JP2017508053A - Lubricant containing a blend of polymers - Google Patents

Abstract

(A) an oil of lubricating viscosity; (b) a (meth) acrylate-containing polymer comprising a plurality of arms comprising at least 20 carbon atoms, wherein the arms are bonded to a polyvalent organic moiety (meta ) An acrylate-containing polymer; and (c) an ethylene / olefin copolymer having a weight average molecular weight of from about 10,000 to about 250,000, said copolymer comprising from about 40 to about 70 weight percent polymerized ethylene monomer. A lubricant composition comprising an ethylene / olefin copolymer comprising and optionally further comprising a polymerized propylene monomer exhibits good viscosity and antiwear properties.

Description

BACKGROUND The technology of the present disclosure relates to a lubricant formulation containing a mixture of a viscosity modifying polymer: a (meth) acrylate containing polymer containing multiple arms and an ethylene / olefin copolymer containing a polymerized propylene monomer.

  Viscosity modifiers containing star polymers and other polymers with various arms are known in the field of lubricants as viscosity index performance, low temperature performance described by Brookfield viscosity and kinematic viscosity performance at 40 ° C and 100 ° C. It is known to provide higher temperature performance as indicated by. The performance of viscosity modifiers has been observed in a wide variety of mechanical devices including hydraulic systems, driveline systems, and internal combustion engines. Olefin copolymers are also known as viscosity modifiers.

  Various applications such as engine lubricants, motorcycle lubricants (typically lubricating both engines and transmissions), driveline lubricants (manual and automatic transmissions and gears), greases and There is a continuing need to further improve the viscosity characteristics of lubricating oils in hydraulic applications. Good wear resistance or friction performance while providing a lubricant with increased (improved) viscosity index and decreased kinematic viscosity (eg at 40 ° C.) and increased (improved) high temperature high shear rate viscosity It is particularly desirable to maintain other lubricant performance characteristics that contain good or even improved. For example, in certain embodiments, such as lubricants for motorcycle engines, the lubricants described herein provide good shear stability under good operating conditions specific to motorcycle gearboxes, good One or more of gear protection and good deposit performance may be exhibited.

  EP 2610332 (Lublizol, July 3, 2013) discloses a star polymer and its lubricating composition. A star polymer has at least two inner blocks, at least one of which is then bonded to one or more outer blocks. The lubricant composition may further comprise a viscosity modifier (typically an olefin copolymer, such as an ethylene-propylene copolymer).

  US Pat. No. 8,513,176 (Baum et al., August 20, 2013) discloses a process for preparing a polymer with a chain transfer agent containing a thiocarbonyl compound. The product may be a star polymer, which may be a block arm star polymer or a heteroarm star polymer. If desired, other performance additives may be present in the lubricant, and the other performance additives contain a viscosity modifier.

  US Patent Application Publication No. 2010/0190671 (Stoehr et al., July 29, 2010) discloses the use of comb polymers to reduce fuel consumption. Lubricating oil formulations comprising comb polymers are also disclosed, which contain in the backbone at least one repeat unit derived from a polyolefin-based macromonomer. In particular, it may also contain additional additives that may be viscosity index improvers. Conventional viscosity index improvers may contain olefin copolymers, particularly poly (ethylene-co-propylene) type olefin copolymers.

US Patent Application Publication No. 2008/0015131 (Vinci et al., January 17, 2008) discloses lubricants containing olefin copolymers and acrylate copolymers. The disclosed polymer is an ethylene aliphatic olefin copolymer, wherein the aliphatic olefin contains from 3 to about 24 carbon atoms, and the copolymer has an _Mn ranging from about 600 to about 5000. Group olefin copolymer. In one embodiment, the ethylene content can be from about 20 mole percent to about 85 mole percent. Preferably the copolymer is an ethylene-propylene copolymer. The lubricant composition is said to exhibit good low temperature performance and shear stability performance. Lubricants include automatic transmission lubricants, manual transmission lubricants, and gear lubricants.

U.S. Patent Application Publication No. 2003-0036488 (Yuki et al., February 20, 2003) discloses a viscosity index improver and a lubricating oil containing a viscosity index improver. The viscosity index improver may contain monomers such as 2-decyl-tetradecyl methacrylate, 2-dodecyl-hexadecyl methacrylate or 2-decyl-tetradecyloxyethyl methacrylate.
Therefore, the disclosed technology provides for one or more various beneficial properties, such as reduced vane and ring wear in hydraulic fluid formulations and good viscosity properties, such as for engine lubricants or motorcycles. Provided is a lubricant that may have a viscosity index in the lubricant.

European Patent No. 2610332 US Pat. No. 8,513,176 US Patent Application Publication No. 2010/0190671 US Patent Application Publication No. 2008/0015131 US Patent Application Publication No. 2003-0036488

SUMMARY The disclosed technology is (a) an oil of lubricating viscosity; (b) a (meth) acrylate-containing polymer comprising a plurality of arms, wherein the arms are at least 20, or at least 50 or 100 or 200 or 350 or 500 or A (meth) acrylate-containing polymer comprising 1000 carbon atoms, wherein the arms are bonded to a polyvalent organic moiety; and (c) 5,000 to 250,000 or 10,000 to about 250,000 An ethylene / olefin copolymer having a weight average molecular weight, the copolymer comprising from about 40 to about 70 weight percent polymerized ethylene monomer, and a polymer of one or more than 3 to 6 carbon atoms Further comprising a modified olefin monomer (eg, α-olefin), Providing a lubricant composition comprising a styrene / olefin copolymer.

  The disclosed technology further provides a method of lubricating a mechanical device, the method comprising supplying the lubricant composition described above thereto.

DETAILED DESCRIPTION Various preferred features and embodiments are described below by way of non-limiting illustration.

Oil of lubricating viscosity One component of the lubricant of the present disclosure is an oil of lubricating viscosity. Such oils include natural and synthetic oils, hydrocracking processes, oils derived from hydrogenation and hydrofinishing, unrefined oils, refined oils, rerefined oils or mixtures thereof. A more detailed description of unrefined, refined and rerefined oils is provided in International Publication WO 2008/147704, paragraphs [0054]-[0056]. More detailed descriptions of natural and synthetic lubricating oils are described in paragraphs [0058] to [0059] of WO 2008/147704, respectively. Synthetic oils may also be produced by a Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas liquefaction procedure, as well as other gas liquefied oils.

グループＩ、ＩＩおよびＩＩＩは、鉱油ベースストック（ｍｉｎｅｒａｌ ｏｉｌ ｂａｓｅ ｓｔｏｃｋ）である。一実施形態において、潤滑粘度の油は、ＡＰＩグループＩの油であり得る。他の実施形態において、潤滑粘度の油は、グループＩＩもしくはグループＩＩＩの油またはグループＩからＶのうちのいずれか１つであり得る。 Oil of lubricating viscosity is also described in the April 2008 edition of “Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3 subtitle 1.3 ck. Can be defined as Oils of lubricating viscosity can also be esters. A summary of API oil classification is as follows:

Groups I, II and III are mineral oil base stocks. In one embodiment, the oil of lubricating viscosity may be an API Group I oil. In other embodiments, the oil of lubricating viscosity can be a Group II or Group III oil or any one of Groups I through V.

  The amount of oil of lubricating viscosity present is typically the residue remaining after the sum of the amount of compounds and other performance additives of the disclosed technology is reduced from 100 wt%.

  The lubricating composition may be in the form of a concentrate and / or a fully formulated lubricant. When the star polymer of the disclosed technology is in the form of a concentrate (which can be combined with additional oil to form a wholly or partially finished lubricant), the constituent star of the disclosed technology The ratio of the lubricating viscosity of the polymer to the oil and / or diluent oil includes a range of 1:99 to 99: 1 on a weight basis, or 80:20 to 10:90 on a weight basis.

(Meth) acrylate polymer having a plurality of arms The lubricant of the present disclosure also contains a (meth) acrylate-containing polymer comprising a plurality of arms, wherein the arms are at least about 20 or at least 50 or 100 or 200 or 350 or 500. Alternatively, it contains 1000 carbon atoms and the arm is attached to a multivalent organic moiety. As used herein, the term (meth) acrylate and its cognate means either methacrylate or acrylate, as will be readily understood. Thus, a multi-arm polymer can be a feature of a “star” polymer, a “comb” polymer, or a polymer having multiple arms or branches separately as described herein.

Star polymers Star polymers are known. They can be prepared by a number of routes including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT) polymerization, nitroxide mediated polymerization or anionic polymerization. A detailed discussion of ATRP can be found in Handbook of Radical Polymerization, Edited by Krzysztof Matyjaszewski and Thomas P. Davis, John Wiley and Sons, Inc. 2002 (hereinafter referred to as “Matyjazewski”), chapter 11, pages 523 to 628. See in particular Reaction Scheme 11.1 on page 524, Reaction Scheme 11.4 on page 556, Reaction Scheme 11.7 on page 571, Reaction Scheme 11.8 on page 572 and Reaction Scheme 11.9 on page 575. .

（式中、Ｒ^１は水素、または１から５個の炭素原子を含む直鎖もしくは分枝アルキル基であり、Ａは、構造（Ｉ）の残りに、その窒素または酸素原子を介して連結しているアミノまたはアルコキシ基であり、Ｙは、臭素、塩素、フッ素またはヨウ素などのハロゲンである）を有する星型ポリマーを調製するために使用することができる。ハロゲンは、重合条件下でラジカル機構によって移動することができる１個もしくは１個より多くの原子、または原子の群を含有するものを含め、開始剤などの好適なハロゲン含有化合物から誘導することができる。一実施形態では、（Ｉ）の構造は、構造（Ｉｚ）：

（式中、Ｚは、架橋ポリマー基などのポリマー基である）としてより詳細に図示することができる。ＡＴＲＰ工程に関するさらなる詳細は、米国特許第６，３９１，９９６号および米国出願第２００７／０２４４０１８号に示されており、この中で、０１３３〜０１４４段落に言及されている。 ATRP
In one embodiment, ATRP is a functional group of formula (I) as the core moiety:

Wherein R ¹ is hydrogen or a linear or branched alkyl group containing 1 to 5 carbon atoms, and A is linked to the rest of structure (I) via its nitrogen or oxygen atom. Can be used to prepare star polymers having amino or alkoxy groups, wherein Y is a halogen such as bromine, chlorine, fluorine or iodine. Halogens can be derived from suitable halogen-containing compounds such as initiators, including those containing one or more atoms, or groups of atoms, that can be transferred by a radical mechanism under polymerization conditions. it can. In one embodiment, the structure of (I) is the structure (Iz):

(Wherein Z is a polymer group such as a crosslinked polymer group) can be illustrated in more detail. Further details regarding the ATRP process are provided in US Pat. No. 6,391,996 and US Application No. 2007/0244018, in which reference is made to paragraphs 0133-0144.

