JP2016522285A - Lubricating composition and method for lubricating a transmission - Google Patents

Abstract

The present invention comprises (a) an oil of lubricating viscosity having a kinematic viscosity of 2.8 to 3.6 cSt (mm2 / s) at 100 ° C. and a viscosity index of 104 to 130, (b) further functionalized with a sulfur or phosphorus moiety. 1.2-5.0 wt% of at least one borated dispersant, (c) a calcium-containing detergent present in an amount that provides at least 110 ppm to 700 ppm of calcium, (d) 360-950 ppm of phosphorus It relates to a lubricating composition comprising at least two phosphorus-containing compounds present in a resulting amount and (e) a linear polymer viscosity modifier having a dispersant functionality of 0.1 wt% to 5 wt%. The present invention further provides a method of lubricating a transmission with the lubricating composition disclosed herein.

Description

FIELD OF THE INVENTION The present invention comprises (a) an oil of lubricating viscosity having a kinematic viscosity of 2.8-3.6 cSt and a viscosity index of 104-130 at 100 ° C., (b) further functionalized with a sulfur or phosphorus moiety. 1.2-5.0 wt% of at least one borated dispersant, (c) a calcium-containing detergent present in an amount that provides at least 110 ppm to 700 ppm of calcium, and (d) 360-950 ppm of phosphorus in lubricating composition At least two phosphorus-containing compounds, and (e) from 0.1 wt% to 5 wt% dispersant functionality, present in an amount that results in at least 150 ppm of phosphorus provided by C _4-6 hydrocarbyl phosphite The present invention relates to a lubricating composition containing a linear polymer viscosity modifier. The present invention further provides a method of lubricating a transmission with the lubricating composition disclosed in the present invention.

BACKGROUND OF THE INVENTION Power transmission line transmissions, particularly automatic transmission fluids (ATF), are the multiple and often lubrication and power transmission conflicting requirements of modern automatic transmissions (including various types of continuously variable transmissions). Presents technical problems and solutions that are very difficult to satisfy. Many additive components are usually included in ATF, lubrication, dispersibility, friction control (for clutches), anti-wear durability (eg gear wear) and pump durability, fuel economy, anti-sway performance Providing performance characteristics such as anti-corrosion and antioxidant performance. However, the additive component is consumed during use, which can adversely damage the transmission.

  US Pat. No. 5,578,236 (Srinivasan, published Nov. 26, 1996) contains about 0.001 to about 0.1% oil soluble boron content by weight, about 0.005 to about 0. Disclosed is a power transmission fluid composition having an oil-soluble phosphorus content of 2% and an oil-soluble metal content such as one or more metal-containing additives that are free of metal additives or less than about 100 ppm. Said composition comprising: a) at least about 50 wt% of one or more hydrotreated mineral oils ranging from about 55N to about 125N, based on the total weight of said composition, b) said composition About 5 to about 40 wt% hydrogenated poly-α-olefin oligomer fluid having a viscosity in the range of about 2 to about 6 cSt at 100 ° C., c) of the solution in an inert solvent 30 or less permanent in form From about 5 to about 20 wt% acrylic viscosity index improver, based on the active component, having a shear stability index, d) oil-soluble dialkyl esters, oil-soluble sulfones, and mixtures thereof An effective seal swell amount of at least one seal swell agent selected from: e) at least one oil soluble ashless dispersant in an amount of dispersant; f) at least one oil soluble friction modifier in an amount of friction adjustment. And g) an oil-soluble inhibitor selected from the group consisting of an anti-foaming agent, a copper corrosion inhibitor, a rust inhibitor, and an antioxidant, provided that the composition is (i) -40 ° C. Brookfield viscosity of 13,000 cP or less, (ii) at least 2.6 mPa.s in the method of ASTM D-4683 at 150 ° C. and (iii) has a viscosity of at least 6.8 cSt after 40 cycles at 100 ° C. in the FISST of ASTM D-5275.

  US Patent Application Publication No. 2011-0239971 (Nelson, published Oct. 6, 2011) contains (a) a major amount of a base oil of lubricating viscosity, and (b) one or more basic nitrogen atoms. A method is disclosed for improving the copper corrosion performance of a lubricating oil composition comprising one or more dispersants, wherein the method comprises adding a lubricant of the general formula Si-X4 (where each X is independently One or more of a copper corrosion performance improver or a hydrolysis product thereof, which is a hydroxyl-containing group, a hydrocarbyloxy-containing group, an acyloxy-containing group, an amino-containing group, a monoalkylamino-containing group or a dialkylamino-containing group) Including adding an effective amount.

  EP 1705235 (Ozbalik, published Mar. 22, 2006) includes (a) a major amount of base oil, (b) one or more friction modifiers (containing the total nitrogen supplied thereby). And an automatic transmission fluid composition comprising (c) one or more ashless dispersants (with a total nitrogen content supplied thereby greater than or equal to about 500 ppm) and Wherein the automatic transmission fluid has a kinematic viscosity of about 4 cSt to about 6.5 cSt at 100 ° C. and a Brookfield viscosity of about 4,000 cP to about 20,000 cP at −40 ° C.

  WO 2005/010134 (Sumiejski et al., February 3, 2005) includes (a) a hydrocarbyl phosphite, (b) a condensation product of at least one fatty acid and a polyamine, (c) a borate ester. , (D) a borated dispersant, and (e) a lubricating composition containing an oil of lubricating viscosity is disclosed. The invention further relates to the use of the composition in an automobile transmission.

  WO 2007/127615 (Tipton et al., November 8, 2007) discloses a lubricating composition containing a polymer such as a star polymer, a phosphorus-containing compound and a dispersant. The present invention further provides a method of lubricating a mechanical device using a lubricating composition.

  International Publication No. 00/70001 (Ward, November 23, 2000) discloses a method of lubricating a continuously variable transmission, wherein (a) an oil of lubricating viscosity, (b) a dispersant, a detergent. Or a composition comprising a mixture of (b) and (c) is fed to the transmission, wherein at least one dispersant (b) and detergent (c) are boride species and the amount of boron Is at least 250 ppm based on the composition and is present in an amount sufficient to impart improved friction and sudden vibration resistant properties to the composition when used in the transmission. It is also noted that the composition is useful for automatic transmissions.

  US Pat. No. 5,840,663 (Nibert et al., Published November 24, 1998) includes a major amount of lubricating oil and the reaction product of an isomerized alkenyl substituted succinic anhydride with a polyamine, Oil-soluble alkyl phosphites, including ashless dispersants with alkyl side chains of molecular weight greater than 1500, nitrogen-containing corrosion inhibitors, and optionally detergents containing metals that are salts of alkali metals or alkaline earth metals Disclosed are compositions and methods for improving the anti-sway durability of power transmission fluids, including combinations of additives in amounts effective to improve anti-sway. The anti-swing durability of these fluids can be improved by incorporating a detergent that optionally includes an overbased metal.

  US Pat. No. 7,737,092 (Ward et al., Published Aug. 11, 2005) includes (a) an oil of lubricating viscosity, (b) a dispersant, (c) a calcium detergent, (d) a magnesium detergent. And (e) a composition suitable as a lubricant for a transmission comprising an inorganic phosphorus compound, wherein at least one of (b), (c), and (d) is borated . The Ward formulation is suitable for use as a fluid for transmissions, particularly continuously variable transmissions. Ward also discloses that a continuously variable transmission (CVT) represents a significant development over conventional automatic transmissions.

  US Patent Application Publication No. 200220151441 (Srinivasan et al., Published Oct. 17, 2002) includes a major amount of base oil, and at least about 0.10% by weight of a metal-containing detergent, a dispersant, and at least two types of An automatic transmission fluid is disclosed that includes a small amount of additives including a mixture of different friction modifiers. The automatic transmission fluid has anti-sway durability and friction durability.

US Patent Application Publication No. 2009059922 (Cha et al., Published Dec. 10, 2009) describes automatic transmission lubricating oil compositions, particularly oils of lubricating viscosity, ashless dispersants, antioxidants, phosphorous antiwears. Automatic transmissions, particularly six-speed automatic transmissions, which comprise a slip clutch up converter and a clutch clutch using a paper-based clutch material and a planetary gear system. An automatic transmission lubricating oil composition useful for lubricating or operating a machine is disclosed.
US Patent Application Publication No. 201220277134 (Deshimaru, published November 1, 2012), wherein a lubricating oil composition is at least one lubricating oil selected from the group consisting of mineral lubricating base oils and synthetic lubricating base oils. Base oil, (a) neutral phosphorus compound, (b) at least one acidic phosphorus compound selected from the group consisting of a specific acidic phosphate amine salt and a specific acidic phosphite, and (c) a sulfur compound Is disclosed. The lubricating oil composition may be an automatic transmission fluid having a kinematic viscosity at 100 ° C. of 5 mm ² / sec.

US Pat. No. 5,578,236 US Patent Application Publication No. 201110239971 European Patent Application No. 1705235 International Publication No. 2005/010134 International Publication No. 2007/127615 International Publication No. 00/70001 US Pat. No. 5,840,663 US Pat. No. 7,737,092 US Patent Application Publication No. 20020151441 US Patent Application Publication No. 20090305922 US Patent Application Publication No. 201220277134

SUMMARY OF THE INVENTION An object of the present invention is to provide a lubricating composition capable of lubricating an automatic transmission. The lubricating composition provides at least one property including friction control (for clutches), improved fuel economy, anti-wear durability (eg, gear wear) and pump durability, and anti-sway performance can do. The lubricating composition may be capable of providing, for example, improved fuel economy and anti-wear durability.

  As used herein, the transitional phrase “comprising” which is synonymous with “including”, “containing”, or “characterized by” is It is inclusive or open and does not exclude additional, unlisted elements or method steps. However, in each description of “comprising” herein, the term, as an alternative embodiment, includes the phrases “consisting essentially of” and “consisting of”. Where “consisting of” excludes any unspecified element or step, and “consisting essentially of” is a fundamental and novel property of the composition or method being considered. The inclusion of additional elements or steps not listed that do not substantially affect

As used herein, the term "C _{4 to 6} hydrocarbyl phosphite" it is intended to include both mono C ₄ ~ ₆ hydrocarbyl phosphite and di C _{4 to 6} hydrocarbyl phosphite. Typically, C _4-6 hydrocarbyl phosphite comprises di-C _4-6 hydrocarbyl phosphite.

  As used herein, the expressions “(meth) acryl, (meth) arylate” and related terms are intended to include both acrylic and methacrylic functionality. Typically, “(meth) acryl”, “(meth) acrylate” and related terms are intended to include methacryl or methacrylate.

In one embodiment, the present invention provides:
(A) an oil of lubricating viscosity having a kinematic viscosity of 2.8 to 3.6 cSt (mm ² / s) at 100 ° C. and a viscosity index of 104 to 130;
(B) 1.2-5.0 wt% of at least one borated dispersant further functionalized with a sulfur or phosphorus moiety;
(C) a calcium-containing detergent present in an amount resulting in at least 110 ppm to 700 ppm calcium;
(D) at least two phosphorus-containing compounds that are present in an amount that provides 360-950 ppm phosphorus to the lubricating composition, wherein at least 150 ppm of the phosphorus is provided by C _4-6 hydrocarbyl phosphite; and (e) linear It can be a lubricating composition comprising a linear polymer viscosity modifier having a dispersant functionality of 0.1 wt% to 5 wt%, wherein the polymer has a weight average molecular weight of 5,000 to 25,000.

In a different embodiment, the present invention
(A) an oil of lubricating viscosity having a kinematic viscosity of 2.8 to 3.6 cSt (mm ² / s) at 100 ° C. and a viscosity index of 104 to 130;
(B) 1.2-5.0 wt% of at least one borated dispersant further functionalized with a sulfur or phosphorus moiety;
(C) a calcium-containing detergent present in an amount that results in at least 160 ppm to 400 ppm calcium;
(D) at least two phosphorus-containing compounds that are present in an amount that provides 525-800 ppm phosphorus to the lubricating composition, wherein at least 150 ppm of the phosphorus is provided by C _4-6 hydrocarbyl phosphite; and (e) linear It can be a lubricating composition comprising a linear polymer viscosity modifier having a dispersant functionality of 0.1 wt% to 5 wt%, wherein the polymer has a weight average molecular weight of 5,000 to 25,000.

  The lubricating composition of the present invention may further include a (meth) acrylic polymer having a star structure of 0.1 wt% to 5 wt%.

  The lubricating composition of the present invention is a linear polymer having a dispersant functionality of 0.1 wt% to 5 wt%, wherein the linear polymer has a weight average molecular weight of greater than 25,000 to 400,000 (or up to 350,000). A (meth) acrylic polymer viscosity modifier may further be included.

  The amount of boron in the lubricating composition disclosed herein may be from 150 to 400 ppm by weight.

  In one embodiment, the lubricating composition disclosed herein further comprises 0.3 wt% to 1.2 wt% amine antioxidant.

  In one embodiment, the lubricating composition disclosed herein further comprises 0.5 wt% to 3.5 wt% of a friction modifier component comprising at least two ashless friction modifiers.

