular weight oligomers or polymers.

Friction modifier

Friction modifiers are any materials or materials that can change the coefficient of friction of any lubricant or fluid containing these material (s). Base oils or lubricant compositions of the invention, if necessary, are friction modifiers, also known as friction reducers, or lubricants or oiliness agents, and these other agents that change the coefficient of friction of lubricant base oils, formulated lubricant compositions, or hydraulic fluids. Can be used effectively with Friction modifiers that lower the coefficient of friction are particularly advantageous with the base oil and lubricating oil compositions of the present invention. Friction modifiers may include metal-containing compounds or materials, and ashless compounds or materials, or mixtures thereof. Metal-containing friction modifiers may include metal salts or metal-ligand complexes in which the metal may comprise an alkali metal, an alkaline earth metal or a transition metal. Such metal-containing friction modifiers may also have ashless characteristics. The transition metal may include Mo, Sb, Sn, Fe, Cu, Zn and the like. The ligands are alcohols, polyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines , Hydrocarbyl derivatives of other polar molecular functional groups containing thiazole, thiadiazole, dithiazole, diazole, triazole and effective amounts of O, N, S or P individually or in combination. In particular, Mo- such as, for example, Mo-dithiocarbamate, Mo (DTC), Mo-dithiophosphate, Mo (DTP), Mo-amine, Mo (Am), Mo-alcoholate, Mo-alcohol-amide, etc. Containing compounds are particularly effective.

Ashless friction modifiers may also include lubricant materials containing effective amounts of polar groups, such as lubricant materials containing hydrocarbyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like. have. The polar group of the friction modifier may comprise a hydrocarbyl group containing an effective amount of O, N, S or P individually or in combination. Other friction modifiers that may be particularly effective are, for example, salts of fatty acids (ash-containing and ashless derivatives), fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates and comparable synthetic long chain hydrocarbyl acids, alcohols, amides, Esters, hydroxy carboxylates, and the like. In some cases, organic fatty acids, fatty amines and sulfurized fatty acids can be used as suitable friction modifiers.

Useful concentrations of friction modifiers may be from about 0.01 to 10 to 15 weight percent or more, often preferably from about 0.1 to 5 weight percent. The concentration of molybdenum containing material is often described as the Mo metal concentration. Advantageous Mo concentrations may be at least about 10-3000 ppm, often preferably about 20-2000 ppm, and in some cases more preferably about 30-1000 ppm. All types of friction modifiers may be used alone or in admixture with the materials of the present invention. Often a mixture of two or more friction modifiers or a mixture of friction modifier (s) and other surface active material (s) is also desirable.

Pour point depressant

Conventional pour point depressants (also known as lubricating oil flow improvers) can be added to the compositions of the present invention if desired. These pour point depressants can be added to the lubricating composition of the present invention to lower the minimum temperature at which fluid can flow or flow. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, haloparaffin waxes and aromatics. Condensation products of compounds, vinyl carboxylate polymers and dialkylfumarates, terpolymers of fatty acid vinyl esters and allyl vinyl ethers. U.S. Pat. Doing. Each of these references is incorporated herein by reference. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Corrosion inhibitor

Corrosion inhibitors are used to reduce degradation of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include thiadiazoles. See, eg, US Pat. Nos. 2,719,125, 2,719,126, and 3,087,932, which are incorporated herein by reference. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Sealing Compatibility Additives

Seal compatibilizers help to swell the elastomeric seal by causing chemical reactions in the fluid or by causing physical changes in the elastomer. Sealing compatibilizers suitable for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters such as butylbenzyl phthalate and polybutenyl succinic anhydride. Additives of this type are commercially available. Such additives may be used in amounts of about 0.01 to 3% by weight, preferably about 0.01 to 2% by weight.

Antifoam

Antifoams can advantageously be added to the lubricant composition. These agents retard the formation of stable bubbles. Silicones and organic polymers are typical antifoams. For example, polysiloxanes such as silicone oils or polydimethyl siloxanes provide antifoam properties. Defoamers are commercially available and can be used in conventional trace amounts with other additives such as demulsifiers, usually combined amounts of these additives being less than 1%, often less than 0.1%.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. Various of these are commercially available, and they are also cited in the above cited documents.