  Examples of halogen-containing compounds include p-chloromethylstyrene, α-dichloroxylene, α, α-dichloroxylene, α, α-dibromoxylene and hexakis (α-bromomethyl) benzene, benzyl chloride, benzyl bromide, 1- Benzyl halides such as bromo-1-phenylethane and 1-chloro-1-phenylethane; propyl 2-bromopropionate, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, 2 A carboxylic acid derivative in which the α-position is halogenated, such as ethyl bromoisobutyrate; a tosyl halide such as p-toluenesulfonyl chloride; tetrachloromethane, tribromomethane, 1-vinylethyl chloride, 1-vinylethyl bromide, etc. Alkyl halides; and dimethyltri It includes a halogen derivatives of phosphoric acid esters such as acid.

In one embodiment, transition metals such as copper may also be present when a halogen compound is used. The transition metal may be in the form of a salt. A transition metal is one in which a metal can form a coordination bond, and the ratio of ligand to metal depends on the coordination number of the ligand and the coordination number of the metal. Dependent. The ligand is a nitrogen or phosphorus containing ligand. In one embodiment, the ligand is triphenylphosphine (PPh ₃ ), a common ligand containing phosphorus. Suitable transition metals for the triphenylphosphine ligand include Rh, Ru, Fe, Re, Ni or Pd.

RAFT
RAFT polymerization can be used when the core portion of the polymer contains a functional group of the above formula (I), in this case, Y is table via -S-C (= S) -R 5 R ⁵ can be an alkyl radical containing 1 to 20 carbon atoms. The functional group Y may be derived from a chain transfer agent or a part thereof. In certain embodiments, the core moiety is a functional group derived from a compound comprising a thiocarbonylthio group and a free radical leaving group, such as those disclosed in paragraph 0146 of U.S. Application No. 2007/0244018. Often from chain transfer agents).

  Examples of RAFT chain transfer agents include benzyl 1- (2-pyrrolidinone) carbodithioate, benzyl (1,2-benzenedicarboximide) carbodithioate, 2-cyanoprop-2-yl 1-pyrrole carbodithioate, 2-cyanobut-2-yl 1-pyrrole carbodithioate, benzyl 1-imidazole carbodithioate, N, N-dimethyl-S- (2-cyanoprop-2-yl) dithiocarbamate, N, N-diethyl-S- Benzyldithiocarbamate, cyanomethyl 1- (2-pyrrolidone) carbodithioate, cumyldithiobenzoate, N, N-diethyl S- (2-ethoxycarbonylprop-2-yl) dithiocarbamate, O-ethyl-S -(1-Phenylethyl) xanthate (Xanthate), O-ethyl-S- (2- (ethoxycarbonyl) prop-2-yl) xanthate, O-ethyl-S- (2-cyanoprop-2-yl) xanthate, O-ethyl-S- (2 -Cyanoprop-2-yl) xanthate, O-ethyl-S-cyanomethylxanthate, O-phenyl-S-benzylxanthate, O-pentafluorophenyl-S-benzylxanthate, 3-benzylthio-5,5- Dimethylcyclohex-2-ene-1-thione or benzyl 3,3-di (benzylthio) prop-2-enedithioate, S, S′-bis- (α, α′-disubstituted-α ″ -acetic acid) -Trithiocarbonate, S, S'-bis- (α, α'-disubstituted-α "-acetic acid) -trithiocarbonate or S-alkyl-S '-(- α, α′-disubstituted-α ″ -acetic acid) -trithiocarbonate, dithiobenzoic acid, 4-chlorodithiobenzoic acid, benzyldithiobenzoate, 1-phenylethyldithiobenzoate, 2-phenylprop-2-yldithiobenzoate, 1-acetoxyethyldithiobenzoate, hexakis (thiobenzoylthiomethyl) benzene, 1,4-bis (thiobenzoylthiomethyl) benzene, 1,2,4,5-tetrakis (thiobenzoylthiomethyl) benzene, 1,4- Bis- (2- (thiobenzoylthio) prop-2-yl) benzene, 1- (4-methoxyphenyl) ethyl dithiobenzoate, benzyl dithioacetate, ethoxycarbonylmethyl dithioacetate, 2- (ethoxycarbonyl) prop-2- Irdithiobenzoate, 2 , 4,4-trimethylpent-2-yldithiobenzoate, 2- (4-chlorophenyl) prop-2-yldithiobenzoate, 3-vinylbenzyldithiobenzoate, 4-vinylbenzyldithiobenzoate, S-benzyldiethoxyphosphini Rudithioformate, tert-butyltrithioperbenzoate, 2-phenylprop-2-yl 4-chlorodithiobenzoate, 2-phenylprop-2-yl 1-dithionaphthalate, 4-cyanopentanoic acid dithiobenzoate, dibenzyl Tetrathioterephthalate, dibenzyltrithiocarbonate, carboxymethyldithiobenzoate, or poly (ethylene oxide) with dithiobenzoate end groups, or mixtures thereof are included.

  RAFT polymerization is also described in greater detail in Matjajaszewski, chapter 12, pages 629-690, especially pages 664-665.

Nitroxide-mediated In the case of nitroxide-mediated polymerization, the core portion of the polymer may contain a functional group of formula (I) above, where Y is an alkyl nitroxide group —O—N (R ⁶ ) (R ⁷ ). R ⁶ and R ⁷ may be an alkyl group of 1 to 8 carbon atoms, or R ⁶ and R ⁷ may be taken together to form a ring. When using nitroxide-mediated techniques, in some cases, a satisfactory polymer uses a TEMPO-based derivative for the reason that a portion of styrene is specified in Matyjazewski, page 477, item 10.4. (For example, the amount of (meth) acrylate can be less than 50 wt% of the star polymer). Alternatively, the presence of styrene is not essential when TEMPO-based nitroxide-mediated techniques using alicyclic nitroxides or non-quaternary nitroxides are used. A list of compounds suitable for nitroxide-mediated techniques is shown in Table 10.1 on pages 479-481 of Matyjaszewski. Nitroxide-mediated polymerization is also described in paragraphs 016 to 0163 of US application 2007/0244018.

  The amount of compound used to impart a halogen, nitroxide or dithioether functional group to the core moiety is, in one embodiment, 0.001 to 0.10 mole per mole of monomer in the polymer arm; In another embodiment, from 0.001 to 0.05 mole per mole of monomer, and in yet another embodiment, from 0.001 to 0.03 mole per mole of monomer.

Anionic polymerization techniques for the preparation of anionic star polymers have also been reported. See for example WO 96/23012. Because anionic polymerization methods can prepare star polymers, including the use of highly pure solvents, a substantially water-free inert atmosphere, low reaction temperatures, and alkali metal carbanion initiators, Requires controlled conditions.

（式中、Ｅは、独立してコアの別の部分、ポリマーアームもしくはモノマー種であるか、または式（Ｉａ）によって定義されている別の構造単位であり、Ｒ^１は、水素、または１から５個の炭素原子を含む直鎖または分枝アルキル基であり、Ａは、窒素または酸素であり、Ｙは、重合条件下でラジカル機構により移動することができる、１個もしくは１個より多くの原子または原子の群からなる群から選択される遊離ラジカル脱離基、ハロゲン、ニトロキシド基あるいはジチオエステル基である）をさらに含む。構造（Ｉｚ）と同様に、構造（Ｉａ）の左に示されている結合は、通常、Ｚ基に結合することができ、この場合、Ｚは、架橋ポリマー基などのポリマー基である。 Star Polymer, Details When the (meth) acrylate-containing polymer containing multiple arms is a star polymer, the polymer is (i) a polyvalent (meth) acrylic monomer, an oligomer or polymer thereof, or a polyvalent divinyl non-polymer. It can comprise an acrylic monomer, a core portion comprising an oligomer or polymer thereof, and (ii) at least two arms of a polymerized (meth) acrylic acid alkyl ester. The core moiety is a functional group of formula (Ia):

Wherein E is independently another portion of the core, a polymer arm or monomeric species, or another structural unit as defined by formula (Ia), R ¹ is hydrogen, or 1 Is a straight chain or branched alkyl group containing from 5 to 5 carbon atoms, A is nitrogen or oxygen, and Y can be transferred by a radical mechanism under polymerization conditions, one or more Or a free radical leaving group selected from the group consisting of atoms or groups of atoms, halogens, nitroxide groups or dithioester groups. Similar to structure (Iz), the bond shown to the left of structure (Ia) can usually be bonded to a Z group, where Z is a polymer group, such as a crosslinked polymer group.

Arms The star polymer arm is itself a (meth) acrylate-containing polymer or oligomer moiety that includes a (meth) acryl moiety that condenses with an alcohol moiety to yield an alkyl group. In certain embodiments, the star polymer arms have up to 40 carbon atoms, or up to 30 carbon atoms, or 1 to 18 carbon atoms, or 1 to 15 carbons in the alkyl group. It may be formed from (meth) acrylic acid alkyl esters containing atoms, or 8 to 15, or 10 to 15, or 12 to 15 carbon atoms. In certain embodiments, one or more than one arm includes units derived from an alkyl acrylate monomer.

  In one embodiment, the (meth) acrylic acid ester is 98% to 100% in the arms of the polymerized (meth) acrylic acid alkyl ester containing 1 to 18 or 1 to 15 carbon atoms. Contains 0% to 2% alkyl groups in the arm of polymerized (meth) acrylic acid alkyl esters containing alkyl groups and containing 19 to 30 or 16 to 30 carbon atoms. ing.