  In one embodiment, the lubricating composition disclosed herein comprises from 0.5 wt% to 3 wt% comprising 0.3 wt% to 1.2 wt% amine antioxidant and at least two ashless friction modifiers. And further includes a 5 wt% friction modifier component.

The lubricating composition disclosed herein may have a kinematic viscosity of 3.6 to 4.8 cSt (mm ² / s) at 100 ° C. and Brookfield at −40 ° C. in one embodiment of the invention. The viscosity may be up to 6,800 cP (mPa · s).

  In one embodiment, the present invention provides a method of lubricating an automatic transmission that includes supplying the automatic transmission with the lubricating composition disclosed herein.

  In one embodiment, the present invention provides friction control (for clutches), improved fuel economy, anti-wear durability (eg, gear wear) and pump durability, and anti-sway performance for automatic transmissions. There is provided the use of the lubricating compositions disclosed herein that provide at least one of the following.

  The automatic transmission includes a continuously variable transmission (CVT), an infinite gear ratio transmission (IVT), an equatorial transmission, a continuous torque conversion slip clutch (CSTCC), a stepped automatic transmission or a double clutch transmission. Machine (DCT).

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method and lubricating composition for lubricating the automatic transmission disclosed above.

  As used herein, the viscosity index is determined by using ASTM method D2270-10e1.

  As used herein, the kinematic viscosity at 100 ° C. is measured by the method of ASTM D445-12.

Brookfield viscosity as used herein is measured by ASTM D2983-09 at -40 ° C (Brookfield viscosity at -40 ° C).
Lubricating composition

The lubricating composition of the present invention has a 3.6 to 4.8 cSt (mm ² / s), or 4.0 to 4.6 cSt (mm ² / s), or 4.0 to 4.4 cSt (mm) at 100 ° C. ² / s), or 4.0-4.2 cSt (mm ² / s).

  The lubricating composition may have a Brookfield viscosity of up to 6,800 cP (mPa · s) at −40C. The Brookfield viscosity at −40 ° C. may be 3,000 to 6,800 cP (mPa · s).

The lubricating composition may have a kinematic viscosity at 100 ° C. of less than 3.6 to 4.5 cSt (mm ² / s) and a Brookfield viscosity at −40 ° C. from 3000 to a maximum of 6,800 cP (mPa · s). s).

The lubricating composition may have a kinematic viscosity of 4.0 to 4.4 cSt (mm ² / s) at 100 ° C. and a Brookfield viscosity at −40 ° C. of 3,000 to 6,800 cP (mPa · s ).
Oil of lubricating viscosity

The oil of lubricating viscosity of the present invention is 2.8 to 3.6 cSt (mm ² / s), 2.9 to 3.5 cSt (mm ² / s), or 3.0 to 3.4 cSt (mm at 100 ° C. ² / s). The kinematic viscosity is measured at 100 ° C. according to ASTM D445-12. The oil of lubricating viscosity of the present invention can also be defined as API standard II + base oil. API standard II + base oils are known and are described, for example, in SAE publication entitled “Design Practice: Passenger Car Automatic Transmissions”, 4th edition, AE-29, 2012, pages 12-9. US 8,216,448 also defines API standard II + as “standard II + base oil” having a viscosity index of greater than 110 or less than 120.

The oil of lubricating viscosity of the present invention can have a viscosity index (VI) of 104-130, or at least 105, or at least 110, or at least 115-130. The viscosity index may range from 104 to 125, or from 110 to less than 120. In one particular embodiment, the oil of lubricating viscosity has a kinematic viscosity at 100 ° C. of 2.8 to 3.6 cSt (mm ² / s) and a viscosity index of 110 to less than 120.

  Examples of oils of lubricating viscosity of the present invention include base oils sold under the registered trademark S-oil, Nexbase, Yubase, Petrocanada, and Chevron neutral oil 110RLV.

  The oil of lubricating viscosity of the present invention can be present at 60 wt% to 97.5 wt%, or 70 wt% to 95 wt%, or 80 wt% to 95 wt% of the lubricating composition.

The oil of lubricating viscosity of the present invention having a kinematic viscosity of 2.8 to 3.6 cSt (mm ² / s) at 100 ° C. is a conventional lubricating viscosity oil (ie, a lubricating viscosity other than that defined by the present invention). Oil). Conventional oils of lubricating viscosity may be defined as specified in the American Petroleum Institute (API) Base Oil Compatibility Guidelines. The five base oil standards are as follows: Standard I (sulfur content> 0.03 wt%, and / or <90 wt% saturation, viscosity index 80-120); Standard II (sulfur content ≦ 0. 03 wt%, and ≧ 90 wt% saturation, viscosity index 80-120); Standard III (sulfur content ≦ 0.03 wt%, and ≧ 90 wt% saturation, viscosity index ≧ 120); Standard IV (all poly α-olefins) (PAO)); and Standard V (all others not included in Standards I, II, III, or IV). The oil of lubricating viscosity comprises API standard I, standard II (excluding oils of lubricating viscosity as defined by the present invention), standard III, standard IV, standard V oils or mixtures thereof.

  Often, the conventional oils of lubricating viscosity are API standard I, standard II (excluding oils of lubricating viscosity as defined by the present invention), standard III, standard IV oils or mixtures thereof. Alternatively, conventional lubricating viscosity oils are often API standard II (excluding oils of lubricating viscosity as defined by the present invention), standard III or standard IV oils or mixtures thereof.

  In one embodiment, conventional oils of lubricating viscosity can be adjusted by a Fischer-Tropsch gas-to-liquid synthesis procedure as well as liquid oils from other gases.

  In one embodiment, the conventional oil of lubricating viscosity may be an API standard IV oil. The amount of standard IV oil may be 0 wt% to 20 wt%, or 0.1 wt% to 20 wt%, or 1 wt% to 15 wt%, or 5 to 10 wt% of the lubricating composition.

  The amount of oil of lubricating viscosity present is typically the residue remaining after subtracting the total amount of performance additive of the present invention from 100 wt%.

The lubricating composition may be in the form of a concentrate and / or a fully formulated lubricant. If the performance additive of the present invention is in the form of a concentrate (which may be combined in whole or in part with the oil added to form the finished lubricant), the lubricating viscosity of the performance additive The ratio of to oil and / or diluent oil includes a range of 1:99 to 99: 1 by weight, or 80:20 to 10:90.
Detergent

  The lubricating composition includes a calcium-containing detergent. The calcium-containing detergent is present in an amount that provides 130 ppm to 600 ppm, or 160 ppm to 400 ppm calcium.

  The calcium-containing detergent may be an overbased detergent, a non-overbased detergent, or a mixture thereof. Usually, the detergent can be overbased.

  The preparation of calcium-containing detergents is known in the art. Patents describing the preparation of overbased calcium-containing detergents are US Pat. Nos. 2,501,731, 2,616,905, 2,616,911, 2,616,925, 2,777,874, 3,256,186, 3,384,585, 3,365,396, 3,320,162, 3,318,809, 3, 488,284, and 3,629,109.

  The TBN values used herein in the context of which TBN is cited and associated are based “as is”, ie, contain conventional amounts of diluent oil. Conventional amounts of diluent oil are typically in the range of 30 wt% to 60 wt% (often 40 wt% to 55 wt%) of the detergent component.

  A more detailed description of the expressions “metal ratio”, TBN and “soap content” is known to the person skilled in the art and is a standard textbook entitled “Chemistry and Technology of Lubricants”, 3rd edition, RM Mortier and ST Edited by Orszulik, Copyright 2010, pp. 219-220, Subheading 7.2.5. Described in Detergent Classification.

  The calcium-containing detergent may be a non-overbased detergent (also referred to as a neutral detergent). Non-overbased TBN may be 20 to less than 200 mg KOH / g, or 30 to 100, or 35 to 50 mg KOH / g. The TBN of the non-overbased calcium-containing detergent may be 20 to 175, or 30 to 100 mg KOH / g. If the non-overbased calcium-containing detergent is prepared from a strong acid such as a sulfonic acid substituted with hydrocarbyl, the TBN may be relatively low (eg, 0-50 mg KOH / g, or 10-20 mg KOH / G).

  The calcium-containing detergent may be an overbased detergent, which can have a TBN greater than 200 mg KOH / g (typically 250-600, or 300-500 mg KOH / g).

  The calcium-containing detergent can be formed by reaction of a basic calcium compound and an acidic detergent base. The acidic detergent base includes alkylphenol, alkylphenol coupled with aldehyde, sulfurized alkylphenol, alkylaromatic sulfonic acid (such as alkylnaphthalenesulfonic acid, alkyltoluenesulfonic acid or alkylbenzenesulfonic acid), aliphatic carboxylic acid, calixarene , Salixarenes, alkylsalicylic acids, or mixtures thereof.

  The basic metal compound of the present invention is used to provide basicity to the detergent. The basic calcium compound is a hydroxide or oxide compound of this metal.

  The oxides and / or hydroxides can be used alone or in combination. The oxide or hydroxide may be hydrated or dehydrated, but is typically hydrated. In one embodiment, the basic calcium compound may be calcium hydroxide, which may be used alone or in a mixture with other basic metal compounds. Calcium hydroxide is often referred to as lime. In one embodiment, the basic metal compound may be calcium oxide, which can be used alone or in a mixture with other basic metal compounds.

  In summary, when an alkylphenol, an alkylphenol coupled with an aldehyde, and a sulfurized alkylphenol are used to prepare a calcium-containing detergent, the detergent can be referred to as calcium phenate. The calcium phenate may be an alkyl phenate, an alkyl phenate coupled with an aldehyde, a sulfurized alkyl phenate, or a mixture thereof.

  The TBN of calcium phenate is less than 200 mg KOH / g, or from 30 to 175 (typically 150 to 175) mg KOH / g (for neutral phenate), 200 mg KOH / g or more to 500 mg KOH / g Or 210-400 (typically 230-270) mg KOH / g (for overbased phenates).

  The alkyl group of the phenate (ie, alkyl phenate) can contain 4 to 80, or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.

  In one embodiment, the calcium-containing detergent may be a sulfonate salt, or a mixture thereof. The sulfonates can be prepared from benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulfonic acid substituted with mono- or di-hydrocarbyl, where 6-40 hydrocarbyl groups. Or 8 to 35 or 9 to 30 carbon atoms.

  The hydrocarbyl group can be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms. Examples of suitable alkyl groups include branched and / or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, doeicosyl, Tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof are included.

In one embodiment, the hydrocarbyl-substituted sulfonic acid can include polypropene benzene sulfonic acid and / or C ₁₆ -C ₂₄ alkyl benzene sulfonic acid, or mixtures thereof.

  In one embodiment, the calcium sulfonate detergent is at least 8 as described in paragraphs [0026] to [0037] of US Patent Publication No. 2005065045 (authorized as US 7,407,919). It may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio. In some embodiments, the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often the 2-position, 3-position of the linear chain. Or in the 4th position and in some cases mainly in the 2nd position.

  When neutral or slightly basic, the calcium sulfonate detergent is less than 100 mg KOH / g, or less than 75 mg KOH / g, typically 20-50 mg KOH / g, or 0-20 mg KOH / g TBN. Can have.

  When overbased, the calcium sulfonate detergent can have a TBN of greater than 200 mg KOH / g, or 300-550, or 350-450 mg KOH / g.

  The detergent may be borated or non-borated.

  The chemical structure of sulfonate detergents and phenate detergents is known to those skilled in the art. Under the standard textbook title “Chemistry and Technology of Lubricants”, third edition, edited by RM Mortier and ST Orszulik, copyright 2010, pp. 220-223, subheading 7.2.6, the detergents and their A general disclosure of the structure is provided.

  In one embodiment, the calcium-containing detergent may be overbased calcium sulfonate, overbased calcium phenate, or a mixture thereof. Typically the detergent may be an overbased calcium sulfonate.

In one embodiment, the calcium-containing detergent may be a mixture with detergents containing zinc, barium, sodium, or magnesium. Detergents containing zinc, barium, sodium, or magnesium are also well known in the art and are described in the same references describing calcium-containing detergents. However, the TBN and metal ratio can be slightly different. The detergent containing zinc, barium, sodium, or magnesium may be phenate, sulfur-containing phenate, sulfonate, salixarate or salicylate. Typically, the detergent containing zinc, barium, sodium, or magnesium may be magnesium phenate, magnesium sulfur-containing phenate, or magnesium sulfonate.
Phosphorus-containing compounds

  The phosphorus-containing compound may be an acid, salt or ester, and may be a friction modifier, antiwear agent, extreme pressure agent, or a mixture thereof. In one embodiment, the phosphorus-containing compound is in the form of a mixture of 2 or 3 or 2 to 4 (typically 2 or 3) phosphorus-containing compounds.

  The phosphorus-containing compound may or may not contain a metal (before being mixed with other components).

  The phosphorus-containing compound can be present in an amount that provides 400 ppm to 900 ppm, or 500 ppm to 850 ppm, or 525 ppm to 800 ppm phosphorus.