One type of antirust additive is a polar compound that preferentially wets the metal surface to protect the metal surface with an oil film. Another type of antirust additive absorbs water by incorporating water into the water-in-oil emulsion such that only oil contacts the metal surface. Another type of antirust additive chemically bonds to the metal to create a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight. Additional types of additives may be further incorporated into the lubricant compositions or working oils of the present invention, which may include one or more additives, such as, for example, demulsifiers, solubilizers, glidants, colorants, colorants, and the like, as desired. In addition, each type of additive may comprise an individual additive or a mixture of additives.

Note that many of the additives, additive concentrates, and additive packages sold from the manufacturer may incorporate certain amounts of base oil solvents or diluents into the formulation. In practical use, however, additive components, additive concentrates and additive packages are used as purchased from the manufacturer and may include a specific amount of base oil solvent or diluent. Unless specifically stated otherwise, the additives and combination ingredients recited in the following examples and comparative examples are used "as is" obtained from the manufacturer or supplier.

Example 1

By adjusting process parameters other than those of the invention well known to those skilled in the art, base stocks are incorporated into the working oils of the invention described herein over low to high viscosity oils typical of the art. Thus, the base stock with the final viscosity between the two endpoints can be blended. In this first example, base stocks were prepared at higher viscosity levels of 6.6 cSt and lower viscosity levels of 4.0 cSt using the method of the present invention. As can be seen in Table 3, Oil A of the present invention was blended into two viscosity targets: 4.0 cSt and 5.7 cSt. Similarly, Oil B of the present invention in this Example was prepared from Fischer-Tropsch wax and blended to a final viscosity target of 4.0 cSt and 6.3 cSt. The control base oil of Example 1 is a commercial base stock blended with viscosity targets of 4cSt, 5cSt and 8cSt.

The viscosity characteristics of the base oils A and B of the present invention and the control base oil 1 at corresponding viscosity indices are described below (Table 3). The kinematic viscosity was measured by ASTM method D445. The CCS viscosity measured was found by using ASTM method D5293. The theoretical viscosity was calculated according to the Walter / Mackol equation described in ASTM D341 (Appendix 1). For this example, the theoretical viscosity straight line of each subject oil was determined from the kinematic viscosity taken at 40 ° C. and 100 ° C., as shown in FIG. 2.

Table 3 shows that the ratio between the measured and theoretical viscosity below −30 ° C. and the theoretical viscosity (ie, ratio = measured / theoretical) is less than 1.2 for the base oil of the present invention but greater than 1.2 at the same temperature for the control base oil. Unexpectedly higher. Similarly it is observed that the base stock of the present invention has a much lower scanning Brookfield viscosity (ASTM D5133) value at low temperatures (<-20 ° C.). Scanning Brookfield viscosity measurements are performed at much lower shear rates and slower cooling rates than the D5293 CCS technique. In certain examples described in Table 4, the (measured / theoretically predicted) viscosity ratios of the base stocks of the present invention range from 2.5 (at -20 ° C) to 7 (at -35 ° C), while similar viscosity and VI Corresponding commercially available base stocks have a ratio of 11 (at -20 ° C) to 63 (at -25 ° C) and their viscosity is too high to be measured below -25 ° C.

Example 2

For Example 2, five blended hydraulic fluids were prepared. Blend 1, the comparative example, is a working oil prepared from commercial Group II base stocks having the same target viscosity levels as the examples of the present invention (see Table 4). Blends 2, 3, 6 and 7 are hydraulic fluids incorporating base stock A of the present invention (specifically 4 cSt viscosity targets) from Example 1. Blends 4 and 5 are hydraulic fluids incorporating the base stock B of the present invention (specifically a 4cSt viscosity target) from Example 1.

The properties of Control Blend 1 and Blends 2-7 of the present invention at the corresponding viscosity index are described in Table 4 below. Kinetic viscosity was measured by ASTM method D445. Brookfield viscosity was measured by ASTM method D2983. Pour point was measured by ASTM D5950. Blend 1 is the average result of blends 1A and 1B described in Table 5.