  In one embodiment, the polymer arm is an alkyl ester group comprising 10 to 15 carbon atoms in which the alkyl group is present in at least 50% to 100%; the alkyl group is present in 0% to 20%, 30% or 40% An alkyl ester group containing 6 to 9 carbon atoms; an alkyl ester group containing 1 to 5 carbon atoms in which the alkyl group is present in 0 to 18% or 20% or 30%; Alkyl ester groups containing 16 to 30 (or 16 to 18) carbon atoms present at 2%; and nitrogen containing monomers present at 0 wt% to 10 wt% of the polymer arms.

  In one embodiment, the polymer arm is an alkyl ester group comprising 10 to 18 carbon atoms in which the alkyl group is present in at least 50% to 100%; the alkyl group is present in 0% to 20%, 30% or 40% An alkyl ester alkyl group containing 6 to 9 carbon atoms; an alkyl ester alkyl group containing 1 to 5 carbon atoms in which the alkyl group is present in 0 to 18% or 20% or 30%; Alkyl ester groups containing 19 to 30 carbon atoms present in% to 2%; and nitrogen containing monomers present in 0 wt% to 10 wt% of the polymer arms.

  The amount of ester alkyl group containing from 10 to 15 carbon atoms present in the star polymer is, in one embodiment, at least 50% of the alkyl group, in another embodiment, at least 60% of the alkyl group, In another embodiment, the alkyl group can be at least 70%, and in another embodiment, the alkyl group can be at least 80%. In one embodiment, the amount of ester alkyl group containing 10 to 15 carbon atoms can be at least 95% or 98%.

  The amount of ester alkyl group containing 6 to 9 carbon atoms present in the star polymer is, in one embodiment, 0% to 15% or 20% or 30% of the alkyl group, another embodiment Then, the alkyl group is 0% to 10%, and in another embodiment, the alkyl group is 0% to 5%.

  The amount of ester alkyl group containing from 1 to 5 carbon atoms present in the star polymer is, in one embodiment, 0% to 13% or 20% or 30% of the alkyl group, another embodiment Then, the alkyl group is 0% to 8%, and in another embodiment, the alkyl group is 0% to 3%.

  The amount of ester alkyl group containing 16 to 30 carbon atoms present in the star polymer is, in one embodiment, 0% to 1% of the alkyl group, and in another embodiment 0% of the alkyl group. It is.

  Examples of alkyl moieties of (meth) acrylic acid esters include methyl methacrylate, butyl methacrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) Acrylate, 2-tert-butylheptyl (meth) acrylate, 3 isopropyl heptyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5 methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2 methyl Dodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hex Decyl (meth) acrylate, 2methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyl eicosyl (meth) acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / Or derived from saturated alcohols such as eicosyltetratriacontyl (meth) acrylate; derived from unsaturated alcohols such as oleyl (meth) acrylate That (meth) acrylate; includes cycloalkyl (meth) acrylates such as well as 3-vinyl-2-butylcyclohexyl (meth) acrylate or bornyl (meth) acrylate. In certain embodiments, the alkyl portion of the ester can be derived from a β-branched alcohol having up to 30 carbon atoms.

  An ester compound having a group derived from a long-chain alcohol can be obtained, for example, by reaction of (meth) acrylic acid (by direct esterification) or methyl methacrylate (by transesterification) with a long-chain fatty alcohol. Reactions of mixtures of esters such as (meth) acrylic acid esters with groups of alcohols of various chain lengths are generally obtained.

  In one embodiment, the star polymer is further functionalized in a polymer arm with a core or nitrogen-containing monomer. Nitrogen-containing monomers can include vinyl-substituted nitrogen heterocyclic monomers, dialkylamine alkyl (meth) acrylate monomers, dialkylaminoalkyl (meth) acrylamide monomers, tertiary (meth) acrylamide monomers, or mixtures thereof.

（式中、各Ｑは独立して、水素またはメチルであり、一実施形態では、Ｑはメチルであり、各Ｒ^２は独立して、水素、または１から８個もしくは１から４個の炭素原子を含むヒドロカルビル基であり、各Ｒ^３は独立して、水素、または１から２個の炭素原子を含むヒドロカルビル基であり、一実施形態では、各Ｒ^３は水素であり、ｇは１から６の整数であり、一実施形態では、ｇは１から３である）を含むことができる。 In one embodiment, the core or polymer arm is a (meth) acrylamide or (meth) acrylate monomer of formula (IIa) or (IIb), respectively:

Wherein each Q is independently hydrogen or methyl, and in one embodiment, Q is methyl and each R ² is independently hydrogen, or 1 to 8 or 1 to 4 carbons. A hydrocarbyl group containing atoms, wherein each R ³ is independently hydrogen, or a hydrocarbyl group containing 1 to 2 carbon atoms, and in one embodiment, each R ³ is hydrogen and g is from 1 to 6 and in one embodiment g is 1 to 3).

  Examples of suitable nitrogen-containing monomers include vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidinone and N-vinyl caprolactam, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate, dimethylamino Propylacrylamide, dimethylaminopropyl ethacrylamide, dimethylaminoethylacrylamide or mixtures thereof are included.

  In one embodiment, the polymer is reacted using an acylating agent and an amine by copolymerizing or grafting onto or within the arm or core to produce a dispersible viscosity modifier (often a DVM And such materials are named as such because they exhibit both dispersion and viscosity modifying properties.

  In one embodiment of the invention, the polymer arm or core (described below) is copolymerized or grafted onto or within the arm or core using an acylating agent, an amine or a mixture thereof. To functionalize. Examples of acylating agents for grafting include unsaturated carboxylic acids such as maleic anhydride, (meth) acrylic acid or itaconic acid or anhydrides or derivatives thereof, which are then nitrogenous such as amines. Can be reacted with a compound. In one embodiment, the acylating agent is a dicarboxylic acid or anhydride. Examples of dicarboxylic acids or anhydrides include itaconic anhydride, maleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, dimethylmaleic anhydride, or mixtures thereof.

（式中、Ｈｙは、アルキレンまたはＣ１〜４アルキレンまたはＣ２アルキレンなどのヒドロカルビレン基であり、Ｈｙ’およびＨｙ”はそれぞれ独立して、水素、またはアルキルもしくはＣ１〜４アルキルもしくはＣ２アルキルなどのヒドロカルビル基であり、Ｑは、＞ＮＨ、＞ＮＲ、＞ＣＨ_２、＞ＣＨＲ、＞ＣＲ_２または−Ｏ−であり、Ｒは、Ｃ１〜４アルキルであり、「＞」は、２つの結合を表す）によって表される、イミダゾリジノン、環式カルバメートまたはピロリジノン（ｐｙｒｒｏｌｄｉｎｉｎｏｎｅ）を含むことができる。通常、Ｑは、＞ＮＨまたは＞ＮＲとすることができる。一実施形態では、アミン化合物はイミダゾリノンとすることができ、これは、１−（２−アミノ−エチル）−イミダゾリジン−２−オン（アミノエチルエチレンウレアと呼ぶこともできる）、１−（３−アミノ−プロピル）−イミダゾリジン−２−オン、１−（２−ヒドロキシ−エチル）−イミダゾリジン−２−オン、１−（３−アミノ−プロピル）−ピロリジン−２−オン、１−（３−アミノ−エチル）−ピロリジン−２−オンまたはそれらの混合物を含むことができる。 In one embodiment, polymer b further reacts with an amine to form a condensed species, such as an amide group, which is a chemical species a that has dispersion properties. Examples of amines include aminohydrocarbyl substituted amines such as 4-aminodiphenylamine, hydrocarbyl substituted morpholines such as 4 (3-aminopropyl) morpholine or 4- (2-aminoethyl) morpholine, or dimethylaminoalkyl (meth) acrylate Of dialkylaminoalkyl (meth) acrylate, or N-vinylpyrrolidinone. In one embodiment, the alkyl group of dimethylaminoalkyl (meth) acrylate is propyl and in another embodiment ethyl. In certain embodiments, the amine compound has the structure

Wherein Hy is alkylene or a hydrocarbylene group such as C1-4 alkylene or C2 alkylene, and Hy ′ and Hy ″ are each independently hydrogen, or alkyl or C1-4 alkyl or C2 alkyl, etc. A hydrocarbyl group, Q is>NH,>NR,> CH ₂ ,>CHR,> CR ₂ or —O—, R is C 1-4 alkyl, and “>” represents two bonds. Imidazolidinone, cyclic carbamate or pyrrolidinone represented by Usually Q can be> NH or> NR. In one embodiment, the amine compound can be imidazolinone, which is 1- (2-amino-ethyl) -imidazolidin-2-one (also referred to as aminoethylethyleneurea), 1- ( 3-amino-propyl) -imidazolidin-2-one, 1- (2-hydroxy-ethyl) -imidazolidin-2-one, 1- (3-amino-propyl) -pyrrolidin-2-one, 1- ( 3-amino-ethyl) -pyrrolidin-2-one or mixtures thereof.

  In one embodiment, the polymer arm of the star polymer is 2 or less, in another embodiment 1.7 or less, in another embodiment 1.5 or less, for example 1 to 1.4. Of polydispersity. In one embodiment, the star polymer has a polydispersity with a bimodal or higher mode distribution. Bimodal or higher distributions indicate the presence of varying amounts of uncoupled polymer chains and / or uncoupled star polymers, or stars and stars formed when the polymer is prepared. This may be due in part to the coupling with the mold.

  In one embodiment, the star polymer has at least 3 arms, in another embodiment, more than 5 arms, in another embodiment, more than 7 arms, in another embodiment, more than 10 arms. It has many arms, for example 12 to 100, 14 to 50, or 16 to 40 arms. In one embodiment, the star polymer has 120 or fewer arms, in another embodiment 80 or fewer arms, and in another embodiment 60 or fewer arms. In certain embodiments, there may be 3 to 20, 5 to 20, or 6 to 15, or 7 to 8 arms per star.