  The phosphorus-containing compound can be derived from phosphoric acid, phosphorous acid, thiophosphoric acid, thiophosphorous acid, or mixtures thereof.

  The phosphorus-containing compound may be a nonionic phosphorus compound.

  In one embodiment, the phosphorus-containing compound comprises two or more (possibly up to four) nonionic phosphorus compounds. Typically, the nonionic phosphorus compound may be oxidized to +3 or +5. Different embodiments include phosphites, phosphates, or mixtures thereof.

In one embodiment, the phosphorus-containing compound comprises a non-ionic phosphorus compound ( _C4-6 hydrocarbyl phosphite) and an amine salt of phosphoric acid or ester.

（式中、各Ｒ’’’は、独立に水素または４〜６個の炭素原子、典型的には４個の炭素原子を有するヒドロカルビル基であってもよく、ただし、Ｒ’’’基のうちの少なくとも１つは、ヒドロカルビルである）。典型的には、該Ｃ_４〜６ヒドロカルビルホスファイトはジブチルホスファイトを含む。 The phosphorus-containing compounds include non-ionic phosphorus compounds that are C _4-6 hydrocarbyl phosphites, or mixtures thereof. C _4-6 hydrocarbyl phosphites of the present invention include those represented by the following formula:

Wherein each R ′ ″ may independently be hydrogen or a hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon atoms, provided that the R ′ ″ group At least one of which is hydrocarbyl). Typically, the _C4-6 hydrocarbyl phosphite comprises dibutyl phosphite.

The _{C 4 to 6} hydrocarbyl phosphite may provide at least 175ppm or at least 200ppm in total of phosphorus provided by the phosphorus-containing compound.

The _{C 4 to 6} hydrocarbyl phosphite may provide at least 45 wt% of the total amount of phosphorus from phosphorus-containing compounds, or 50 wt% 100 wt%, or 50 wt% 90 wt% or 60 wt% 80 wt%.

The phosphorus-containing compound can include a second phosphite, and the formula indicates that R ′ ″ can contain 2 to 40, 8 to 24, or 11 to 20 carbon atoms. Except as disclosed above except that the second phosphite is not a _C4-6 hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexadecenyl, or octadecenyl group.

  As used herein, the term “alk (en) yl” is intended to include moieties having alkyl and / or alkenyl groups.

In one embodiment, the phosphorus-containing compound comprises a mixture of C _4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and C _12-18 alk (en) yl hydrogen phosphite and optionally phosphoric acid. . In different embodiments, phosphate is present or absent.

In one embodiment, the phosphorus-containing compound comprises a mixture of C _4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and C _16-18 alk (en) yl hydrogen phosphite. The alkyl hydrogen phosphite may be an alkyl hydrogen phosphite and an alkenyl hydrogen phosphite, or a mixture of an alkenyl hydrogen phosphite and an alkyl hydrogen phosphite. In one embodiment, the alkenyl hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid. Phosphoric acid may or may not be present.

In one embodiment, the phosphorus-containing compound comprises a mixture of C _4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and C _11-14 alk (en) yl hydrogen phosphite. The alkyl hydrogen phosphite may be an alkyl hydrogen phosphite and an alkenyl hydrogen phosphite, or a mixture of an alkenyl hydrogen phosphite and an alkyl hydrogen phosphite. In one embodiment, the alkyl hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.

In one embodiment, the phosphorus-containing compound comprises a mixture of C _4-6 hydrocarbyl phosphite (typically dibutyl phosphite) and phosphoric acid.

  In one embodiment, the lubricating composition of the present invention comprises a package comprising a phosphorus-containing compound and a nonionic phosphorus compound that is a hydrocarbyl phosphite.

In one embodiment, the lubricating composition further comprises C _8-20 hydrocarbyl phosphite, or C _12-18 hydrocarbyl phosphite, or C _16-18 hydrocarbyl phosphite.

In different embodiments, the lubricating composition of the present invention may or may not contain phosphoric acid. In one embodiment, the lubricating composition further comprises phosphoric acid.
Dispersant

  The borated dispersant of the present invention may be a succinimide dispersant, a Mannich dispersant, a polyolefin succinic ester, an amide, or an ester amide, or a mixture thereof. In one embodiment, the non-boron dispersant may be a borated succinimide dispersant.

  The borated dispersant can be based on a borated polyisobutylene succinimide dispersant, in which case the polyisobutylene of the borated polyisobutylene succinimide has a number average molecular weight of 750-2200, or 750-1350, or 750-1150. .

  The borated dispersant can be used alone or as part of a mixture of borated dispersants. When a mixture of borated dispersants is used, 2-5, or 2-3, or 2 borated dispersants may be present.

  The second borated dispersant may be a borated polyisobutylene succinimide dispersant (provided that it is chemically different from the first borated dispersant), where the borated polyisobutylene succinimide is Of polyisobutylene has a number average molecular weight of 750-2200, or 750-1350, or 750-1150.

  The lubricating composition containing one or more borated dispersants can further include a non-borated dispersant. The non-borated dispersant may be polyisobutylene succinimide, and the polyisobutylene of the borated polyisobutylene succinimide has a number average molecular weight of 750-2200, or 750-1350, or 750-1150.

  Borated and non-borated polyisobutylene succinimides are known in the art and can be prepared using polyisobutylene having a number average molecular weight of 950.

  Borated and non-borated dispersants can be formed by reaction of substituted acylating agents with polyamines (typically having 2 or more reactive sites). For example, the substituted acylating agent may be polyisobutylene succinic anhydride and polyamine.

  The polyamine may be an alkylene polyamine. The alkylene polyamine can comprise ethylene polyamine, propylene polyamine, butylene polyamine, or mixtures thereof. Examples of propylene polyamines include propylene diamine, dipropylene triamine and mixtures thereof.

  In one embodiment, the polyamine is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine kettle residue and mixtures thereof.

  The borated and non-borated dispersants may or may be obtained from the reaction of succinic anhydride by a reaction referred to as a “direct alkylation process” by an “ene” reaction or a “thermal” reaction. . The mechanism of the “ene” reaction and general reaction conditions are summarized in “Maleic Anhydride”, pages 147-149, edited by B.C. Trivedi and B.C. Culbertson, Plenum Press, 1982. Non-borated dispersants prepared by processes involving the “ene” reaction are present at less than 50 mol%, or less than 0-30 mol%, or less than 0-20 mol%, or 0 mol% of the dispersant molecule. It may be a polyisobutylene succinimide having a carbocyclic ring. The “ene” reaction may have a reaction temperature of 180 ° C. to less than 300 ° C., or 200 ° C. to 250 ° C., or 200 ° C. to 220 ° C.

  The borated and non-borated dispersants may or may be obtained by processes leading to the formation of carbocyclic linkages promoted by chlorine, often including Diels-Alder chemistry. The process is known to those skilled in the art. The process promoted by chlorine is a polyisobutylene succinimide having a carbocyclic ring present at 50 mol% or more of the dispersant molecule, or at 60-100 mol% (typically 100 mol%). Non-boron dispersants can be produced. Both heat-promoted and chlorine-promoted processes are described in further detail in US Pat. No. 7,615,521, columns 4-5 and Preparation Examples A and B.

  The borated dispersant (s) of the present invention can be from 0.9: 1 to 1.6: 1, or 0.95: 1 to 1.5: 1, or 1: 1 to 1: 4 N: CO. Can be prepared to have a ratio.

  Non-boron dispersants are from 5: 1 to 1:10, 2: 1 to 1:10, or 1: 1 to 1:10, or 1: 1 to 1: 5, or 1: 1 to 1: 2. It can have a carbonyl to nitrogen ratio (CO: N ratio). In one embodiment, the non-borated dispersant can have a CO: N ratio of 1: 1 to 1:10, or 1: 1 to 1: 5, or 1: 1 to 1: 2.

  Borated and non-borated dispersants can also be post-treated by conventional methods by reaction with any of a variety of reagents. Among these are urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, and phosphorus compounds.

  Non-boron dispersants are typically 0.1 wt% to 10 wt%, or 0.5 wt% to 7 wt%, or 1 wt% to 4 wt%, or 1.5 wt% to 3 wt% of the lubricating oil composition. Exists.

  The dispersant comprises (a) a dispersant (such as polyisobutylene succinimide) and (b) 2,5-dimercapto-1,3,4 which is substituted with 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl. -Thiadiazole (substantially insoluble in hydrocarbon oil of lubricating viscosity at 25 ° C), and further (c) either a boring agent or (d) an inorganic phosphorus compound, or both (c) and (d) It may be a reaction product prepared by heating together, the heating comprising the reaction product of (a), (b), and (c) or (d) (the hydrocarbon oil at 25 ° C. Heat sufficient to provide solubility).

  The reaction product typically contains 0.5 to 2.5 weight percent sulfur from component (b), or 1 to 2 weight percent, or 1.25 to 1.5 weight percent sulfur. Can be contained. The product is also 0.2 to 0.6 weight percent boron from component (c), or 0.3 to 1.1 percent phosphorus from component (d), or components (c) and ( Such amounts from both of d) can be included.

Boron dispersants are various forms of boric acid (including metaboric acid, HBO ₂ , orthoboric acid, H ₃ BO ₃ , and tetraboric acid, H ₂ B ₄ O ₇ ), boron oxide, boron trioxide, and alkyl. It can be prepared by boring using various reagents selected from the group consisting of borates. These reagents are described in more detail above. In one embodiment, the borated agent is boric acid, which can be used alone or in combination with other borated agents.

  Boron dispersants blend boron compounds and N-substituted long chain alkenyl succinimides and bring them to a suitable temperature, typically 80 ° C to 250 ° C, 90 ° C to 230 ° C, or 100 ° C. It can be prepared by heating at ~ 210 ° C until the desired reaction occurs. An inert liquid can be used in carrying out the reaction. The liquid can include, but is not limited to, toluene, xylene, chlorobenzene, dimethylformamide, and mixtures thereof.

The borated dispersant is:
(I) a dispersant base;
(Ii) 2,5-dimercapto-1,3,4-thiadiazole or 2,5-dimercapto-1,3,4-thiadiazole substituted with hydrocarbyl or an oligomer thereof;
(Iii) a borinizing agent; and (iv) an optionally dicarboxylic acid of an aromatic compound selected from the group consisting of 1,3-dioic acid and 1,4-diacid; or (v) optionally phosphorous A product prepared by heating together an acid compound of
The heating is sufficient to provide (i), (ii), (iii) and optionally a product of (iv) or (v), which is soluble in an oil of lubricating viscosity. It is.

  A mixture of dispersant base, aromatic dicarboxylic acid and mercaptothiadiazole is treated with a boring agent and optionally also a phosphorus acid or acid anhydride. The components may be combined and reacted in any order. In particular, the boriding agent may be a pre-treatment process or a post-treatment process. Thus, for example, boric acid (and optionally phosphoric acid) is reacted in one step with a dispersant base, after which the intermediate borated dispersant is combined with mercaptothiadiazole and an aromatic dicarboxylic acid. You may make it react. Alternatively, the dispersant base, the aromatic dicarboxylic acid and the mercaptothiadiazole are first reacted and then the product is treated with a boring agent (and optionally with phosphoric acid, phosphoric acid). May be. In yet another variation, a phosphorylated succinimide dispersant is reacted with a phosphorus acid and a succinic anhydride substituted with a hydrocarbyl to prepare a mixed anhydride-acid precursor, which is then combined with the polyamine. To form a phosphorus-containing dispersant. The phosphorus-containing dispersant can then be reacted with the aromatic dicarboxylic acids and mercaptothiadiazoles, and with borinizing agents.

The ingredients typically comprise a borating agent and optionally the phosphorus acid compound (together or sequentially) with the remaining ingredients, ie, a dispersant base, an aromatic dicarboxylic acid and dimercaptothiadiazole. While reacting by heating, other reaction sequences are possible as described above. Heating is performed at a time and temperature sufficient to ensure solubility of the resulting product, typically at 80-200 ° C, or 90-180 ° C, or 120-170 ° C, or 150-170 ° C. Is called. The reaction time is typically at least 0.5 hours, such as 1 to 24 hours, 2 to 12 hours, 4 to 10 hours, or 6 to 8 hours. The length of time required for the reaction will be determined in part by the temperature of the reaction, as will be apparent to those skilled in the art. The progress of the reaction is generally manifested by the evolution of H ₂ S or water from the reaction mixture. Typically, H ₂ S is derived from one or more sulfur atoms in dimercaptothiadiazole.

  The reaction product typically contains 0.5 to 2.5 weight percent sulfur from component (iii), or 1 to 2 weight percent, or 1.25 to 1.5 weight percent sulfur. May be contained. It can likewise be 0.2 to 0.6 weight percent boron from component (iv), or 0.3 to 1.1 percent phosphorus from component (e), or components (iv) and (v) May contain such amounts from both.