An unexpected finding of the present invention is that the Brookfield viscosity of the working oil of the present invention, measured at -40 ° C, is drastically lower than that found using a control hydrolyzed (HC) Group II base stock. This observed phenomenon occurred even though the pour point and cloud point of the base stock of the present invention were the same as those of the Group II base stock hydrolyzed (HC). Even more surprising is that the working oils of the invention, prepared using Group II base stocks of 50% or less, still exhibited excellent Brookfield viscosity at -40 ° C. The inventors found that this surprising result also appeared in blends containing up to 80% of Group II base stocks.

Example 3

In an effort to derive the results of the present invention using dewaxing by catalyst, a third experiment was conducted by using standard solvent dewaxing base oil extraction techniques. For the commercial Group II base stocks of Example 2, 18 modifications that were commonly used to improve the low temperature properties of the base stocks were performed. These modified materials were incorporated into the hydraulic oil and the Brookfield viscosity of each hydraulic oil was measured. The results are compared in Table 5 with the Brookfield viscosity of the inventive working oils (blends 2 to 5) from Example 2.

Table 5 shows that none of the modifications to the Group II base oil extraction techniques resulted in Brookfield viscosity that is close to the Brookfield viscosity of the hydraulic fluid of the present invention. These results are shown graphically in FIG. 3.

Example 4

In order to demonstrate that the benefits of the present invention span a wide range of viscosity targets, the inventive base oil A of Example 1 was mixed with various viscosity targets. Likewise, the control base oil of Example 1 was blended to the same target viscosity. The CCS viscosity of each blend was measured.

As shown in Table 6, the viscosity-temperature performance of the control base oil and the base oil of the present invention differs significantly over the base oil viscosity range measured as the kinematic viscosity at 100 ° C. At the corresponding kinematic viscosity at 100 ° C., it is evident that the base oil of the invention has a lower (lower) low temperature viscosity than the low temperature viscosity of Control Base Oil 1, for example at temperatures such as −30 ° C. and −35 ° C. Do.

Example 5

The advantageous properties of the base stock and base oil of the present invention advantageously lower the CCS viscosity of the hydraulic oil blended with the Group I base stock and the hydraulic oil blended with the Group II base stock. For Example 5, the inventive base oil A of Example 1, blended to a target of 5 cSt, was further blended into the Group I base stock. The commercial control base oil of Example 1 was also blended with the Group I base stock. To each blend, equal amounts of performance additive packages and standard viscosity modifiers customary in commercial hydraulic fluids were added. The results of the CCS viscosity test are shown in Table 7.

Table 7 shows that formulations incorporating Group I base stocks when blended with the base oils of the present invention over their corresponding formulations using Control Base Oil 1 are advantageous in terms of CCS viscosity at -20 ° C and -25 ° C. Ie lower CCS viscosity). Even more surprisingly, for the formulated lubricants based on the base oil of the present invention (Example 4) compared to Control Base Oil 1 (Comparative Example 4), the difference in CCS viscosity advantage becomes even greater with decreasing temperature (Table 7). .

Claims (28)