  The portion of the star polymer, when formed, may have uncoupled polymer arms present (also referred to as polymer chains or linear polymers). In one embodiment, the conversion of polymer chains to star polymer is at least 10%, in another embodiment at least 20%, in another embodiment at least 40%, in another embodiment at least 55%. For example 70%, 75% or 80%. In one embodiment, the conversion of polymer chains to star polymers is about 90%, 95%, or 100%. In one embodiment, a portion of the polymer chain does not form a star polymer and remains as a linear polymer. In one embodiment, the linear polymer is substantially free or free of halogen, nitroxide groups or dithioether groups. In one embodiment, the linear polymer has a composition and weight average molecular weight that is substantially similar or identical to an arm of a star polymer containing a polymerized (meth) acrylic acid alkyl ester.

  In one embodiment, one or more arms of the star polymer is a diblock AB type copolymer, in another embodiment, a triblock ABA type copolymer, in another embodiment, a tapered block polymer, In another embodiment, it is an alternating polymer.

  The star polymer in one embodiment is a block arm star (co) polymer (where “(co) polymer” is used to mean “polymer or copolymer”), In embodiments, a hetero-arm star (co) polymer (described below), and in another embodiment, the star polymer is a tapered arm copolymer. Tapered arm copolymers have various compositions along the length of the polymer chain. For example, a tapered arm copolymer is composed of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle part of the polymer arm is rather a graded composition of the above two monomers. Tapered block copolymers can be coupled to form block arm star polymers.

  Block arm star (co) polymers contain one or more polymer arms derived from two or more monomers in the same arm. A more detailed description of block-arm star polymers can be found in Henry Hsieh and Roder Quirk, “Anionic Polymerization, Principles and Practical Applications” (Marcel Dekker, Inc., et al., New York, 19). Chapter 13 (pp. 333-368).

  Heteroarm or “mikto arm” star polymers are described in Hsieh et al. Contains arms that may be of varying molecular weight, composition, or both, as defined in. For example, a portion of a given star polymer arm can be part of one polymer type and part of a second polymer type. More complex heteroarm star polymers can be formed by combining parts of three or more polymer arms with a coupling agent.

  In certain embodiments, the arms may be random copolymers. In certain embodiments, they are alkyl methacrylates 73 to 85 or 78 to 84 weight percent predominantly or exclusively 12 to 25 carbon atoms in the alkyl group, methyl methacrylate monomers 14 to 25 or 16 to 20 weights. Percent, and alkyl methacrylate monomers having C6 to C10 carbon atoms in the alkyl group (such as 2-ethylhexyl methacrylate) 0.05 to 10, or 0.1 to 3, or 0.5 to 2 weight percent copolymer be able to.

Core In star polymers, the polymer arm is attached to (or radiates from) the core, which core usually has a polymer or oligomeric structure itself. The core portion can be a polyvalent (meth) acrylic monomer, oligomer or polymer thereof, or a polyvalent divinyl non-acrylic monomer, oligomer or polymer thereof. The polyvalent monomer, its oligomer or polymer can be used alone or as a mixture.

  In one embodiment, the polyvalent divinyl non-acrylic monomer is divinylbenzene. In one embodiment, the polyvalent (meth) acrylic monomer is an acrylic ester or methacrylic ester of a polyol, or a polyamine methacrylamide such as a polyamine amide, such as methacrylamide or acrylamide. In one embodiment, the polyvalent (meth) acrylic monomer is an acrylic or methacrylic polyol, or a polyamine condensation product.

  The polyol comprises in one embodiment 2 to 20 or in another embodiment 3 to 15 or 4 to 12 carbon atoms. The number of hydroxyl groups present is 2 to 10 in one embodiment, 2 to 4 in another embodiment, and 2 in another embodiment. Examples of polyols include triols such as ethylene glycol, poly (ethylene glycol), alkanediols such as 1,6-hexanediol, or trimethylolpropane or oligomerized trimethylolpropane. Examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyalkylenepolyamines such as pentaethylenehexamine, and mixtures thereof.

  Examples of polyunsaturated (meth) acrylic monomers include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol diacrylate, glycerol triacrylate, mannitol hexaacrylate, 4-cyclohexanediol di- Acrylate, 1,4-benzenediol dimethacrylate, pentaerythritol tetraacrylate, 1,3-propanediol diacrylate, 1,5-pentanediol dimethacrylate, bisacrylate and methacrylate of polyethylene glycol having a molecular weight of 200 to 4000, polycaprolactone diol Diacrylate, pentaerythritol triacrylate, 1,1,1-to Methylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,1,1-trimethylolpropane trimethacrylate, hexamethylenediol diacrylate or Hexamethylenediol dimethacrylate or alkylene bis- (meth) acrylamide is included.

  The amount of polyvalent coupling agent is an amount suitable for coupling a polymer already prepared as an arm onto a core containing a coupling agent in monomeric, oligomeric or polymeric form, resulting in a star polymer. It can be. As noted above, suitable amounts can be readily determined by one of ordinary skill in the art with minimal experimentation, even if several variables may be involved. For example, crosslinking can occur rather than star formation if an excess of coupling agent is used or if excess unreacted monomer from the formation of polymer arms remains in the system. Typically, the molar ratio of polymer arm to coupling agent is 50: 1 to 1.5: 1 (or 1: 1), or 30: 1 to 2: 1, or 10: 1 to 3: 1, or 7 : 1 to 4: 1, or 4: 1 to 1: 1. In other embodiments, the molar ratio of polymer arm to coupling agent can be 50: 1 to 0.5: 1, or 30: 1 to 1: 1, or 7: 1 to 2: 1. . The desired ratio can also be adjusted to take into account the length of the arm, with longer arms sometimes allowing or requiring more coupling agent than shorter arms. To do. In certain embodiments, 1 to 5 parts by weight, or 2 to 4 or 2.5 to 3 parts by weight of a coupling agent (such as ethylene glycol dimethacrylate) is used to provide 100 parts by weight of (meth) acrylate monomer. Can be reacted with a preformed arm prepared by If desired, the polymers prepared by coupling the arm and coupling agent may be added to various monomers such as additional acrylate or methacrylate monomers such as methyl methacrylate, methyl acrylate, ethyl hexyl methacrylate, ethyl hexyl acrylate or lauryl methacrylate. It may be further treated with or reacted with. Such further processing can be in relatively small amounts of such monomers, for example 0.05 to 2 or 0.5 to 1.5 weight percent. Typically, the prepared material is soluble in oils of lubricating viscosity.

  In certain embodiments, each star polymer arm is independently from 4,000 to 200,000, or 10,000 to 100,000, or 15,000 to 50,000, or 10,000. It can have a number average molecular weight of 200,000, or 20,000 to 100,000, or 35,000 to 50,000.

In one embodiment, the star polymer as a whole is 5000 to 1,000,000, in another embodiment 10,000 to 1,000,000, in another embodiment 10,000 to 600,000, In another embodiment, it has a weight average molecular weight (M _w ) of 15,000 to 500,000 or 8,000 to 1,000,000 or 8,000 to 700,000. Examples of suitable M _w include 15,000 to 350,000, 15,000 to 50,000, 150,000 to 280,000, or 25,000 to 140,000 or 280,000 or 600,000. included.

In one embodiment, the star polymer as a whole is greater than 1.3 or 2, in one embodiment greater than 3 or 3, in another embodiment 4 or greater than 4, in another embodiment 5 or Polydispersity (M _w / M _n ) greater than 5. The upper range for polydispersity can include 30 or 20 or 15 or 10. Examples of suitable ranges include 1.3 to 30, 3 to 15 or 1.3 to 10. In one embodiment, the star polymer comprises a mixture of star polymer and linear polymer. The polydispersity of the mixture is the same as, similar to, or slightly greater than the range just described.

Comb Polymer In another embodiment, the (meth) acrylate-containing polymer comprising a plurality of arms can be a comb polymer, as described in more detail in US Pat. No. 8,067,349. Such materials may include a backbone from which the arms are radial. The backbone is styrene or substituted styrene, an alkyl (meth) acrylate having 1 to 10 carbon atoms in an alcohol (alkyl) group, a vinyl ester, a vinyl ether, and claim 1, US Pat. No. 8,067,349. Repeating units derived from low molecular weight monomers, such as others, can be included. There are also a plurality of polyolefin-based macromonomers that may have a number average molecular weight in the range of 700 to 10,000, and may also contain non-olefin monomers. Macromonomers usually have exactly one polymerizable double bond, which may be a terminal bond. For example, cationic polymerization of isobutylene can form polyisobutylene with terminal double bonds. Typical macromonomers are obtained by reacting macroamines (long chain amines) or macroalcohols (long chain alcohols, each based on a polyolefin) with methyl methacrylate by aminolysis or transesterification. Can be prepared. Further details of their synthesis are reported in the aforementioned US 8,067,349. The molecular weights and compositions of the above-mentioned branched bodies for star polymers can also be applied to the branched bodies of comb polymers.

  Other polymers having multiple arms include those described in US application 2003-0036488 (Yuki et al., February 20, 2003). The materials disclosed therein can include polymers prepared from monomers such as 2-decyl-tetradecyl methacrylate, 2-dodecyl-hexadecyl methacrylate or 2-decyl-tetradecyloxyethyl methacrylate. These specific monomers can have arms with 20 to 30 or 24 to 28 carbon atoms and can also contain ether functional groups. In some embodiments, these arms have a branch at the β-position. In some embodiments, the alcohol from which they are derived is referred to as Gerve alcohol. Gerve alcohol usually has one or more carbon chains with a branch at the β-position or higher. Gerve alcohol can generally contain 10 to 60, or 12 to 60, or 16 to 40, or 20 to 30 carbon atoms in various embodiments. A method for preparing Gerve alcohol is disclosed in US Pat. No. 4,767,815 (see column 5 line 39 to column 6 line 32). Accordingly, longer arms may also be used.