  The reaction can be carried out in a hydrophobic medium such as an oil of lubricating viscosity that can be retained in the final product if desired. The oil, however, should typically be an oil that itself does not react or decompose under the reaction conditions. Thus, oils containing reactive ester functionality are not normally used as diluents. Oils of lubricating viscosity are described in more detail above.

  In the absence of dicarboxylic acid, the relative amounts of the components reacted are expressed as parts by weight prior to the reaction and are typically (i) 100 parts dispersant, (ii) dimercaptothiadiazole or substituted dimercaptothiadiazole 0 .75-6 parts, and (iii) 0 or 0.01-7.5 parts of a boring agent, and (v) 0.01-7.5 parts of a phosphoric acid compound, provided that (iii) The relative amount of + (v) is at least 0.075 parts. In one embodiment, the relative amounts are 100 parts of (i), 1.5-3 parts of (ii), 0-4.5 parts of (iii), and 0-4.5 parts of (v). Provided that (iii) + (v) is at least 1.5 parts. In another embodiment, the relative amounts are (i) 100 parts, (ii) 1.5-2.2 parts, (iii) 3.7-4.4 parts, (v) 1.5-4.4. Part. The amounts and ranges of the various components, particularly (iii) and (v), for example, so that there is 3.7-4.4 parts of (iii), with or without (v), and Similarly, whether (iii) is present or not, (v) can be independently combined so that there are 1.5 to 4.4 parts.

When a dicarboxylic acid is present, the relative amounts of the components to be reacted, expressed as parts by weight before the reaction, are typically (i) 100 parts of dispersant, (ii) 5 to 5000 ppm of dicarboxylic acid of the aromatic compound. , (Iii) 0.75-6 parts of dimercaptothiadiazole or substituted dimercaptothiadiazole, and (iv) 0-7.5 parts of borinizing agent and (v) phosphorus acid compounds 0-7. 5 parts, provided that the relative amount of (ii) + (iii) + (iv) + (v) is at least 1.5 parts. In one embodiment, the relative amount is 100 parts of (i), 1.5-6 parts of (ii), 5-1000 ppm of (iii), 0 or 0.01-4.5 parts of (iv); And (v) from 0 to 4.5 parts, provided that (iii) + (iv) + (v) is at least 1.5 parts. In another embodiment, the relative amount is (i) 100 parts: (ii) 1.5-5.0 parts: (iii) 25-500 ppm: (iv) 3.7-4.4 parts: (v) 0 to 4.4 parts. The amounts and ranges of the various components, in particular (iv) and (v), are similar, for example there are 3.7 to 4.4 parts of (iv) with or without (v) present (Iv) may or may not be present in (v) in the range of 1.5 to 4.4.
Dispersant base

  The product prepared by heating contains a dispersant base. The dispersants of the present invention are well known and include succinimide dispersants (eg N-substituted long chain alkenyl succinimides), Mannich dispersants, ester-containing dispersants, aliphatic hydrocarbyl monocarboxylic acylating agents and amines or ammonia. Condensation products, alkylaminophenol dispersants, hydrocarbyl-amine dispersants, polyether dispersants, polyetheramine dispersants, viscosity modifiers containing dispersant functionality (eg viscosity of polymers containing dispersant functionality) Index modifier (VM)), or mixtures thereof. Typically, the dispersant base is succinimide, or a mixture thereof. The dispersant base may be polyisobutylene succinimide.

  In one embodiment, the borated dispersant is prepared by reaction in the presence of the aromatic compound 1,3-dicarboxylic acid or 1,4-dicarboxylic acid, or reactive equivalents thereof, or mixtures thereof; It reacts or complexes with the dispersant. The term “reactive equivalents thereof” includes acid halides, esters, amides or mixtures thereof. The “aromatic component” is typically a benzene (phenylene) ring or a substituted benzene ring, although other aromatic materials such as fused ring compounds or heterocyclic compounds are also contemplated. Dicarboxylic aromatic compounds (which are not intended to be bound by any theory) may form salts, but rather form a covalently linked structure such as an amide that may not play a very important role. Or it is thought that it can couple | bond with a dispersing agent by complexation. Typically, the presence of a dicarboxylic aromatic compound in the present invention is believed to impart corrosion inhibiting properties to the composition. Examples of suitable dicarboxylic acids include 1,3-dicarboxylic acids such as isophthalic acid and alkyl congeners such as 2-methylisophthalic acid, 4-methylisophthalic acid or 5-methylisophthalic acid; and 1, such as terephthalic acid Alkyl congeners such as 4-dicarboxylic acid and 2-methylterephthalic acid are included. Other ring substituents such as hydroxy or alkoxy (eg, methoxy) groups can also be present in certain embodiments. In one embodiment, the aromatic compound is terephthalic acid.

  In one embodiment, the borated dispersant is prepared by reaction in the presence of dimercaptothiadiazole that reacts as part of the “product prepared by heating”. This is in addition to any dimercaptothiadiazole that may be present as another corrosion inhibitor in the lubricating composition. Examples include 2,5-dimercapto-1,3-4-thiadiazole or 2,5-dimercapto-1,3-4-thiadiazole substituted with hydrocarbyl, or oligomers thereof. Hydrocarbyl-substituted 2,5-dimercapto-1,3-4-thiadiazole oligomers typically form sulfur-sulfur bonds between 2,5-dimercapto-1,3-4-thiadiazole units. Formed by forming oligomers of the two or more thiadiazole units.

In one embodiment, the borated dispersant is prepared by reaction in the presence of a phosphorus acid compound. The phosphorus acid compound may contain an oxygen atom and / or a sulfur atom as a constituent element, and is typically phosphoric acid or an acid anhydride. As this component, the following examples: phosphorous acid, phosphoric acid, hypophosphorous acid, polyphosphoric acid, phosphorus trioxide, phosphorus tetroxide, phosphorus pentoxide (P ₂ O ₅ ), phosphorotetrathioic acid (H ₃ PS) ₄ ), phosphoromonothioic acid (H ₃ PO ₃ S), phosphorodithioic acid (H ₃ PO ₂ S ₂ ), phosphorotrithionic acid (H ₃ PO ₂ S ₃ ), and P ₂ S ₅ . Among these, phosphorous acid and phosphoric acid or their acid anhydrides are usually used. Salts such as amine salts of phosphorus acid compounds can also be used. It is also possible to use a plurality of these phosphorus acid compounds together. The phosphorus acid compound is often phosphoric acid or phosphorous acid or their anhydrides.

  The phosphorus acid compound may also include a phosphorus compound in which phosphorus is oxidized to +3 or +5, such as phosphate, phosphonate, phosphinate, or phosphine oxide. A more detailed description of these suitable phosphorus acid compounds is given in US Pat. No. 6,103,673, column 9, line 64 to column 11, line 8.

  In one embodiment, the phosphorus acid compound is an inorganic phosphorus compound.

  The borated dispersant is typically present at 0.1 wt% to 10 wt%, or 0.5 wt% to 7 wt%, or 1 wt% to 4 wt% of the lubricating oil composition.

In one embodiment, the dispersant package comprises:
(I) a non-borated dispersant comprising polyisobutylene succinimide, wherein the polyisobutylene used to prepare the non-borated dispersant is a number average of 550 to 1150, or 750 to 1150, or 900 to 1000 A dispersant having a molecular weight (commercially often has a number average molecular weight of about 950); and (ii) a borated dispersant comprising polyisobutylene succinimide for preparing the non-borated dispersant The polyisobutylene used can include a dispersant having a number average molecular weight of 550-1150, or 750-1150, or 900-1000 (commercially often has a number average molecular weight of about 950).

In one embodiment, the dispersant package is
(A) a non-borated dispersant comprising polyisobutylene succinimide, the polyisobutylene used to prepare the non-borated dispersant is a number average of 550-1150, or 750-1150, or 900-1000 A dispersant having a molecular weight (commercially often has a number average molecular weight of about 950), and (b)
(I) a dispersant base,
(Ii) 2,5-dimercapto-1,3,4-thiadiazole substituted with 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl, or oligomers thereof,
(Iii) a borinizing agent; and (iv) an aromatic dicarboxylic acid, optionally selected from the group consisting of 1,3-dioic acid and 1,4-diacid, or (v) optionally A borated dispersant, which may be a product prepared by heating together a compound of a phosphorus acid,
The heating is sufficient to provide a product that is soluble in an oil of lubricating viscosity (i), (ii), (iii) and optionally (iv) or (v). Can be included.
Viscosity modifier

  The lower range used herein for viscosity modifiers is measured by GPC using a polystyrene standard having a weight average molecular weight in the range of 350-2,000,000.

The lubricating composition contains a linear polymer having a dispersant functionality of 0.1 wt% to 5 wt% (or 0.5 wt% to 4 wt%). This type of compound is known in the art and, unlike dispersants, is believed to have a lower molecular weight than the linear polymer of the present invention.
Linear polymer

  The lubricating composition of the present invention comprises, in one embodiment, a linear polymer having a weight average molecular weight of 5,000 to 25,000, or 8000 to 20,000.

  In one embodiment, the linear polymer comprises poly (meth) acrylate, or a mixture thereof. The linear polymer is present in the compositions described herein in an amount of 0.1 wt% to 5 wt%, or 0.1 wt% to 4 wt%, or 0.2 wt% to 3 wt%, or 0, of the lubricating composition. 0.5 wt% to 3 wt%, 0.5 wt% to 4 wt%.

  The linear polymer has (a) 50 wt% to 95 wt%, or 60 wt% to 80 wt% alkyl (meth) acrylate having 10 to 15 carbon atoms, and (b) 1 to 9 alkyl groups. 1 wt% to 40 wt%, or 4 wt% to 35 wt% of alkyl (meth) acrylate, (c) 1 wt% to 10 wt%, or 1 wt% to 8 wt% of a dispersant monomer having a carbon atom of (d) 0 wt% to 4 wt%, or 0 wt% to 2 wt%, or 0 wt% vinyl aromatic monomer (typically styrene), and (e) 0 wt% to 9 wt%, or 0 wt%, where the alkyl group has 16 to 18 carbon atoms A composition comprising a poly (meth) acrylate polymer derived from a monomer composition comprising from 6% to 6% by weight alkyl (meth) acrylate It can be. In one embodiment, the linear polymer may contain 0 wt% to 20 wt% of 16-18 units of alkyl (meth) acrylate.

The star polymer is a C _12-15 alkyl (meth) acrylate (about 80 wt%) and a mixture of monomers composed of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth) acrylate (About 20 wt%) can be derived from the monomer composition. Bifunctional. The linear polymer comprises 2-ethylhexyl (meth) acrylate (30 wt%), C _12-15 alkyl (meth) acrylate (68.2 wt%), and dimethylaminopropyl (meth) acrylate (1.8 wt%). It can be derived from the monomer composition.

In one embodiment, the linear polymer comprises (a) 8-24, or 10-18, or 12-15 carbon atoms in the alcohol-derived portion of the ester group, and (b) an alcohol of the ester group. An alkyl (meth) acrylate ester monomer containing 6-11 or 8-11, or 8 carbon atoms in the portion of origin and having a 2- ( _C1-4alkyl ) substituent, and optionally A (meth) acrylic acid ester, vinyl aromatic compound (or vinyl), which is different from (meth) acrylic acid esters (a) and (b), containing 1 to 7 carbon atoms in the alcohol-derived portion of the ester group An aromatic monomer) and a poly (meth) a having units derived from a mixture of at least one monomer selected from the group consisting of nitrogen-containing vinyl monomers Acrylate (typically polymethacrylate), provided that no more than 60 wt%, or no more than 50 wt%, or no more than 35 wt% of the ester contains no more than 10 carbons in the alcohol-derived portion of the ester group. Contains atoms. This type of linear polymer is described in more detail in US Pat. No. 6,124,249 or paragraphs [0019] and [0031] to [0067] of EP09377769A1. (When “alcohol-derived moiety” is written as R′C (═O) —OR, the “—OR” portion of the ester is not necessarily prepared by reaction with the alcohol. Point). Optionally, the linear polymer may further comprise a third monomer. The third monomer may be styrene or a mixture thereof. The third monomer is in an amount of 0% to 25% of the polymer composition, or 1% to 15% of the composition, 2% to 10% of the composition, or even 1% to 3% of the composition. Can exist.

  Typically, the molar ratio of ester (a) to ester (b) in the copolymer is in the range of 95: 5-35: 65, or 90: 10-60: 40, or 80: 20-50: 50. is there.

The ester is usually an aliphatic ester, typically an alkyl ester. In one embodiment, the ester of (a) may be a C _12-15 alkyl (meth) acrylate and the ester of (b) may be 2-ethylhexyl (meth) acrylate.

  In one embodiment, the ester group in ester (a) contains a branched alkyl group. The ester group can have an ester group with 2 to 65%, or 5 to 60% branched alkyl groups. The branched alkyl group may be β-branched and may have 8 to 60, or 8 to 30, or 8 to 16 carbon atoms. For example, the branched alkyl group may be 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof, or Isofol® available from Sasol. It can be derived from commercially available alcohols such as branched Guerbet alcohol.