a) (i) a viscosity index (VI) of at least about 130; (ii) a pour point of about −10 ° C. or less; (iii) a base stock or base oil having a ratio of measured cold viscosity to theoretical cold viscosity of about 1.2 or less at about −30 ° C. or lower; And b) at least one additive, wherein The measured viscosity is a cold-crank simulator viscosity and the theoretical viscosity is calculated at the same temperature using the Walter-MacCoull equation, and the base stock or base oil is a Group IV base. Functional fluids, not stock or base oils. a) (i) an effective valence that converts less than 5% by weight of the feedstock to a 650 ° F (343 ° C) minus product such that the VI increase produces less than 4 greater hydrogenated feedstock than the feedstock VI Under bovine treatment conditions, using a hydrogenation catalyst, hydrotreating a feedstock having a wax content of at least about 60% by weight based on the feedstock; (ii) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (iii) Under effective hydrogen dewaxing conditions with a catalyst, ZSM-48, ZSM-57, ZSM-23, ZSM-22, ZSM-35, ferrierite, ECR-42, ITQ-13, MCM Prepared by a process comprising hydrogen dewaxing a liquid product using a dewaxing catalyst of at least one of -71, MCM-68, beta, fluoridated alumina, silica-alumina or fluorinated silica alumina. One or more base stocks or base oils; And b) at least one additive, wherein Hydraulic oil wherein the base stock or base oil has at least 130 VI and the dewaxing catalyst contains at least one Group 9 or Group 10 precious metal. a) (i) an effective valence that converts less than 5% by weight of the feedstock to a 650 ° F (343 ° C) minus product such that the VI increase produces less than 4 greater hydrogenated feedstock than the feedstock VI Under bovine treatment conditions, using a hydrogenation catalyst, hydrotreating the feedstock having a wax content of at least about 50% by weight based on the feedstock; (ii) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (iii) under effective hydrogen dewaxing conditions with a catalyst, ZSM-22, ZSM-23, ZSM-35, ferrierite, ZSM-48, ZSM-57, ECR-42, ITQ-13, MCM-68, Hydrogenated waxing of the liquid product using a dewaxing catalyst of at least one of MCM-71, beta, fluorinated alumina, silica-alumina or fluorinated silica-alumina; (iv) at least one base prepared by a process comprising subjecting the product from step (iii) to a hydrogenation using a mesoporous hydrogenation finishing catalyst from the M41S class under hydrogenation finishing conditions. Stock or base oils; And b) at least one additive, wherein The base oil has a VI of 130 or more and the dewaxing catalyst contains at least one Group 9 or Group 10 precious metal. a) (i) an effective valence that converts less than 5% by weight of the feedstock to a 650 ° F (343 ° C) minus product such that the VI increase produces less than 4 greater hydrogenated feedstock than the feedstock VI Under bovine treatment conditions, using a hydrogenation catalyst, hydrotreating a feedstock having a wax content of at least about 60% by weight based on the feedstock; (ii) stripping the hydrotreated feedstock to separate the gaseous product from the liquid product; (iii) under effective hydrogeno dewaxing conditions with a catalyst, a hydrogenation wax of the liquid product using a dewaxing catalyst, ZSM-48; (iv) optionally one or more base stocks prepared by a process comprising subjecting the product from step (iii) to a hydrofinishing using MCM-41 under hydrofinishing conditions; And b) at least one additive, wherein The base oil has a VI of 130 or more and the dewaxing catalyst contains at least one Group 9 or Group 10 precious metal. (I) (a) a kinematic viscosity of about 1.5 to about 8.5 mm ² / sec at 100 ° C., (b) a viscosity index of about 110 to about 160, (c) a pour point of less than about −9 ° C., and (d) about 92 to One or more base stocks having a saturate content of about 100% by mass; And (II) optionally from about 0 to about 80 volume percent of a hydrolyzed Group II or Group III base stock mixture; And (III) Hydraulic fluid optionally comprising one or more performance additives. The method of claim 5, Hydraulic oil having a kinematic viscosity of about 4.5 to about 9.5 mm ² / sec at 100 ° C., a viscosity index of about 150 to about 230, a pour point of about −42 ° C. or less, and a Brookfield viscosity of about 20,000 cP or less at −40 ° C. The method of claim 6, Hydraulic fluid having a kinematic viscosity of from about 5.5 to about 8.5 mm ² / sec at 100 ° C. The method of claim 6, Hydraulic fluid having Brookfield viscosity of about 15,000 cP or less at -40 ° C. The method of claim 6, Hydraulic fluid having Brookfield viscosity of about 10,000 cP or less at -40 ° C. The method of claim 6, Hydraulic fluid having a kinematic viscosity of from about 2.0 to about 6.0 mm ² / sec at 100 ° C. The method of claim 6, Hydraulic fluid having a kinematic viscosity of from about 3.0 to about 5.0 mm ² / sec at 100 ° C. The