  In some embodiments, for example, if a (meth) acrylate-containing polymer having multiple arms (but not exclusively) is in the form of a comb polymer, the arms can include hydrocarbyl groups; Or it may contain hydrocarbyl monomer units. In one embodiment, the arm may be a polymer entity comprising conjugated diene monomer units (optionally hydrogenated) or isobutylene monomer units. In one embodiment, the conjugated diene can comprise butadiene, ie 1,3-butadiene or isoprene. (The expression “comprising a [some] monomer unit”, as used herein, is intended to refer to a monomer unit polymerized by polymerization, or a unit derived from the indicated monomer. (It is understood that the original unpolymerized form of the monomer units is usually not present in any significant amount and is not intended to imply the opposite.)

  The amount of (meth) acrylate-containing polymer comprising a plurality of arms is 0.1 to 5 weight percent or 0.1 to 2.5 weight percent, or 0.25 to 5 weight percent, or 0.25 to 2.5 weight percent. Present in the lubricating composition in an amount of weight percent, or 0.5 to 4, or 1 to 3.5, or 1.3 to 3.4 weight percent. It may be provided as a concentrate in oil or other medium, in which case the amount in the concentrate is accordingly high, such as 1 to 25, or 2.5 to 25 or 50 weight percent Become.

The olefin copolymer lubricant composition may also be from 5,000 to 250,000 or 10,000 to 250,000, or alternatively 10,000 to 200,000 or 20,000 to 180,000 or 15,000 to 150,000. Or a second polymer which is an ethylene / olefin copolymer having a weight average molecular weight of 20,000 to 100,000 or 20,000 to 80,000, or alternatively 100,000 to 200,000 or 100,000 to 180,000 Containing. The polymer may also be in the form with long arms, but it may also be a more conventional linear or branched structure.

  The second copolymer itself, the ethylene-olefin copolymer, contains 40 to 75 or 40 to 70 weight percent polymerized ethylene monomer and is a polymer of one or more than 3 to 6 carbon atoms. Further comprising a modified olefin monomer. In certain embodiments, the olefin monomer can include at least one of propylene monomer units or butylene monomer units, and in one embodiment can include propylene monomer units. In certain embodiments, the second polymer can comprise 40 to 50 weight percent ethylene monomer units and 50 to 60 weight percent other olefin monomer units such as propylene monomer units. Other monomers such as optionally hydrogenated non-conjugated diene units may also be present, usually in an amount of 0 to 10 percent by weight, or 1 to 5 percent.

  The amount of ethylene / olefin copolymer in the fully formulated lubricant is 0.03 to 1, or 0.05 to 0.5, or 0.1 to 0.4, or 0.1 to 10, or 0. .1 to 2.5 weight percent. It may be provided as a concentrate in oil or other media, in which case its amount in the concentrate will be increased accordingly, such as 5 to 15 weight percent. Both polymers may be present in the same concentrate in specified amounts.

  Suitable olefin copolymers are well known and are described, for example, in US application 2008/0015131 (Vinci et al.). Such polymers are commercially available as Lucant ™ polymer, Triline ™ polymer, Nordel ™ polymer, Paratone ™ polymer, Lubrizol® 70XY series of polymers, and Royalene ™ polymer.

Thus, the aliphatic olefin copolymer may comprise an ethylene-aliphatic olefin copolymer, wherein the aliphatic olefin, usually an alpha olefin, comprises from 3 to 24 carbon atoms, said copolymer comprising from 800 to 4000 or It has a Mn of 500 to 5000, such as 2000 to 4000. At least some propylene monomer is usually present. The polydispersity (M _w / M _n ) can be from 1.1 to 3, such as from 1.3 to 2.5 or from 2.0 to 2.4. Such polymers can be formed by copolymerization of ethylene with one or more aliphatic olefins under conditions known in the art. Examples include polymerizations performed using a Ziegler-Natta catalyst or a metallocene catalyst.

Other components Other components commonly used in lubricants may also be present. One such material can be an overbased detergent. Others, overbased materials, referred to as overbased or superbasic salts, generally neutralize the metal content according to the stoichiometry of the metal and the particular acidic organic compound that reacts with the metal. It is a single-phase homogeneous Newtonian system characterized by being in excess of that present. An overbased substance is an acidic substance (usually an inorganic acid such as carbon dioxide or a lower carboxylic acid), an acidic organic compound, at least one inert organic solvent for the acidic organic substance (mineral oil, naphtha, toluene). , Xylene, etc.), a reaction medium containing a stoichiometric excess metal base, and a mixture containing a promoter such as phenol or alcohol. Acidic organic materials typically have a sufficient number of carbon atoms to provide some degree of solubility in the oil. The amount of excess metal is generally expressed as a metal ratio. The term “metal ratio” is the ratio of the total equivalent of metal to the equivalent of acidic organic compound. Neutral metal salts have a metal ratio of 1. A salt with 4.5 times more metal than is present in a normal salt will have a 3.5 equivalent excess of metal, or a ratio of 4.5.

  Such overbased materials are well known to those skilled in the art. They are useful for a variety of purposes when used in engine lubricants, including cleansing and neutralization of acidic byproducts of combustion. They can also provide friction control or corrosion control. Patents describing techniques for making sulfonic acid, carboxylic acid, phenol, phosphonic acid basic salts, and any two or more mixtures thereof include US Pat. No. 2,501,731. No. 2,616,905, No. 2,616,911, No. 2,616,925, No. 2,777,874, No. 3,256,186, No. 3 No. 3,384,585, No. 3,365,396, No. 3,320,162, No. 3,318,809, No. 3,488,284 and No. 3,629,109. Is included. Other detergents include salixarate detergents. They and their methods of preparation are described in more detail in US Pat. No. 6,200,936 and PCT Publication WO 01/56968. Similarly, salicylate detergents described in more detail in US Pat. Nos. 4,710,023 and 3,372,116 are also known. In one embodiment, the lubricant comprises an overbased sulfonate detergent, an overbased phenol-containing detergent, or a mixture thereof.

  The amount of detergent in a fully formulated lubricant, if present, can be 0.01 to 15 weight percent, or 0.1 to 5, or 0.5 to 2, or 1 to 3 percent. it can.

（式中、各Ｒ^１は独立して、アルキル基、多くの場合、ポリイソブチレン前駆体に基づいて５００〜５０００の分子量（Ｍｎ）を有するポリイソブチレン基であり、Ｒ^２は、アルキレン基、一般には、エチレン（Ｃ_２Ｈ_４）基である）を含む、様々な化学構造を有する、Ｎ置換長鎖アルケニルスクシンイミドが含まれる。こうした分子は、一般に、アルケニルアシル化剤とポリアミンとの反応に由来しており、様々なアミドおよび第四級アンモニウム塩を含む、上で示されている単純なイミド構造の他に、上記２つの部分の間の幅広い様々な連結部が可能である。上記の構造では、アミン部分は、ポリエチレンポリアミンなどのアルキレンポリアミンとして示されているが、アミノジフェニルアミンなどの他の脂肪族ならびに芳香族モノアミンおよびポリアミンもまた使用することができる。同様に、様々な環式連結部を含む、イミド構造上のＲ^１基の様々な様式の連結部が可能である。分散剤は、塩素の使用を含むプロセス、または熱的な「エン」プロセス、もしくは遊離ラジカルプロセスによって形成することができる。Ｒ^１基（例えば、ポリイソブチレン基）に結合しているコハク酸基の平均数は、ある特定の実施形態では、１．１から２．０、または１．１５から１．３５、１．３０から１．８、または１．４から１．７とすることができる。アシル化剤のカルボニル基とアミンの窒素原子との比は、１：０．５から１：３とすることができ、他の例では、１：１から１：２．７５または１：１．５から１：２．５とすることができる。スクシンイミド分散剤は、米国特許第４，２３４，４３５号および同第３，１７２，８９２号、ならびにＥＰ０３５５８９５に一層十分に記載されている。 Dispersants are also well known additives in the field of lubricants, including mainly those known as ashless dispersants and polymer dispersants. Ashless dispersants are so called because they do not contain metal as provided and therefore do not normally contribute to sulfated ash when added to lubricants. However, they can, of course, interact with surrounding metals when added to lubricants containing metal-containing species. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants usually include

Wherein each R ¹ is independently an alkyl group, often a polyisobutylene group having a molecular weight (Mn) of 500 to 5000 based on the polyisobutylene precursor, and R ² is an alkylene group, generally Includes N-substituted long chain alkenyl succinimides having various chemical structures, including ethylene (C ₂ H ₄ ) groups. Such molecules are generally derived from the reaction of an alkenyl acylating agent with a polyamine, and in addition to the simple imide structure shown above, including various amides and quaternary ammonium salts, A wide variety of connections between the parts is possible. In the above structure, the amine moiety is shown as an alkylene polyamine such as a polyethylene polyamine, but other aliphatic and aromatic monoamines and polyamines such as aminodiphenylamine can also be used. Similarly, various types of linkages of the R ¹ group on the imide structure are possible, including various cyclic linkages. The dispersant can be formed by a process involving the use of chlorine, or a thermal “ene” process, or a free radical process. The average number of succinic groups attached to R ¹ groups (eg, polyisobutylene groups) is 1.1 to 2.0, or 1.15 to 1.35, 1.30 in certain embodiments. To 1.8, or 1.4 to 1.7. The ratio of the carbonyl group of the acylating agent to the nitrogen atom of the amine can be from 1: 0.5 to 1: 3, in other examples from 1: 1 to 1: 2.75 or 1: 1. 5 to 1: 2.5. Succinimide dispersants are more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892, and EP 0355895.

  Another class of ashless dispersants are high molecular weight esters. These materials are similar to the succinimides described above, except that they can be considered prepared by reaction of a hydrocarbyl acylating agent with a polyhydric aliphatic alcohol such as glycerol, pentaerythritol or sorbitol. Yes. Such materials are described in more detail in US Pat. No. 3,381,022.

  Another class of ashless dispersant is Mannich bases. These are substances formed by the condensation of higher molecular weight alkyl-substituted phenols, alkylene polyamines and aldehydes such as formaldehyde. Such materials are described in more detail in US Pat. No. 3,634,515.

  Other dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers that contain polar functional groups that impart characteristic dispersibility to the polymer.