The C _1-4 alkyl substituent may be methyl, ethyl, and any isomer of propyl and butyl.

  The weight average molecular weight of the linear poly (meth) acrylate is 45,000 or less, or 35,000 or less, or 25,000 or less, or 8000 to 25,000, or 10,000 to It may be 35,000, or 12,000-20,000.

Linear polymer viscosity modifier with dispersant functionality is used as the only dispersant viscosity modifier present in linear (meth) acrylic polymer viscosity modifier with dispersant functionality of 0.5 wt% to 4 wt% The linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000, and an oil of lubricating viscosity is 2.8 to 3.1 cSt (at 100 ° C.). mm < ² > / s) and a viscosity index of 104-130.

  The lubricating composition is, in one embodiment, only two linear with dispersant functionality, where the linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000. Polymer viscosity modifiers can be included.

  In one embodiment, the lubricating composition of the present invention comprises a viscosity modifier comprising a star polymer and a linear polymer as described herein.

  In one embodiment, the lubricating composition has a weight average molecular weight of 0.1 wt% to 4 wt%, where the linear polymer has a weight average molecular weight of greater than 25,000 to 400,000 (or up to 350,000) or 30,000 to 150,000. % (Or 0.2 wt% to 3 wt%) of a linear (meth) acrylic polymer viscosity modifier with dispersant functionality. A linear (meth) acrylic polymer having a weight average molecular weight of more than 25,000 to 400,000 (or up to 350,000) is a linear (meth) acrylic polymer having a weight average molecular weight of 5,000 to 25,000; It may be considered chemically similar except that the weight average molecular weights are different.

  The lubricating composition is linear with a dispersant functionality of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%), where the linear polymer has a weight average molecular weight of 10,000 to 20,000. The (meth) acrylic polymer viscosity modifier, and the linear polymer has a weight average molecular weight of greater than 20,000 to 250,000 (or 30,000 to 150,000), 0.1 wt% to 4 wt% (or 0.00. A linear polymer viscosity modifier with dispersant functionality can be included, including a linear (meth) acrylic polymer viscosity modifier with a dispersant functionality of 2 wt% to 3 wt%).

  The lubricating composition comprises 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%) of the linear polymer having a weight average molecular weight of 5,000 to 25,000 or 10,000 to 20,000. A linear polymer viscosity modifier with dispersant functionality can be included, including a linear (meth) acrylic polymer with dispersant functionality, and the composition can be from 0.1 wt% to 4 wt% (or 0.005%). It further includes a (meth) acrylic polymer having a star structure of 2 wt% to 3 wt%.

  A detailed description of the star polymers disclosed herein is also set forth in WO 2007/127660 (published Nov. 8, 2007, assigned to Lubrizol Corporation by Baker et al.), Paragraphs [0021]-[0061]. It may be. Baker discloses various star polymer compositions and methods of preparation.

  In different embodiments, the star polymer comprises more than 50 wt%, or 55 wt% or more, or 70 wt% or more, or 90 wt% or more, or 95 wt% or more, or 100 wt% non-diene monomer ( That is, it may contain non-diene monomer unit (s) derived from the polymerization of one or more non-diene monomers. Examples of diene monomers include 1,3-butadiene or isoprene. In contrast, examples of non-dienes of the present invention can include styrene, (meth) acrylates, acrylates, or mixtures thereof. In one embodiment, the star polymer may be a polymer derived from (meth) acrylates, or mixtures thereof, and does not include styrene.

  As described below, the molecular weight of the viscosity modifier was determined using known methods such as GPC analysis using polystyrene standards. Methods for determining the molecular weight of polymers are well known. The method is described, for example, in (i) PJ Flory, “Principles of star polymer Chemistry”, Cornell University Press 91953), chapter VII, pages 266-315, or (ii) “Macromolecules, an Introduction to star polymer Science”, FA Bovey and FH Winslow, Academic Press (1979), pages 296-312. As used herein, the weight average and number average molecular weights of the polymers of the present invention are usually the major high molecular weights, excluding peaks associated with diluents, impurities, uncoupled star polymer chains and other additives. It is obtained by integrating the area under the peak corresponding to the star polymer of the present invention, which is the peak.

  The (meth) acrylic polymer having a star structure has (a) 50 wt% to 100 wt% alkyl (meth) acrylate having 12 to 15 carbon atoms, and (b) 1 to 9 alkyl groups. 0 wt% to 40 wt% alkyl (meth) acrylates having the following carbon atoms: (c) 0 wt% to 10 wt% dispersant monomer, (d) 0 wt% to 5 wt%, or 0 wt% to 2 wt%, or 0 wt% Vinyl aromatic monomers (typically styrene), and (e) 0 wt% to 20 wt%, or 0 wt% to 10 wt%, or 0 wt% alkyl (meth) acrylates in which the alkyl group has 16 to 18 carbon atoms Having three or more arms comprising a poly (meth) acrylate polymer derived from a monomer composition comprising

  The (meth) acrylic polymer having a star structure has (a) 60 wt% to 95 wt% alkyl (meth) acrylate having 12 to 15 carbon atoms, and (b) 1 to 9 alkyl groups. 5 wt% to 30 wt% alkyl (meth) acrylate having 5 carbon atoms, (c) 0 wt% to 10 wt% dispersant monomer, (d) 0 wt% to 5 wt%, or 0 wt% to 2 wt%, or 0 wt% Vinyl aromatic monomers (typically styrene), and (e) 0 wt% to 20 wt%, or 0 wt% to 10 wt%, or 0 wt% alkyl (meth) acrylates in which the alkyl group has 16 to 18 carbon atoms Can have three or more arms comprising a poly (meth) acrylate polymer derived from a monomer composition comprising .

  The star polymer has a weight average molecular weight of 100,000 to 1,300,000, or 125,000 to 1,000,000, or 150,000 to 950,000, or 200,000 to 800,000. Can do. As used herein, the shear stability index (SSI) of a star polymer can be determined by the 20 hour KRL test (Volkswagen Tapered Bearing Roller Test). The test procedure is detailed in both CEC-L-45-99 or equivalent test method DIN 51350-6-KRL / C.

  The star polymer SSI can be in the range of 0-100, or 0-80, or 0-60, or 0-50, 0-20, or 0-15, or 0-10, or 0-5. Examples of suitable ranges of SSI include 1-5, 10-25, or 25-65.

  A star polymer may be a homopolymer or a copolymer, ie its arms may be homopolymeric or copolymeric (ie contain 2 or more monomer types). In one embodiment, the star polymer may be a copolymer. The star polymer may be a star polymer having a random, tapered, diblock, triblock or multiblock structure. Typically, star polymers have a random or tapered structure.

  The star polymer can have an arm that may have a block arm structure, a hetero arm structure, or a tapered arm structure. The tapered arm structure has a variable composition over the length of the star polymer arm. For example, the tapered arm may be composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of the arm is rich in a gradient composition of two monomers.

  Hsieh et al. (Henry Hsieh and Roderic Quirk, “Anionic Polymerization, Principles and Practical Applications” (Marcel Dekker, Inc, New York, 1996), Chapter 13 (333-368)) (hereinafter referred to as Hsieh et al.). As noted, hetero-arm, or “Mikto-arm” star polymers contain arms that may differ from each other in either molecular weight, composition, or both. For example, a portion of a given star polymer arm can be one polymer type and a portion can be a second polymer type. More complex hetero-arm star polymers can be formed by joining three or more polymer arm portions with a coupling agent. In one embodiment, hetero-armed stars can be prepared by combining several batches of polymers with living properties prior to ligation and core formation.

  The above monomers used in the disclosed technique for the formation of the “arm” portion of the polymer are based on methacrylic acid rather than acrylic acid. In certain embodiments, the methacrylic polymer has better low temperature properties than the acrylic polymer. Generally, the amount of acrylic monomer present in the reaction mixture to form the polymer arm or in the resulting polymer arm itself is 0 to 5 mole percent, or 0.001 to 2 mole percent, or 0.01 to 1 mole percent. Or 0.05 to 0.5 mole percent, or less than 0.1 mole percent.

  A star polymer having a branched, comb-like, radial or star structure is composed of 2 or more arms, or 5 or more arms, or 7 or more arms, or 10 or more arms, For example, it can have 12-100, or 14-50, or 16-40 arms. A star polymer having a branched, comb-like, radial or star structure can have 120 arms or less, or 80 arms or less, or 60 arms or less.

  The star polymer may or may be obtained by controlled radical polymerization techniques. Examples of controlled radical polymerization techniques include RAFT, ATRP or nitroxide mediated processes. The star polymer may or may be obtained by an anionic polymerization process. In one embodiment, the star polymer may or may be obtained by RAFT, ATRP or an anionic polymerization process. In one embodiment, the star polymer may or may be obtained by a RAFT or ATRP polymerization process. In one embodiment, the star polymer may or may be obtained by a RAFT polymerization process.

  When preparing star polymers, the RAFT or ATRP polymerization process is preferred over other polymerization techniques because polar vinyl monomers including (meth) acrylates and (meth) acrylamides undergo side reactions during anionic polymerization. This is because it tends to occur and can make anionic polymerization less desirable.

  Methods for preparing polymers using ATRP, RAFT or nitroxide mediated techniques are disclosed in the Examples section of International Publication WO 2006/047398, so please refer to Examples 1-47.

  A more detailed description of the polymerization mechanism and related chemistry can be found in the Handbook of Radical Polymerization, edited by Krzysztof Matyjaszewski and Thomas P. Davis, 2002, published by John Wiley and Sons Inc (hereinafter referred to as “Matyjaszewski et al.”). Chapter 10, pages 463-522), ATRP (Chapter 11, pages 523-628) and RAFT (Chapter 12, pages 629-690).

  A discussion of the star polymer mechanism of ATRP polymerization is given in Mattyjaszewski et al., Page 524, Reaction Scheme 11.1, page 666, Reaction Scheme 11.4, page 571, Reaction Scheme 11.7, page 572, Reaction Schemes 11.8 and 575. Reaction scheme 11.9 on page. In ATRP polymerization, groups that can be transferred by a radical mechanism include halogens (from halogen-containing compounds) or various ligands. A more detailed review of groups that can be transferred is described in US Pat. No. 6,391,996 or paragraphs 61-65 of International Publication WO 2006/047398.

  Chain transfer agents are important in RAFT polymerization. A more detailed review of suitable chain transfer agents can be found in paragraphs [0066] to [0071] of International Publication WO 2006/047398. In one embodiment, suitable RAFT chain transfer agents include 2-dodecylsulfanyl-thiocarbonylsulfanyl-2-methyl-propionic acid butyl ester, cumyl dithiobenzoate or mixtures thereof. A discussion of the star polymer mechanism of RAFT polymerization is given in Matyjaszewski et al., Section 12.4.4, pages 664-665.

  Star polymers can be prepared by techniques known in the art for preparing with either a core-first or arm-first approach. Typically, star polymers are prepared by an “arm first” approach using RAFT or ATRP (typically RAFT) polymerization techniques.

  A (meth) acrylic polymer having a star structure can be prepared from a known monomer such as an alkyl (meth) acrylate. Examples of the alkyl (meth) acrylate include compounds derived from saturated alcohols such as methyl (meth) acrylate, butyl (meth) acrylate, 2-methylpentyl (meth) acrylate, 2-propylheptyl (meth) acrylate, 2-butyloctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-tert-butylheptyl (meth) Acrylate, 3-isopropylheptyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-meth Ludodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, Heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyl eicosyl (meth) acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyl Tetratriacontyl (meth) acrylate, etc .; (meth) acrylates derived from unsaturated alcohols, such as oleyl (meth) acrylate, etc .; and Black alkyl (meth) acrylate, for example, and the like 3-vinyl-2-butylcyclohexyl (meth) acrylate or bornyl (meth) acrylate.

  Alkyl (meth) acrylates having groups derived from long chain alcohols, for example, reaction of (meth) acrylic acid (by direct esterification) or methyl (meth) acrylate (by transesterification) with long chain aliphatic alcohols The reaction generally gives a mixture of esters such as (meth) acrylates having alkyl groups of various chain lengths. These aliphatic alcohols include Monsanto's Oxo Alcohol (R) 7911, Oxo Alcohol (R) 7900 and Oxo Alcohol (R) 1100; ICI Alphanol (R) 79; Condea (now Sasol) Nafol (R) 1620, Alfol (R) 610 and Alfol (R) 810; Ethyl Corporation's Epal (R) 610 and Epal (R) 810; Shell AG's Linevol (R) 79, Linevol (R) Trademark) 911 and Dobanol <(R)> 25L; Lial <(R)> 125 from Condea Augusta (Milan); Henkel KGaA (currently Co) Dehydad of nis) (R) and Lorol (R) and Ugine Kuhlmann of Linopol (R) 7-11 and Acropol (R) 91, as well as Isofol (R) branched Guerbet alcohol from Sasol.