method of claim 6, Hydraulic oil in which the base stock incorporated in the hydraulic oil has a viscosity index of about 120 to about 150. The method of claim 6, Hydraulic oil in which the base stock incorporated in the hydraulic oil has a viscosity index of about 130 to about 150. The method of claim 6, Hydraulic fluid having a pour point of less than about -12 ° C. The method of claim 6, Hydraulic fluid having a pour point of less than about -15 ° C. The method of claim 6, Hydraulic oil having a saturate content of about 96% to about 100% by mass of the base stock incorporated in the hydraulic oil. The method of claim 6, Hydraulic fluid in which the hydrolyzed Group II or III base stock incorporated in the hydraulic oil is from about 0 to about 50 volume percent of the final blend. The method of claim 6, The hydrolyzed Group II or III base stock incorporated into the hydraulic fluid has a kinematic viscosity of from about 1.5 to about 8.5 mm ² / sec at 100 ° C., a viscosity index of at least about 90, a pour point of up to about −15 ° C., and about Hydraulic oil having a saturate content of 92 to about 100% by mass. The method of claim 6, Hydraulic oil having a saturate content of about 92% to about 100% by mass of said hydrolyzed Group II or III base stock incorporated into said hydraulic oil. The method of claim 6, Hydraulic oil wherein the base stock is present in an amount of about 20 to about 100 volume percent. The method of claim 6, Hydraulic oil wherein the base stock is present in an amount from about 40 to about 100 volume percent of the base oil blend. (I) (a) a kinematic viscosity of 3.0 to about 5.0 mm ² / sec at 100 ° C., (b) a viscosity index of about 130 to about 150, (c) a pour point of less than about −15 ° C., (d) about 96 to about One or more base stocks having a saturate content of 100% by mass; And (II) optionally, (a) a kinematic viscosity of from about 1.5 to about 6.5 mm ² / sec at 100 ° C., (b) a viscosity index of at least about 90, (c) a pour point of less than about −15 ° C., and (d) from about 92 to about From about 0 to about 50 volume percent of a hydrolyzed Group II or III base stock mixture comprising at least one hydrolyzed base stock having a saturate content of about 100 mass%; And (III) optionally a hydraulic oil comprising at least one performance additive, The mixture of base stocks having the base stock blend has (a) a kinematic viscosity of from about 3.5 to about 5.5 mm ² / sec at 100 ° C., (b) a viscosity index of from about 120 to about 150, and (c) less than about −15 ° C. Have a pour point, The working oil has a viscosity of (a) a kinematic viscosity of about 5.5 to about 8.5 mm ² / sec at 100 ° C., (b) a viscosity index of about 150 to about 230, (c) a pour point of about −42 ° C. or less, (d) −40 ° C. Hydraulic oil having a Brookfield viscosity of about 15,000 cP or less. The method according to any one of claims 1 to 22, Hydraulic fluid used as Automatic Transmission Fluid. A method for improving the Brookfield viscosity of hydraulic fluid by incorporating said base stock according to claim 1. A process for producing hydraulic oil by incorporating said base stock according to claim 1. A method for producing an automatic transmission fluid by incorporating said base stock according to claim 1. (I) (a) a kinematic viscosity of 3.0 to about 5.0 mm ² / sec at 100 ° C., (b) a viscosity index of about 130 to about 150, (c) a pour point of less than about −15 ° C., (d) about 96 to about One or more base stocks having a saturate content of 100% by mass; And (II) optionally, (a) a kinematic viscosity of from about 1.5 to about 6.5 mm ² / sec at 100 ° C., (b) a viscosity index of at least about 90, (c) a pour point of less than about −15 ° C., and (d) from about 92 to about From about 0 to about 50 volume percent of a hydrolyzed Group II or III base stock mixture comprising at least one hydrolyzed base stock having a saturate content of about 100 mass%; And (III) optionally, an automatic transmission fluid comprising at least one performance additive, The mixture of base stocks having the base stock blend has (a) a kinematic viscosity of from about 3.5 to about 5.5 mm ² / sec at 100 ° C., (b) a viscosity index of from about 120 to about 150, and (c) less than about −15 ° C. Have a pour point, The working oil has a viscosity of (a) a kinematic viscosity of about 5.5 to about 8.5 mm ² / sec at 100 ° C., (b) a viscosity index of about 150 to about 230, (c) a pour point of about −42 ° C. or less, (d) −40 ° C. Has a Brookfield viscosity of about 15,000 cP or less, The working oil has a viscosity of (a) a kinematic viscosity of about 5.5 to about 8.5 mm ² / sec at 100 ° C., (b) a viscosity index of about 150 to about 230, (c) a pour point of about −42 ° C. or less, (d) −40 ° C. Automatic transmission fluid having a Brookfield viscosity of about 10,000 cP or less. The method according to any one of claims 2 to 4, Hydraulic oil wherein the feedstock is a gas-to-liquid feedstock.