  The dispersant can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, succinic anhydrides substituted with hydrocarbons, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such processing are listed in US Pat. No. 4,654,403. In one embodiment, the lubricant composition includes at least one boron-containing dispersant.

  The amount of dispersant in a fully formulated lubricant of the present technology can be at least 0.1%, or at least 0.3% or 0.5% or 1% of the lubricant composition In certain embodiments, it can be at most 9%, or 8%, or 6%, or 4%, or 3%, or 2% by weight.

The lubricant may also contain a metal salt of phosphoric acid. Formula ^{[(R 8 O) (R} 9 O) P (= S) -S] n -M
Where R ⁸ and R ⁹ are independently hydrocarbyl groups containing 3 to 30 carbon atoms, heating phosphorus pentasulfide (P ₂ S ₅ ) and alcohol or phenol. And can be easily obtained by forming O, O-dihydrocarbyl phosphorodithioic acid. The alcohol that reacts to yield the R ⁸ and R ⁹ groups can be a mixture of alcohols, for example, a mixture of isopropanol and 4-methyl-2-pentanol, and in some embodiments, isopropanol and 2- It can be a mixture of a secondary alcohol and a primary alcohol, such as ethylhexanol. Other alcohols can include secondary butyl alcohol or isooctyl alcohol. The resulting acid can react with a basic metal compound to form a salt. The metal M having a valence n is generally aluminum, lead, tin, manganese, cobalt, nickel, zinc or copper, and in many cases zinc which forms zinc dialkyldithiophosphate. Such materials are well known and readily available to those skilled in the art of lubricant formulations. Suitable modifications that result in good phosphorus retention in the engine are disclosed, for example, in US Published Application 2008-0015129, see for example the claims.

  The amount of phosphorus acid metal salt in the fully formulated lubricant, if present, is typically 0.1 to 4 weight percent, such as 0.5 to 2 weight percent or 0.75 to 1.25 weight percent. Percent. The amount is, in some embodiments, an amount that provides phosphorus to the lubricant at 0.01 to 0.15 weight percent, or 0.03 to 0.08, or 0.03 to 0.06 weight percent. be able to.

  Another component that can be used is an auxiliary viscosity modifier, which is shown above in addition to the polymer viscosity modifier combinations of the disclosed technology. Viscosity modifiers (VM) and dispersible viscosity modifiers (DVM) are well known. Examples of VM and DVM are polymethacrylates, polyacrylates, polyolefins, vinyl hydride aromatic-diene copolymers (eg styrene-butadiene, styrene-isoprene), styrene-maleic acid ester copolymers, and homopolymers, copolymers and graft copolymers Similar polymeric materials can be included. The DVM can include nitrogen-containing methacrylate polymers, such as nitrogen-containing methacrylate polymers derived from methyl methacrylate and dimethylaminopropylamine.

  Examples of commercially available VMs, DVMs and their chemical types are: polyisobutylene (such as Indopol ™ from BP Amoco or Parapol ™ from ExxonMobil); olefin copolymer (Lublizol ™ 7060 from Lubrizol), 7065 and 7067, and Lucant ™ HC-2000L and HC-600 from Mitsui; hydrogenated styrene-diene copolymers (Shellvis ™ 40 and 50 from Shell, and LZ® 7308 from Lubrizol. A dispersible copolymer, such as a styrene / maleate copolymer (such as LZ® 3702 and 3715 from Lubrizol); Polymethacrylates with dispersive properties (Viscoplex ™ series from RohMax, Hitec ™ series of viscosity index improvers from Afton, and LZ® 7702, LZ® 7727, LZ from Lubrizol (R) 7725 and LZ (R) 7720C); olefin grafted polymethacrylate polymers (such as Viscoplex® 2-500 and 2-600 from RohMax); and hydrogenated polyisoprene star polymers (from Shell). Shellvis ™ 200 and 260, etc.). Viscosity modifiers that can be used are described in US Pat. Nos. 5,157,088, 5,256,752, and 5,395,539. The VM and / or DVM can be used in the functional fluid at a concentration of up to 20% by weight. Concentrations from 1 to 12% or 3 to 10% by weight can be used.

（式中、Ｒ^３は、例えば、１から１８個、または２から１２個、または２から８個、または２から６個の炭素原子を含むアルキル基などのヒドロカルビル基であり、ｔ−アルキルはｔ−ブチルとすることができる）の酸化防止剤などのエステル含有基により占有されている。こうした酸化防止剤は、米国特許第６，５５９，１０５号に、より詳細に記載されている。 Another component can be an antioxidant. Antioxidants include phenolic antioxidants, which are sterically hindered phenols in which one or both of the ortho positions of the phenol ring are occupied by bulky groups such as t-butyl. Antioxidant. The para position may also be occupied by a hydrocarbyl group or a group that bridges two aromatic rings. In certain embodiments, the para position can be, for example, a formula

Wherein R ³ is a hydrocarbyl group such as an alkyl group containing, for example, 1 to 18, or 2 to 12, or 2 to 8, or 2 to 6 carbon atoms; occupied by ester-containing groups such as antioxidants (which can be t-butyl). Such antioxidants are described in more detail in US Pat. No. 6,559,105.

  Antioxidants also include aromatic amines. In one embodiment, the aromatic amine antioxidant can comprise an alkylated diphenylamine, such as nonylated diphenylamine, or a mixture of dinonylated diphenylamine and monononylated diphenylamine. Other amine antioxidants include phenyl naphthylamine and alkylated phenyl naphthylamine.

  Antioxidants also include monosulfides or disulfides, or mixtures thereof, for example, sulfurized olefins such as sulfurized diisobutylene or sulfurized α-olefins. These materials generally have a sulfide linkage of 1 to 10, for example 1 to 4, or 1 or 2 sulfur atoms. Materials that can be sulfurized to form the sulfurized organic compositions of the present invention include oils, fatty acids and esters, olefins and polyolefins made therefrom, terpenes, or Diels-Alder adducts. Details of methods for preparing some of these sulfide materials can be found in US Pat. Nos. 3,471,404 and 4,191,659.

  Molybdenum compounds can also act as antioxidants, and these materials can also serve in various other functions such as anti-wear or friction modifiers. U.S. Pat. No. 4,285,822 combines a polar solvent, an acidic molybdenum compound and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex, which is contacted with carbon disulfide to contain molybdenum and sulfur. Disclosed is a lubricating oil composition containing a molybdenum and sulfur containing composition prepared by forming the composition. Molybdenum dithiocarbamate and other molybdenum compounds are commercially available. In addition, titanium compounds such as titanium alkoxides such as titanium 2-ethylhexoxide or titanium carboxylates such as neodecanoate can provide various benefits, including antioxidant and anti-wear performance.

  Dithiocarbamates can also act as antioxidants.

  The typical amount of antioxidant will, of course, depend on the specific antioxidant and its individual potency, but exemplary total amounts are from 0.01 to 5 weight percent, or from 0.15 to 4. It can be 5 percent, or 0.2 to 4 percent, or 0.5 to 2 percent, or 0.05 to 0.1 percent.

  Another additive is an antiwear agent. Examples of antiwear agents include phosphorus-containing antiwear / extreme pressure agents such as metal thiophosphates, phosphate esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers and amides, and phosphites. In certain embodiments, the phosphorus antiwear agent is 0.01 to 0.2, or 0.015 to 0.15, or 0.02 to 0.1, or 0.025 to 0.08 percent phosphorus. Can be present in amounts. In some embodiments, the antiwear agent can comprise an ashless (metal free) dithiophosphate. In many cases, the antiwear agent is zinc dialkyldithiophosphate (ZDP) as described above. For a typical ZDP, this can include 11 percent P (calculated on an oil-free basis), and suitable amounts can include 0.09 to 0.82 percent. Phosphorus-free antiwear agents include boric acid esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.

  Other materials that can be used as antiwear agents (also called ashless antiwear agents) include tartaric acid esters, tartaramides, and tartarimides. Examples include oleyl tartarimide (an imide formed from oleylamine and tartaric acid) and oleyl diester (eg, from mixed C12-16 alcohols). Other related materials that may be useful generally include acids such as hydroxy-polycarboxylic acids such as tartaric acid, malic acid, citric acid, lactic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, and mixtures thereof. , Esters of other hydroxy-carboxylic acids, amides and imides. These materials can also impart additional functionality to the lubricant beyond its anti-wear performance. These materials are described in more detail in US Publication No. 2006-0079413 and PCT Publication WO 2010/077630. Such derivatives of hydroxy-carboxylic acid (or compounds derived from hydroxy-carboxylic acid), if present, are from 0.1% to 5%, or from 0.2% to 3%, or 0.2% It can usually be present in a lubricating composition in an amount of greater than 3% to 3% by weight.

Another component that can be used in the compositions used in the art is a friction modifier. Friction modifiers are well known to those skilled in the art. A list of friction modifiers that can be used is given in U.S. Pat. Nos. 4,792,410, 5,395,539, 5,484,543, and 6,660,695. include. U.S. Pat. No. 5,110,488 discloses metal salts of fatty acids, especially zinc salts, useful as friction modifiers. For a list of friction modifiers that can be useful,
Fatty phosphites Boronated alkoxylated fatty amines Fatty acid amides Metal salts of fatty acids Fatty epoxides Sulfurized olefins Boronated fatty epoxides Fatty amine carboxylic acids other than fatty amines discussed on fatty imidazolines and polyalkylene-polyamines Glycerol esters such as glycerol oleate Metal salts of alkyl salicylates Borated glycerol esters Alkyl phosphate amine salts Alkoxylated fatty amines Ethoxylated alcohol oxazolines Imidazoline hydroxyalkylamides Polyhydroxy tertiary amines Dialkyl tartrate Molybdenum compounds and their 2 A seed or a mixture of more than two can be included. When a lubricant is used to lubricate a device that includes a wet (lubricated) clutch, it controls the amount of slip between the components of the clutch, ie at the friction plate-steel interface There may be additives that provide a relatively high and stable coefficient of friction between the clutch components. Such materials can be borated dispersants, certain phosphorus-containing compounds, and certain amide compounds. Other materials that may be useful in providing such performance may include branched alkyl sulfonate calcium detergents and calcium alkyl phenate detergents.