  In one embodiment, the star polymer may be further functionalized with nitrogen-containing monomers in the core or polymer arm. The nitrogen-containing monomer can also be referred to as a dispersant monomer. The nitrogen-containing monomers include vinyl-substituted nitrogen heterocyclic monomers, dialkylaminoalkyl (meth) acrylate monomers, dialkylaminoalkyl (meth) acrylamide monomers, tertiary (meth) acrylamide monomers, ureido (meth) acrylates, Or mixtures thereof may be included.

  In one embodiment, the core or polymer arm further comprises (meth) acrylamide or nitrogen-containing (meth) acrylate monomers. Examples of suitable nitrogen-containing vinyl monomers include N, N-dimethylacrylamide, N-vinylcarbonamide such as N-vinyl-formamide, vinylpyridine, N-vinylacetamide, N-vinyl-n-propionamide, N-vinyl. Hydroxyacetamide, N-vinylimidazole, N-vinylpyrrolidinone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl (meth) acrylate (DMAEMA), dimethylaminobutylacrylamide, diethylamine-propyl (meth) acrylate ( DMAPMA), dimethylamine-propyl-acrylamide, dimethylaminopropylmethacrylamide, dimethylaminoethyl-acrylamide, or mixtures thereof. The dispersant monomer may be an oxygen-containing compound. The oxygen-containing compound is a hydroxyalkyl (meth) acrylate such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate, carbonyl-containing (meth) acrylate, for example, 2-carboxyethyl (meth) acrylate, Carboxymethyl (meth) acrylate, oxazolidinylethyl (meth) acrylate, N- (methacryloyloxy) formamide, acetonyl (meth) acrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrole Non, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2-pyrrolidinone, N- (2-methacryloyloxypentadecyl) -2-pyrrolidinone, N- (3- Methacryloyloxyheptadecyl) -2-pyrrolidinone, glycol di (meth) acrylate, such as ethylene glycol di (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- Ethoxide ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or mixtures thereof can be included.

  Other examples of suitable non-carbonyl oxygen-containing compounds that can be incorporated into the copolymer include (meth) acrylates of ether alcohols such as tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate, methoxyethoxyethyl ( (Meth) acrylate, 1-butoxypropyl (meth) acrylate, 1-methyl- (2-vinyloxy) ethyl (meth) acrylate, cyclohexyloxymethyl (meth) acrylate, methoxymethoxyethyl (meth) acrylate, benzoyloxymethyl (meth) Acrylate, furfuryl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, allyl Xymethyl (meth) acrylate, 1-ethoxybutyl (meth) acrylate, methoxymethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and typically 1-20, or 2 Ethoxylated (meth) acrylates having -8 ethoxy groups or mixtures thereof are included.

  The star polymer is difunctional divinylbenzene, dipentaerythritol hexamethacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octamethacrylate, tripentaerythritol octaacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, bis-acrylate. And a polyethylene glycol methacrylate having a molecular weight of 200 to 4000, polycaprolactone diol diacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 1,1,1-trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol tetraacrylate, ethylene Glico Preparing from dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,1,1-trimethylolpropane trimethacrylate, hexamethylenediol diacrylate or hexamethylenediol dimethacrylate or alkylene bis- (meth) acrylamide Can do. Typically, the bifunctional monomer comprises a bifunctional methacrylate monomer.

The linear or star-shaped (meth) acrylate may contain a _C 1 _{-C 10} or _C 1 -C ₈ acrylate groups, of 0 wt% 30 wt% or 0 wt% 20 wt%. The acrylate group may be, for example, ethyl acrylate or 2-ethylhexyl acrylate.

  The lubricating composition of the present invention may further include a polymer having a comb structure of 0.1 wt% to 5 wt% (0.1 wt% to 4 wt% or 0.2 wt% to 3 wt%).

  The polymer having a comb structure is composed of a repeating unit derived from a polyolefin-based macromonomer in the main chain, a styrene monomer having 8 to 17 carbon atoms, and an alkyl having 1 to 15 carbon atoms in an alcohol group. (Meth) acrylate, vinyl ester having 1 to 11 carbon atoms in acyl group, vinyl ether having 1 to 10 carbon atoms in alcohol group, 1 to 10 carbon atoms in alcohol group ( Including repeating units derived from low molecular weight monomers selected from the group consisting of di) alkyl fumarate, (di) alkyl maleates having 1-10 carbon atoms in the alcohol group, and mixtures of these monomers , The degree of molar branching may be a comb polymer in the range of 0.1 to 10 mol%, the comb polymer is Styrene monomer having a total of at least 80% by weight of repeating units derived from polyolefin-based macromonomer and 8 to 17 carbon atoms, alkyl having 1 to 15 carbon atoms in the alcohol group, based on the amount (Meth) acrylate, vinyl ester having 1 to 11 carbon atoms in acyl group, vinyl ether having 1 to 10 carbon atoms in alcohol group, 1 to 10 carbon atoms in alcohol group ( Including repeating units derived from low molecular weight monomers selected from the group consisting of di) alkyl fumarate, (di) alkyl maleates having 1-10 carbon atoms in the alcohol group, and mixtures of these monomers .

  In one embodiment, the polymer having a comb structure may have a glass transition temperature in the range of −30 to 100 ° C.

  The polymer having a comb structure may have a repeating unit derived from a polyolefin-based macromonomer having a number average molecular weight in the range of 500 to 10,000 g / mol.

  The polymer having a comb structure comprises at least 90% by weight of repeating units derived from a polyolefin-based macromonomer, as well as a styrene monomer having 8 to 17 carbon atoms, 1 to 15 carbon atoms in the alcohol group. Alkyl (meth) acrylate having vinyl ester having 1 to 11 carbon atoms in acyl group, vinyl ether having 1 to 10 carbon atoms in alcohol group, 1 to 10 carbon atoms in alcohol group A repeating unit derived from a low molecular weight monomer selected from the group consisting of (di) alkyl fumarate having, (di) alkyl maleate having 1-10 carbon atoms in the alcohol group, and mixtures of these monomers Can have.

  The polymer having a comb structure may have a degree of molar branching in the range of 0.8% to 6.0%, or 0.8% to 3.4%.

  The polymer having a comb structure can have an iodine number of less than or equal to 0.2 g / g comb polymer.

  The polymer having a comb structure may have repeating units derived from a polyolefin-based macromonomer derived from a monomer selected from the group consisting of C2-C10-alkene and / or C4-C10-alkadiene.

  The repeating unit comprises at least 80% by weight of a group derived from a monomer selected from the group consisting of C2-C10-alkene and / or C4-C10-alkadiene (based on the weight of the repeating unit derived from a polyolefin-based macromonomer). On the basis of) polyolefin-based macromonomers.

  The polymer having a comb structure is a repeat derived from a polyolefin-based macromonomer containing groups derived from non-olefinic monomers selected from the group of styrene, (meth) acrylates, vinyl esters, vinyl ethers, fumarate and maleate Can have units.

  The repeating unit comprises up to 20% by weight, based on the weight of the repeating unit, of groups derived from non-olefinic monomers selected from the group of styrene, (meth) acrylates, vinyl esters, vinyl ethers, fumarate and maleate It can be derived from a polyolefin-based macromonomer.

  The polymer having a comb structure can have repeating units derived from a polyolefin-based macromonomer having a melting point less than or equal to −10 ° C.

  The polymer having a comb structure can have repeating units derived from styrene and repeating units derived from n-butyl methacrylate. The repeating unit can be derived from repeating units derived from styrene and n-butyl acrylate.

  The polymer having a comb structure can have repeating units derived from methyl methacrylate and repeating units derived from n-butyl methacrylate.

  The polymer having a comb structure can have a weight average molecular weight in the range of 50,000 to 500,000 g / mol.

  The process of preparing the polymer having a comb structure may be continuous or batch mode, typically batch mode.

  The process of preparing the polymer having a comb structure can be carried out in the absence or presence of a solubilized carrier medium, typically in the presence of a solubilized carrier medium. When present, the carrier medium is selected from the group of base oils and / or aromatic hydrocarbons.

A more detailed description of the comb polymer is described in US2008 / 194443. The comb polymer can also be prepared as disclosed in paragraphs [0142] to [0160] of US2008 / 194443. A more detailed description of comb polymers is described in US 2008/194443. The comb polymer can also be prepared as disclosed in paragraphs [0142] to [0160] of US2008 / 194443.
Friction modifier

  The lubricating composition of the present invention can optionally contain at least two friction modifiers. Friction modifiers useful for the present invention are described below.

In one embodiment, the friction modifier can be formed by condensation of a hydroxyalkyl compound with an acylating agent or amine. A more detailed description of hydroxyalkyl compounds can be found in paragraphs 8, 19-21 of US Patent Application No. 60/725360 (filed Oct. 11, 2005, inventor Bartley, Lahiri, Baker and Tipton). The friction modifier disclosed in U.S. Patent Application No. 60/725360 has the formula R ¹ R ² N—C (O) R ³ , wherein R ¹ and R ² are each independently at least 6 carbon atoms. R ³ is a hydroxyalkyl group of 1 to 6 carbon atoms, or a group formed by condensation of the hydroxyalkyl group with an acylating agent through the hydroxyl group). Amide. Examples of preparation are disclosed in Examples 1 and 2 (paragraphs 68 and 69). In one embodiment, the amide of the hydroxyl alkyl compound is prepared by reacting glycolic acid, ie, hydroxyacetic acid, HO—CH ₂ —COOH, with an amine.

In one embodiment, the friction modifier is of the formula R ⁴ R ⁵ NR ⁶ , wherein R ⁴ and R ⁵ are each independently an alkyl group of at least 6 carbon atoms, and R ⁶ is hydrogen, hydrocarbyl Or a secondary or tertiary amine represented by a group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group. A more detailed description of the friction modifier is described in paragraphs 8 and 19-22 of US Patent Application No. 05/037897.

  In one embodiment, the friction modifier can be derived from the reaction of a carboxylic acid or reactive equivalent thereof with an amino alcohol, the friction modifier being at least 2 each containing at least 6 carbon atoms. Contains some hydrocarbyl groups. Examples of such friction modifiers include the reaction product of isostearic acid or alkyl succinic anhydride and trishydroxymethylaminomethane. A more detailed description of such friction modifiers is disclosed in paragraphs 8 and 9-14 of WO 04/007652.

  Examples of friction modifiers include aliphatic amines, borated glycerin esters, fatty acid amides, non-borated aliphatic epoxides, borated aliphatic epoxides, alkoxylated aliphatic amines, borated alkoxylated aliphatic amines, fatty acid metal salts, Aliphatic imidazolines, metal salts of alkyl salicylates (also referred to as detergents), metal salts of sulfonic acids (also referred to as detergents), carboxylic acids or polyalkylene-polyamines or amides of hydroxyalkyl compounds These condensation products are included.

In one embodiment, the friction modifier comprises a fatty acid ester of glycerin. The final product can be in the form of a metal salt, amide, imidazoline, or a mixture thereof. The fatty acid can have 6 to 24, or 8 to 18 carbon atoms. The fatty acid may be branched or linear, saturated or unsaturated. Suitable acids include 2-ethylhexanoic acid, decanoic acid, oleic acid, stearic acid, isostearic acid, palmitic acid, myristic acid, palmitoleic acid, linoleic acid, lauric acid, and linolenic acid, and natural product tallow, Acids from palm oil, olive oil, peanut oil, corn oil, and cow leg oil are included. In one embodiment, the fatty acid is oleic acid. When in the form of a metal salt, typically the metal comprises zinc or calcium and the product comprises overbased and non-overbased products. Examples are overbased calcium salts and basic oleic acid-zinc salt complexes that can be represented by the general formula Zn ₄ Oleate ₆ O. When in the amide form, condensation products include those prepared using ammonia or primary or secondary amines such as diethylamine and diethanolamine. A condensation product of an acid with a diamine or a polyamine such as a polyethylene polyamine when in the form of an imidazoline. In one embodiment, the friction modifier is a condensation product of a fatty acid having a C8-C24 atom and a polyalkylene polyamine, in particular a product of isostearic acid and tetraethylenepentamine.

In one embodiment, friction modifiers include those formed by condensation of hydroxyalkyl compounds with acylating agents or amines. A more detailed description of the hydroxyalkyl compound is described in WO 2007/0044820, paragraphs 9 and 20-22. The friction modifier disclosed in WO 2007/044820 is of the formula R ¹² R ¹³ N—C (O) R ¹⁴ , wherein R ¹² and R ¹³ are each independently a hydrocarbyl group of at least 6 carbon atoms. , R ¹⁴ is a hydroxyalkyl group of 1 to 6 carbon atoms, or a group formed by condensation of said hydroxyalkyl group with an acylating agent through its hydroxyl group. Examples of preparations are disclosed in Examples 1 and 2 (WO 2007/0444820 paragraphs 72 and 73). In one embodiment, the amide of the hydroxyl alkyl compound is prepared by reacting glycolic acid, ie, hydroxyacetic acid, HO—CH ₂ —COOH, with an amine.

In one embodiment, the friction modifier is of the formula R ¹⁵ R ¹⁶ NR ¹⁷ , wherein R ¹⁵ and R ¹⁶ are each independently an alkyl group of at least 6 carbon atoms, and R ¹⁷ is a hydrogen, hydrocarbyl group , A hydroxyl-containing alkyl group, or an amine-containing alkyl group). A more detailed description of the friction modifier is described in paragraphs 8 and 19-22 of US Patent Application No. 2005/037897.

  In one embodiment, the friction modifier comprises a reaction product of di-cocoalkylamine (or dicocoamine) and glycolic acid. The friction modifier comprises the compound prepared in Examples 1 and 2 of the preparation of WO2008 / 014319.

  In one embodiment, the friction modifier comprises one derived from the reaction product of a carboxylic acid or their reactive equivalent and an amino alcohol, each friction modifier containing at least 6 carbon atoms. Containing at least two hydrocarbyl groups. Examples of such friction modifiers include the reaction product of isostearic acid or alkyl succinic anhydride and tris-hydroxymethylaminomethane. A more detailed description of such friction modifiers is disclosed in paragraphs 8 and 9-14 of US patent application 2003/22000 (or international publication WO 04/007652).

  In one embodiment, the friction modifier comprises an alkoxylated alcohol. A detailed description of suitable alkoxylated alcohols is described in US Patent Application Publication No. 2005/0101497, paragraphs 19 and 20. The alkoxylated amine is also described in US Pat. No. 5,641,732 at column 7, lines 15-9, line 25.

  In one embodiment, the friction modifier comprises a hydroxylamine compound as defined in US Pat. No. 5,534,170 at column 37, line 19-39, line 38. Optionally, the hydroxylamine comprises a borated product as described in US Pat. No. 5,534,170, column 39, line 39-40, line 8.

  In one embodiment, the friction modifier is an alkoxylated amine, for example, 1.8% Ethomeen ™ as described in Example 5, US Pat. No. 5,703,023, column 28, lines 30-46. ) Containing ethoxylated amines derived from T-12 and 0.90% Tomah ™ PA-1. Other suitable alkoxylated amine compounds include the commercially available alkoxylated aliphatic amines available from Akzo Nobel, known by the trademark “ETHOMEEN”. Representative examples of these ETHOMEEN ™ materials include ETHOMEEN ™ C / 12 (bis [2-hydroxyethyl] -coco-amine), ETHOMEEN ™ C / 20 (polyoxyethylene [10] cocoamine. ), ETHOMEEN ™ S / 12 (bis [2-hydroxyethyl] soiamine), ETHOMEEN ™ T / 12 (bis [2-hydroxyethyl] -tallow-amine), ETHOMEEN ™ T / 15 (poly Oxyethylene- [5] tallowamine), ETHOMEEN ™ 0/12 (bis [2-hydroxyethyl] oleyl-amine), ETHOMEEN ™ 18/12 (bis [2-hydroxyethyl] octadecylamine), and ETHOMEEN (Trademark) 18/25 (Polyoxyethylene [15] octadecyl amine). Aliphatic amines and ethoxylated aliphatic amines are also described in US Pat. No. 4,741,848.

  In one embodiment, the friction modifier comprises a polyol ester described in US Pat. No. 5,750,476, column 8, lines 40-9, line 28.

  In one embodiment, the friction modifier comprises a low efficacy friction modifier described in US Pat. No. 5,840,662, column 2, lines 28-3, line 26. US Pat. No. 5,840,662 further discloses certain materials and methods for preparing low-efficiency friction modifiers in columns 3, lines 48-6, lines 25.

  In one embodiment, the friction modifier comprises the reaction product of an isomerized alkenyl-substituted succinic anhydride and polyamine as described in US Pat. No. 5,840,663 at column 2, lines 18-43. Particular embodiments of the friction modifier described in US Pat. No. 5,840,663 are further disclosed in column 3, line 23 to column 4, line 35. Examples of preparation are further disclosed in US Pat. No. 5,840,663 at column 4, lines 45-5, line 37.

  In one embodiment, the friction modifier comprises an alkyl phosphonate mono- or di-ester marketed by Rhodia under the trademark Duraphos® DMODP.

  The condensation of the fatty acids of the present invention with polyamines typically results in the formation of at least one compound selected from hydrocarbyl amides, hydrocarbyl imidazolines and mixtures thereof. In one embodiment, the condensation product is hydrocarbyl imidazoline. In one embodiment, the condensation product is hydrocarbyl amide. In one embodiment, the condensation product is a mixture of hydrocarbyl imidazoline and hydrocarbyl amide. Typically, the condensation product is a mixture of hydrocarbyl imidazoline and hydrocarbyl amide.

  The fatty acids of the present invention can be derived from hydrocarbyl carboxylic acids. The hydrocarbyl group may be alkyl, cycloalkyl, or aryl, but is typically alkyl, and the hydrocarbyl group may be linear or branched. Typically, the fatty acid contains 8 or more, 10 or more, and further 13 or 14 or more carbon atoms, including the carbon of the carboxy group. Typically, the fatty acid contains 8-30, 12-24, or 16-18 carbon atoms. Other suitable carboxylic acids may include polycarboxylic acids or carboxylic acids or acid anhydrides having 2 to 4, typically 2 carbonyl groups. The polycarboxylic acid is produced by Diels-Alder reaction of succinic acid and acid anhydride and unsaturated monocarboxylic acid with unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid). Things can also be included. The aliphatic carboxylic acids include aliphatic monocarboxylic acids containing 8 to 30, 10 to 26, or 12 to 24 carbon atoms.

  Examples of suitable fatty acids can include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid, and tall oil acid. In one embodiment, the fatty acid is stearic acid, which can be used alone or in combination with other fatty acids.

  The polyamine of the present invention may be acyclic or cyclic, preferably acyclic, may be linear or branched, and is preferably linear.

  In one embodiment, the polyamine may be an alkylene polyamine selected from the group consisting of ethylene polyamine, propylene polyamine, butylene polyamine, and mixtures thereof. Examples of propylene polyamines can include propylene diamine and dipropylene triamine.

  Particularly useful ethylene polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -N ′-[2-[(2-aminoethyl) amino] ethyl]. -1,2-ethanediamine, selected from the group consisting of polyamine residue and mixtures thereof.

  In one embodiment, the polyamine may be an α, β-diaminoalkane. Suitable α, β-diaminoalkanes can include diaminopropane, diaminobutane or mixtures thereof. Specific diaminoalkanes include N- (2-aminoethyl) -1,3-propanediamine, 3,3′-diamino-N-methyldipropylamine, tris (2-aminoethyl) amine, N, N-bis. It is selected from the group consisting of (3-aminopropyl) -1,3-propanediamine, N, N′-1,2-ethanediylbis- (1,3-propanediamine) and mixtures thereof.

  In one embodiment, the other polyamines can include di- (trimethylene) triamine, piperazine, diaminocyclohexane, and mixtures thereof.

  In one embodiment, one or both friction modifiers may be nitrogen-containing compounds, and typically both friction modifiers are nitrogen-containing compounds.

  In one embodiment, one type of friction modifier is a condensation product of a fatty acid having a C8-C24 atom and a polyalkylene polyamine, in particular a product of isostearic acid and tetraethylenepentamine.

The mixture of at least two friction modifiers is 0.1 wt% to 1 wt%, or 0.2 wt% to 0.9 wt%, or 0.1 wt% to 0.4 wt%, or 0.4 wt% to Antioxidant that can be present at 1.0 wt%

In one embodiment, the lubricating composition of the present invention comprises an amine antioxidant. The amine antioxidant may be phenyl-α-naphthylamine (PANA) or hydrocarbyl substituted diphenylamine, or a mixture thereof. Hydrocarbyl-substituted diphenylamine, mono- - or di _-C 4 _{-C 16} -, or _C 6 _{-C 12} -, or _{C 9} - may comprise an alkyl diphenylamine. For example, the hydrocarbyl substituted diphenylamine can be octyl diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, and typically can be dinonyl diphenylamine.

  When present, the amine antioxidant is 0.2 wt% to 1.2 wt%, or 0.3 wt% to 1.0 wt%, or 0.4 wt% to 0.9 wt% or 0.5 wt% of the lubricating composition. % To 0.8 wt%.

  The lubricating composition optionally includes at least one other known antioxidant and includes sulfurized olefins, hindered phenols, molybdenum dithiocarbamates, and mixtures thereof.

  Hindered phenol antioxidants often contain secondary and / or tertiary butyl groups as sterically hindering groups. The phenolic group is often further substituted with a bridging group linked to a hydrocarbyl group and / or a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol or 4-dodecyl-2,6-di-tert-butylphenol is included. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox ™ L-135 from Ciba, or butyl 3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propanoate.

  If present, the secondary antioxidant is 0.1 wt% to 1 wt%, or 0.2 wt% to 0.9 wt%, or 0.1 wt% to 0.4 wt%, or 0.4 wt% of the lubricating composition. % To 1.0 wt%.

  Optionally, the lubricating composition may further contain other performance additives. Other performance additives include corrosion inhibitors, antifoaming agents, pour point depressants, demulsifiers, metal deactivators or seal swell agents.

  Corrosion inhibitors include 1-amino-2-propanol, amines, triazole derivatives including tolyltriazole, dimercaptothiadiazole derivatives, octylamine octanoate, dodecenyl succinic acid or acid anhydride and / or oleic acid and polyamines And condensation products.

  Antifoaming agents that may be useful in the compositions of the present invention include copolymers of polysiloxane, ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate, and the demulsifier is a fluorinated polysiloxane, trialkyl phosphate. Polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers.

  Pour point depressants that may be useful in the compositions of the present invention include poly alpha olefins, esters of maleic anhydride-styrene copolymers, poly (meth) acrylates, polyacrylates or polyacrylamides.

  Demulsifiers include trialkyl phosphates and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.

  Metal deactivators include derivatives of benzotriazole (typically tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole. The metal deactivator can also be described as a corrosion inhibitor.

  Seal swelling agents include sulfolene derivatives, Exxon Necton-37 ™ (FN1380) and Exxon Mineral Seal Oil ™ (FN3200).

  The following examples illustrate the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

脚注：
Ｕｌｔｒａ Ｓ−３油およびＳ−８油は、両方共１１０から１２０未満の間の粘度指数を有するＡＰＩ規格ＩＩ＋基油である。
耐摩耗剤の混合物は、リン酸、ジブチルホスファイト、およびジヒドロカルビルＣ１６〜１８水素ホスファイト（ここでヒドロカルビル基はアルキル基とアルケニル基の混合物である）を含む。
摩擦調整剤の混合物は、３から６種の間の摩擦調整剤を含む。
４．２４ｗｔ％で処理された他の添加剤は、フェノール性抗酸化剤とアミン性抗酸化剤の混合物、カルボン酸エステル、ホウ酸エステル、腐食防止剤、流動点降下剤、消泡剤、シール膨潤剤、および希釈剤油を含む。
該線状ポリマーは、メチルメタクリレート（１４．１ｗｔ％）、２−エチルヘキシルメタクリレート（４．７ｗｔ％）、Ｃ_{１２〜１５}アルキルメタクリレート（７５．１ｗｔ％）、およびエチレングリコールジメタクリレート（６．１ｗｔ％）を含むモノマー組成物から誘導することができる。該線状ポリマーの重量平均分子量は１５，０００である。
比較例は、ＦｏｒｄタイプＡ ＭＥＲＣＯＮ（登録商標）ＬＶ ＡＴＦおよびＳｈｅｌｌ ＡＴＦ（商標）１３４ＦＥに基づいて評価される。 Lubricant: Invention and Reference Lubricating Oil Compositions Four fluids of the present invention (INV1 to INV4) add 13.85 wt% of the following additive package to the specified base oil (or oil of lubricating viscosity) To prepare as summarized below. The base oil of each lubricant of the present invention has a kinematic viscosity in the range of 2.8 to 3.6 cSt (mm ² / s) at 100 ° C. and a viscosity index between 110 and less than 120.

footnote:
Ultra S-3 and S-8 oils are API standard II + base oils, both having a viscosity index between 110 and less than 120.
The antiwear mixture includes phosphoric acid, dibutyl phosphite, and dihydrocarbyl C16-18 hydrogen phosphite, where the hydrocarbyl group is a mixture of alkyl and alkenyl groups.
The mixture of friction modifiers contains between 3 and 6 friction modifiers.
Other additives treated with 4.24 wt% are mixtures of phenolic and amine antioxidants, carboxylic esters, boric esters, corrosion inhibitors, pour point depressants, antifoams, seals Includes swelling agent and diluent oil.
The linear polymer includes methyl methacrylate (14.1 wt%), 2-ethylhexyl methacrylate (4.7 wt%), C _12-15 alkyl methacrylate (75.1 wt%), and ethylene glycol dimethacrylate (6.1 wt%). Can be derived from a monomer composition comprising The linear polymer has a weight average molecular weight of 15,000.
Comparative examples are evaluated based on Ford Type A MERCON® LV ATF and Shell ATF ™ 134FE.