  Other additives that may optionally be used in lubricating oils include pour point depressants, extreme pressure agents, antiwear agents, color stabilizers, demulsifiers, rust inhibitors, metal deactivators, and antifoaming agents. 1 type or more than 1 type.

  Antifoaming agents, also known as antifoaming agents, are known in the art and include, but are not limited to, organosilicones and non-silicon antifoaming agents. Some examples of organosilicones include dimethyl silicone and polysiloxane. Some examples of non-silicon antifoaming agents include copolymers of ethyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate, copolymers of 2-ethylhexyl acrylate and vinyl acetate, polyethers, polyacrylates, and mixtures thereof It is. In some embodiments, the antifoaming agent can be a polyacrylate. The antifoaming agent can be present in the lubricant composition in an amount of 0.001 to 0.012 weight percent or 0.004 percent, or 0.001 to 0.003 weight percent.

  Demulsifiers are known in the art and include, but are not limited to, propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, aminoalcohols, diamines, reacted sequentially with ethylene oxide or substituted ethylene oxide or mixtures thereof. Or a derivative of a polyamine. Examples of the demulsifier include polyethylene glycol, polyethylene oxide, polypropylene oxide (such as ethylene oxide-propylene oxide polymer), and mixtures thereof. In some embodiments, the demulsifier can be a polyether. The demulsifier can be present in the lubricant at 0.002 to 0.012 weight percent.

  Pour point depressants are known in the art and include, but are not limited to, esters of maleic anhydride-styrene copolymers; polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes with aromatic compounds. Vinyl carboxylate polymers; copolymers containing dialkyl fumarate; polyalphaolefins, vinyl esters of fatty acids; ethylene-vinyl acetate copolymers; alkylphenol formaldehyde condensation resins; alkyl vinyl ethers and mixtures thereof.

  Antirust agents include hydrocarbyl amine salts of alkyl phosphates, hydrocarbyl amine salts of dialkyldithiophosphates, hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids, fatty carboxylic acids or esters thereof (alkyl substituted succinic acids and salts thereof, esters, amides or Imides), esters of nitrogen-containing carboxylic acids, ammonium sulfonates, imidazolines, or combinations or mixtures thereof. The rust inhibitor is in the lubricant in an amount of 0.02 to 0.2 weight percent, or 0.03 to 0.15, or 0.04 to 0.12, or 0.05 to 0.10 weight percent. Can exist in

  Metal deactivators can be used to neutralize the catalytic action of metals that promote oxidation in lubricating oils. Suitable metal deactivators include, but are not limited to, triazoles, tolyltriazoles, thiadiazoles, and combinations or derivatives thereof. Examples include benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N'-dialkyldithio-carbamoyl) benzothiazole, 2,5-bis (alkyldithio)- 1,3,4-thiadiazole, 2,5-bis- (N, N′-dialkyldithiocarbamoyl-1,3,4-thiadiazole, derivatives of 2-alkyldithio-5-mercaptothiadiazole, and their The metal deactivator can be present in an amount of 0.001 to 0.1, or 0.1 to 0.04, or 0.15 to 0.03 weight percent.

  In one embodiment, the lubricant comprises (in addition to the polymers disclosed herein) detergents, dispersants, antioxidants, antiwear agents, friction modifiers, pour point depressants, corrosion inhibitors and It further comprises at least one of an antifoaming agent, a demulsifier, a metal deactivator, or a metal salt of phosphorus acid. In one embodiment, the lubricant composition further comprises an overbased detergent in an amount of 0.5 to 2.0 weight percent and an ashless dispersant in an amount of 0.5 to 3 weight percent.

Lubrication Method The additive and the lubricant composition described above can be used to lubricate a mechanical device, such lubrication to or from the device that permits the lubricant described herein. A supply to a portion of the device can be included. Examples of suitable devices may include internal combustion engines such as spark ignition engines, passenger car engines or motorcycle engines; gears, clutches, transmissions, hydraulic devices and turbines. The lubricant may be a liquid lubricant or grease.

  Engines include gasoline engines such as passenger car engines or spark ignition engines, diesel engines for passenger cars, diesel engines such as diesel engines for heavy trucks, compression ignition engines, natural gas fuel engines such as stationary output engines, alcohol fuel engines, mixed gasoline / Alcohol fuel engines, biodiesel fuel engines, hydrogen fuel engines, two-stroke engines, aviation piston engines or turbine engines, or internal combustion engines such as marine or railroad diesel engines. In one embodiment, the internal combustion engine can be a diesel fuel engine, and in another embodiment, it can be a gasoline fuel engine or a hydrogen fuel engine. The internal combustion engine may be fitted with an exhaust purification system or a turbocharger. Examples of emission purification systems include systems that use diesel particulate collection filters (DPF), exhaust gas recirculation (EGR), and selective catalytic reduction (SCR).

  The engine may also be a motorcycle engine, and the lubricant may be considered a motorcycle lubricant. Lubricants for motorcycles typically provide lubrication for engines (crank chambers) and wet clutches. These two devices are often lubricated by the same fluid, but often have different lubrication requirements. For example, engine lubrication is desirable to provide low metal-on-metal friction to promote good fuel economy. (What is commonly referred to as "metal" is steel.) However, the coefficient of friction at the metal-composition interface located within the wet clutch ensures good engagement and power transmission. It may be desirable to be relatively high. In addition, motorcycle lubricants also lubricate other devices such as gears or bearings, each of which has its own lubrication requirements. In one embodiment, the lubricant described herein can lubricate both motorcycle engines and wet clutches.

  The hydraulic fluid can be more generally described as an industrial fluid or can be considered a species of industrial fluid, which fluid can include hydraulic fluid, turbine oil, circulating oil, or combinations thereof. Hydraulic fluid can be viewed as a fluid that propagates forces through the device due to its fluid properties. The hydraulic system can include a hydraulic pump such as a piston pump, vane pump, gear pump, or combinations thereof. The hydraulic system can also contain hydraulic motors or pistons that are used to actuate wheels or tracks for the movement and / or manipulation of instruments such as buckets, rigs or rams. Portable hydraulic systems include those used in wheel loaders, backhoes, excavators, rollers, and agricultural equipment. The hydraulic fluid and hydraulic equipment can be used in transport vehicle systems, such as a hydraulic launch assist or hydraulic brake system, and stationary devices. In one embodiment, the hydraulic system can have the ability to transfer rotational energy to a storage energy reservoir for later reconversion to rotational energy. The hydraulic fluid can optionally be zinc-free, metal-free, or ashless, and can optionally contain any of the features described above.

  As used herein, the term “condensation product” and the like (eg, “condensed”) refers to whether the condensation reaction actually takes place and the product is directly directed. Including esters, amides, imides, and other such materials that can be prepared by condensation reactions of acids or reactive equivalents of acids (eg, acid halides, anhydrides or esters) with alcohols or amines. Is intended to be. Thus, for example, certain esters may be prepared by transesterification rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

  The amounts of each chemical component listed are indicated, excluding any solvent or diluent oil that may conventionally be present in commercially available materials, ie on an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be construed as a commercial grade material, which is present in a commercial grade. It may contain isomers, by-products, derivatives and other such substances that are commonly understood to be present.

  As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense and is well known to those skilled in the art. Specifically, the above group refers to a group having a carbon atom that is bonded directly to the rest of the molecule and has predominantly hydrocarbon character. Examples of hydrocarbyl groups include hydrocarbon substituents (including aliphatic substituents, alicyclic substituents and aromatic substituents); substituted hydrocarbon substituents (ie, the main carbonization of the substituents in the context of the present invention). Substituents containing non-hydrocarbon groups that do not change the hydrogen properties); and hetero substituents (ie, having similar hydrocarbon properties primarily but containing other than carbon in the ring or chain) Substituents). A more detailed definition of the term “hydrocarbyl substituent” or “hydrocarbyl group” is found in paragraphs [0137] to [0141] of US Published Application 2010-0197536.

  It is known that some of the above materials may interact in the final formulation, and therefore the components of the final formulation may be different from those originally added. For example, metal ions (eg, in detergents) can migrate to other acidic or anionic sites of other molecules. The product formed thereby may not be easily described, including the product formed when using the composition of the invention in its intended use. Nonetheless, all such modifications and reaction products are included within the scope of the present invention. The present invention includes a composition prepared by mixing the above components.

  The invention herein is useful for applications in hydraulic systems and engines and can be better understood with reference to the following examples.

ａ．相対量、合計で１００％の油； 示されている通り、ＡＰＩグループＩまたはＡＰＩグループＩＩＩ。
ｂ．油不含量。提供されている通り、５３％の油を含有する。ポリマーは、平均で６〜１５アームを有する星型ポリマーであり、アームは、約３５，０００から５０，０００のＭ_ｎを有する。アームは、アルキレングリコールジメタクリレートから調製されたコアに連結されている、Ｃ１０〜１８アルキルメタクリレートモノマーおよびＣ１〜９アルキルメタクリレートモノマーを含む、ランダムコポリマーである。
ｃ．油不含量。提供されている通り、８７％の油を含有する。ポリマーは、約１５０，０００のＭ_ｗを有する、エチレンモノマー単位が約４５重量パーセントの市販のエチレン／プロピレンコポリマーである。 (Examples 1-5)
Lubricants are prepared in formulations having a viscosity index of about 140 with various ISO grades (expressed by kinematic viscosity in mm ² / s at 40 ° C.). Lubricants are prepared from the indicated base oils, and each formulation contains about 0.85% of a commercial dispersant / inhibitor ("DI") package, and the above formulation is ultimately , Zinc dialkyldithiophosphates, phenolic antioxidants, calcium detergents (alkyl sulfonates and phenates), alkyl substituted carboxylic acid anhydrides, and small amounts of other inhibitors and other conventional materials, and diluent oils. Formulations can be made in various viscosity grades, exemplified in Table I.

a. Relative amount, 100% total oil; API group I or API group III as indicated.
b. Oil-free. As provided, it contains 53% oil. The polymer is a star polymer with an average of 6-15 arms, with the arms having a M _n of about 35,000 to 50,000. The arm is a random copolymer comprising a C10-18 alkyl methacrylate monomer and a C1-9 alkyl methacrylate monomer linked to a core prepared from alkylene glycol dimethacrylate.
c. Oil-free. As provided, contains 87% oil. The polymer is a commercially available ethylene / propylene copolymer having an _Mw of about 150,000 and about 45 weight percent ethylene monomer units.