  Each lubricant INV1-INV4 and comparative ATF are assessed by comparing CAFE diagrams using 2011Ford melt AT (6HP6) using the following procedure.

  ASTM D2882 Pump Test: This procedure assesses lubricant wear resistance using a Vickers 104-C wing pump driven by an electric motor. Pump blade and cam ring weight loss is recorded after 100 hours of continuous operation, followed by visual inspection for cuts and surface damage.

  The Falex wear / EP test described in ASTM D-3233 is used to assess the friction, wear and extreme pressure (EP) properties of the lubricating fluid. A rotating steel shaft neck is operated between two fixed steel V-blocks immersed in the test fluid. The load was applied to the V-block, increasing by 250-lbf (1112 N), keeping each increased load constant for 1 minute, increasing the load until the torque could no longer be maintained, or until the block seized against the pin. The test was conducted at fluid temperatures of 100 and 150 ° C.

The results obtained for the Falex EP test and the pump test are as follows:

The lubricating composition is then evaluated by determining kinematic and Brookfield viscosities (ASTM method D445 at 40 ° C. and 100 ° C. (kinematic viscosity at 40 ° C .: KV 40, and kinematic viscosity at 100 ° C .: KV100) as well as D2983 at −40 ° C. (by Brookfield viscosity at −40 ° C .: BV-40), respectively. The results obtained are also shown in the table. The results obtained for each lubricant are as follows:

  Overall, the data is measured by a sliding blade rotary pump test while the lubricating composition of the present invention maintains a low lubricant viscosity at a higher passing load as measured by a 150 ° C. Falex wear test. Indicates reduced wear.

脚注：
線状分散剤のポリ（メタ）アクリレートは、２−エチルヘキシル（メタ）アクリレート（３０ｗｔ％）、Ｃ_{１２〜１５}アルキル（メタ）アクリレート（６８．２ｗｔ％）、およびジメチルアミノプロピル（メタ）アクリレート（１．８ｗｔ％）を含むモノマー組成物から誘導される。
ＩＮＶ７〜ＩＮＶ１０のスターポリマーは、それぞれ約５４０，０００、７４０，０００、９２０，０００、および１，２００，０００の重量平均分子量を有する。該スターポリマーは、下記のメタクリレートモノマー混合物から調製される。該スターポリマーは、ＲＡＦＴ重合プロセスにより調製される。

E=エチレングリコールジメタクリレート

脚注：
^＊は、２エチルヘキシルアクリレートである
線状分散剤ポリメタクリレートコポリマー（ＨＬＷ）は第２の分散剤粘度調整剤である。ＩＮＶ５のＨＬＷは１５，０００の重量平均分子量を有し、６８．２ｗｔ％のＣ_{１２〜１５}アルキルメタクリレート、３０ｗｔ％の２−エチルヘキシルメタクリレート、および１．８ｗｔ％のジメチルアミノプロピル（メタ）アクリレートのモノマー混合物から誘導される。
耐摩耗剤の混合物は、リン酸、ジブチルホスファイト、およびジヒドロカルビルＣ１６〜１８水素ホスファイト（ヒドロカルビル基はアルキル基とアルケニル基の混合物である）を含む。
摩擦調整剤の混合物は、３種から６種の間の摩擦調整剤を含む。
４．２４ｗｔ％で処理された他の添加剤は、フェノール性およびアミン性抗酸化剤、カルボン酸エステル、ホウ酸エステル、腐食防止剤、流動点降下剤、消泡剤、シール膨潤剤、および希釈剤油の混合物を含む。 Examples 5 to 11 (INV5 to INV12) of the present invention are prepared in the same manner as INV1, except that the lubricating composition of each lubricant is summarized as follows:

footnote:
The poly (meth) acrylate of the linear dispersant includes 2-ethylhexyl (meth) acrylate (30 wt%), C _12-15 alkyl (meth) acrylate (68.2 wt%), and dimethylaminopropyl (meth) acrylate (1 .8 wt%) derived from the monomer composition.
INV7 to INV10 star polymers have weight average molecular weights of about 540,000, 740,000, 920,000, and 1,200,000, respectively. The star polymer is prepared from the following methacrylate monomer mixture. The star polymer is prepared by a RAFT polymerization process.

E = ethylene glycol dimethacrylate

footnote:
^* Linear dispersant polymethacrylate copolymer (HLW), which is 2-ethylhexyl acrylate, is the second dispersant viscosity modifier. INV5 HLW has a weight average molecular weight of 15,000 and is a monomer of 68.2 wt% C _12-15 alkyl methacrylate, 30 wt% 2-ethylhexyl methacrylate, and 1.8 wt% dimethylaminopropyl (meth) acrylate Derived from the mixture.
The antiwear mixture includes phosphoric acid, dibutyl phosphite, and dihydrocarbyl C16-18 hydrogen phosphite (the hydrocarbyl group is a mixture of alkyl and alkenyl groups).
The mixture of friction modifiers includes between 3 and 6 friction modifiers.
Other additives treated with 4.24 wt% include phenolic and amine antioxidants, carboxylic esters, boric esters, corrosion inhibitors, pour point depressants, antifoams, seal swells, and dilutions Contains a mixture of oils.

INV5 to INV10 were evaluated for viscosity properties and summarized below.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. In particular, the term refers to a group having a carbon atom bonded directly to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups are:
(I) substituted with hydrocarbon substituents, ie, aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic Aromatic substituents, as well as cyclic substituents (the ring completes through another part of the molecule (eg, the two substituents together form a ring));
(Ii) substituted hydrocarbon substituents, ie non-hydrocarbon groups that do not change the predominantly hydrocarbon nature of the substituent in the context of the present invention (eg halo (especially chloro and fluoro), hydroxy, alkoxy, Substituents containing mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
(Iii) Hetero substituents, ie, in the context of the present invention, include substituents that have predominantly hydrocarbon properties but otherwise contain other than carbon in a ring or chain composed of carbon atoms It is.
Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and typically there will be no non-hydrocarbon substituents in the hydrocarbyl group. I will.

  It is known that some of the above materials may interact in the final formulation and the components of the final formulation may differ from those originally added. The product formed thereby may not be readily accounted for, including the product formed when the lubricating composition of the present invention is used in its intended application. Nevertheless, all such modifications and reaction products are included within the scope of the present invention, which includes a lubricating composition prepared by admixing the components described above.

  Each of the documents referred to above is incorporated herein by reference. All quantities in this description specifying the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc., unless otherwise expressly stated in the examples, are expressed in the word “about”. Should be understood to be modified by Unless otherwise stated, each chemical or composition listed herein may include isomers, by-products, derivatives, and other materials that are commonly understood to exist in commercial specifications. It should not be interpreted as a commercial standard material. However, the amount of each chemical component is provided except for any solvent or diluent oil that may typically be present in commercially available materials, unless stated otherwise. It should be understood that the upper and lower amount, range, and ratio limits set forth herein may be combined independently. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any other element.

  Although the present invention has been described with respect to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Therefore, it is to be understood that the invention disclosed herein is intended to encompass such modifications as falling within the scope of the appended claims.

Claims (19)

(A) an oil of lubricating viscosity having a kinematic viscosity of 2.8 to 3.6 cSt (mm ² / s) at 100 ° C. and a viscosity index of 104 to 130;
(B) 1.2-5.0 wt% of at least one borated dispersant further functionalized with a sulfur or phosphorus moiety;
(C) a calcium-containing detergent present in an amount resulting in at least 110 ppm to 700 ppm calcium;
(D) at least two phosphorus-containing compounds that are present in an amount that provides 360-950 ppm phosphorus to the lubricating composition, wherein at least 150 ppm of the phosphorus is provided by C _4-6 hydrocarbyl phosphite; and (e) linear A lubricating composition comprising a linear polymer viscosity modifier having a dispersant functionality of 0.1 wt% to 5 wt%, wherein the polymer has a weight average molecular weight of 5,000 to 25,000.   The composition of claim 1, wherein the calcium-containing detergent is present in an amount that provides 130 ppm to 600 ppm, or 160 ppm to 400 ppm calcium. The C _{4 to 6} hydrocarbyl phosphite is C ₄ alkyl phosphite composition according to any one of the preceding claims.   The preceding claim, wherein the borated dispersant is a borated polyisobutylene succinimide dispersant and the polyisobutylene of the borated polyisobutylene succinimide has a number average molecular weight of 750-2200, or 750-1350, or 750-1150. The composition according to any one of Items.   And further comprising a second borated dispersant, wherein the borated dispersant is a borated polyisobutylene succinimide dispersant, and the polyisobutylene of the polyisobutylene succinimide is 750-2200, or 750-1350, or 750-1150. A composition according to any preceding claim having a number average molecular weight.   A composition according to any preceding claim, further comprising a non-boron dispersant.   7. The non-borated dispersant is polyisobutylene succinimide, and the polyisobutylene of the borated polyisobutylene succinimide has a number average molecular weight of 750-2200, or 750-1350, or 750-1150. Composition.   Preceding, wherein the borated dispersant has an N: CO ratio of 0.9: 1 to 1.6: 1, or 0.95: 1 to 1.5: 1, or 1.0: 1 to 1: 4 A composition according to any preceding claim.   The linear polymer has a weight average molecular weight of greater than 25,000 to 400,000 (or up to 350,000) and has a dispersant functionality of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%). 9. A composition according to any preceding claim, further comprising a linear (meth) acrylic polymer viscosity modifier. The linear polymer viscosity modifier having dispersant functionality is
Linear (meth) acrylic polymer viscosity with dispersant functionality of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%), where the linear polymer has a weight average molecular weight of 10,000 to 20,000 Regulators, and linear having a dispersant functionality of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%), wherein the linear polymer has a weight average molecular weight of greater than 20,000 to 250,000 9. A composition according to any preceding claim comprising a (meth) acrylic polymer viscosity modifier. The linear polymer viscosity modifier having dispersant functionality is
The linear polymer has a weight average molecular weight of 5,000 to 25,000 or 10,000 to 20,000 and has a dispersant functionality of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%). Comprising a linear (meth) acrylic polymer, the composition comprising:
The composition according to any of the preceding claims, further comprising a (meth) acrylic polymer having a star structure of 0.1 wt% to 4 wt% (or 0.2 wt% to 3 wt%). The (meth) acrylic polymer having a star structure is
(A) 50 wt% to 100 wt% alkyl (meth) acrylate, wherein the alkyl group has 12 to 15 carbon atoms,
(B) 0 wt% to 40 wt% alkyl (meth) acrylate in which the alkyl group has 1 to 9 carbon atoms,
(C) 0 wt% to 10 wt% dispersant monomer,
(D) 0 wt% to 5 wt%, or 0 wt% to 2 wt%, or 0 wt% vinyl aromatic monomer (typically styrene), and (e) 0 wt% where the alkyl group has 16 to 18 carbon atoms 12. having three or more arms comprising a poly (meth) acrylate polymer derived from a monomer composition comprising ˜20 wt%, or 0 wt% to 10 wt%, or 0 wt% alkyl (meth) acrylate. A composition according to 1. The (meth) acrylic polymer having a star structure is
(A) 60 wt% to 95 wt% alkyl (meth) acrylate, wherein the alkyl group has 12 to 15 carbon atoms,
(B) 5 wt% to 30 wt% alkyl (meth) acrylate in which the alkyl group has 1 to 9 carbon atoms,
(C) 0 wt% to 10 wt% dispersant monomer,
(D) 0 wt% to 5 wt%, or 0 wt% to 2 wt%, or 0 wt% vinyl aromatic monomer (typically styrene), and (e) 0 wt% where the alkyl group has 16 to 18 carbon atoms 12. having three or more arms comprising a poly (meth) acrylate polymer derived from a monomer composition comprising ˜20 wt%, or 0 wt% to 10 wt%, or 0 wt% alkyl (meth) acrylate. A composition according to 1. The linear polymer viscosity modifier having a dispersant functionality is the only dispersant viscosity modifier present in a linear (meth) acrylic polymer viscosity modifier having a dispersant functionality of 0.5 wt% to 4 wt%. The linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000,
Oil of lubricating viscosity has a kinematic viscosity and viscosity index of 104 to 130 of 2.8~3.1cSt ^(mm 2 / s) at 100 ° C., composition according to any one of claims 1 to the preceding 8. _21. The composition of any preceding claim, further comprising _C8-20 hydrocarbyl phosphite, or _C12-18 hydrocarbyl phosphite, or _C16-18 hydrocarbyl phosphite.   A composition according to any preceding claim, wherein the calcium-containing detergent is calcium sulfonate or calcium phenate.   A composition according to any preceding claim, wherein the calcium-containing detergent is calcium sulfonate. Any of the oils of lubricating viscosity having a kinematic viscosity and viscosity index of less than 110 to 120 of 2.8~3.6cSt ^(mm 2 / s) at 100 ° C., from claims 1 to 14 or 16 the preceding 17 A composition according to 1.   A method of lubricating an automatic transmission, comprising supplying the automatic transmission with a composition according to any preceding claim.