(Examples 6 to 11)
Lubricants are prepared targeting ISO 46 viscosity grade using varying amounts of star polymers and ethylene / olefin copolymers and their various relative ratios. The DI package is the same commercially available package as used in Examples 1-5. Applicable to footnotes a, b and c in Table I.

  These results illustrate that varying ratios of polymers of the disclosed technology can be used to easily formulate various viscosity grade lubricants with high viscosity indices.

(Examples 12 and 13)
Lubricants are prepared using the formulations described in Table III (corresponding to footnotes a, b and c in Table I).

  The lubricant was also subjected to the 104c (“Conestoga”) pump test, which is described in more detail in ISO 20863, and these results are also reported in Table III. In this test, the pump cam rings and vanes are weighed before and after the test and the weight loss from these rings and vanes is measured. The test period is 250 hours, the temperature is 69 ° C., the pressure is 14 MPa (140 bar), and 1440 r. p. m. The lubricant sample size is 70 L at a flow rate of about 25 L / min. These results show that the materials of the present disclosure provide a dramatic reduction in wear compared to similar formulations using conventional linear methacrylate copolymer viscosity modifiers.

ａ．相対量、合計で１００％の基油
ｂ．表Ｉの脚注を参照
ｃ．表Ｉの脚注を参照
ｄ．油不含量；提供された通り、６０％の油を含有している。Ｃ１２〜１５アルキルメタクリレート５重量％、Ｃ４メタクリレート８３重量％、およびアルキルメタクリレートを含むマクロモノマー１２重量％を含む櫛型ポリマーであり、アルキル基は、約３５５個の炭素原子を有する（水素化されている）ポリブタジエンから誘導されている。Ｍ_ｗ １８２，０００。
ｅ．油不含量；提供された通り、６０％の油を含有している。スチレン１４重量％、Ｃ４アルキルメタクリレート５８重量％、および脚注ｄに一覧表示されているマクロモノマー２８重量％を含む、櫛型ポリマー。Ｍｗ １４０，０００。
ｊ．油不含量；表ＩＩＩと同様。 (Examples 14 to 17)
Formulations are prepared as shown in Table IV below using a comb polymer identified as footnote d or e, or a linear methacrylate polymer for reference.

a. Relative amount, 100% total base oil b. See footnote in Table I c. See footnote in Table I d. No oil content; as provided, contains 60% oil. A comb polymer comprising 5% by weight of C12-15 alkyl methacrylate, 83% by weight of C4 methacrylate, and 12% by weight of a macromonomer containing alkyl methacrylate, wherein the alkyl group has about 355 carbon atoms (hydrogenated) It is derived from polybutadiene. _Mw 182,000.
e. No oil content; as provided, contains 60% oil. Comb polymer comprising 14% by weight styrene, 58% by weight C4 alkyl methacrylate, and 28% by weight macromonomer listed in footnote d. Mw 140,000.
j. Oil-free content: Same as Table III.

ｂ．５４％の油を含有していることを除き、表Ｉに定義されている通りである（表中に示されている量は、油不含基準である）。
ｃ．油不含固体物質としてここで提示されているものを除き、表Ｉに定義されている、エチレン／プロピレンコポリマー。
ｆ．ＮａおよびＣａ過塩基性清浄剤約１７％、分散剤４４％、ジアルキルジチオリン酸亜鉛９％、酸化防止剤１７％およびアルキル酒石酸イミド８％を含有する、市販の乗用車用エンジン油の分散剤／防止剤パッケージ。上記のそれぞれは、従来量（ある場合）の希釈油、ならびにさらなる希釈油、および少量の他の従来の構成成分を含有している。
ｇ．メタクリレートコポリマー；量は約５０％の希釈油を含む。 (Examples 18 (reference) and 19)
Lubricant formulations are prepared as shown in Table V. (The amount of base oil is given as a percentage of the lubricant formulation.)

b. As defined in Table I, except that it contains 54% oil (the amounts shown in the table are on an oil free basis).
c. An ethylene / propylene copolymer, as defined in Table I, except as presented herein as an oil-free solid material.
f. Dispersant / prevention of commercial passenger car engine oils containing about 17% Na and Ca overbased detergent, 44% dispersant, 9% zinc dialkyldithiophosphate, 17% antioxidant and 8% alkyl tartarimide Agent package. Each of the above contains conventional amounts (if any) of diluent oil, as well as additional diluent oil and small amounts of other conventional components.
g. Methacrylate copolymer; amount contains about 50% diluent oil.

（２５℃での結果は、ベースラインを超える変化がほとんどないことを示している。平均トルク低下：参照例１８の場合、＋０．４２％であり、実施例１９の場合、−０．５７％である。） The lubricants of Example 18 (reference) and Example 19, formulated as SAE 0W-20 grade lubricants, were tested with an external propulsion engine assembly friction test apparatus and tested at 88, 60, and 25 ° C at 500 ° C. To 2,500 r. p. m. Measure torque at speed of. The percent decrease in torque of the candidate fluid is compared to that of the baseline SAE 0W-20 fluid. While both fluids showed reduced torque at 60 and 88 ° C. compared to the baseline lubricant, the formulation containing a mixture of star polymer and ethylene-propylene copolymer (Example 19) was It shows that the torque drop is larger. The results at 60 and 88 ° C. are shown in Table Va below.

(The result at 25 ° C. shows that there is almost no change beyond the baseline. Average torque reduction: + 0.42% for Reference Example 18, -0.57% for Example 19 .)

ｂ．表Ｉと同様、油不含量
ｃ．表Ｉと同様、油不含量
ｇ．表Ｖと同様
ｈ．約３３％の希釈油を含む。ＤＩパッケージ中に存在している分散剤に加えて、ホウ素化分散剤。
ｍ．過塩基性清浄剤２１％、分散剤５４％、酸化防止剤１２％およびジアルキルジチオリン酸亜鉛１０％を含有する市販の多目的添加剤パッケージであり、上記のそれぞれは、従来量（存在する場合）の希釈油、ならびにさらなる希釈油、および少量の他の従来の構成成分を含有している。 (Examples 20 to 26)
Lubricants are prepared and tested as shown in Table VI.

b. As in Table I, no oil content c. As in Table I, no oil content g. Same as Table V h. Contains about 33% diluent oil. A borated dispersant in addition to the dispersant present in the DI package.
m. A commercial multi-purpose additive package containing 21% overbased detergent, 54% dispersant, 12% antioxidant and 10% zinc dialkyldithiophosphate, each of the above in conventional amounts (if present) Contains diluent oil, as well as additional diluent oil and small amounts of other conventional components.

  ASTM D7109 (90 “Orbahn” shear stability test in which the polymer-containing fluid passes through a Bosch ™ diesel injector nozzle at high pressure. This treatment causes degradation of the polymer molecules. 100 before and after shearing. The lubricant containing a mixture of a star polymer and an olefin copolymer has a reduced MRV viscosity with good viscosity retention after shearing, It shows that the viscosity index is improved.

  Each of the documents referred to above is incorporated herein by reference, including any prior applications from which priority is claimed, whether specifically listed above. Yes. Reference to any document does not admit that either document is recognized as prior art or constitutes general knowledge of one of ordinary skill in any power. Except where specifically stated in the examples or otherwise, all numerical amounts in this description specifying the amount of substances, reaction conditions, molecular weight, number of carbon atoms, etc. may vary from case to case. Should be understood as being modified by the word “about”. The upper and lower limits for amounts, ranges, and ratios described herein can be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.

  As used herein, the transition term “comprising”, which is synonymous with “including”, “containing” or “characterized by” Or open-ended, and does not exclude additional undescribed elements or method steps. However, in each of the statements “comprising” herein, the term is also referred to as “consisting essentially of” and “consisting of” as alternative embodiments. It is intended to encompass wording, where “consisting of” excludes any element or step not specified, and “consisting essentially of” of the composition or method being considered, It is acceptable to include additional elements or steps not described which do not substantially affect essential or basic and novel features. The expression “consisting of” or “consisting essentially of” when applied to an element of a claim, regardless of whether the term “includes” exists anywhere in the claim Is intended to limit all species of the type represented by

  While certain representative embodiments and details are presented for purposes of illustrating the invention, it is to be understood that various changes and modifications can be made in the invention without departing from the scope of the invention. It is clear to the contractor. In this respect, the scope of the present invention is limited only by the following claims. In certain authorities, a description of one or more narrow values for a numerical range, or a description of a narrower selection of elements from a wider listing means that such a description represents a preferred embodiment. doing.

Claims (30)

(A) an oil of lubricating viscosity;
(B) a (meth) acrylate-containing polymer comprising a plurality of arms, wherein the arms comprise at least about 20, or at least 50 or 100 or 200 or 350 or 500 or 1000 carbon atoms; A (meth) acrylate-containing polymer bonded to the organic moiety of: and (c) an ethylene / olefin copolymer having a weight average molecular weight of from about 5,000 to about 250,000 or from about 10,000 to about 250,000 Wherein the copolymer comprises from about 40 to about 70 weight percent polymerized ethylene monomer, and further comprises one or more polymerized olefin monomers of 3 to 6 carbon atoms. / Lubricant composition comprising an olefin copolymer.   The lubricant composition of claim 1, wherein the arm is a polymer entity comprising non-olefin monomer units.   The lubricant composition according to claim 1 or 2, wherein the arm is a polymer entity containing an alkyl (meth) acrylate monomer unit.   The lubricant composition according to any one of claims 1 to 3, wherein the arm is a polymer entity including a comonomer of a C10 to C18 alkyl methacrylate group and a C1 to C9 alkyl methacrylate group.   The lubricant composition according to claim 1, wherein the arm comprises a random copolymer.   The lubricant composition according to claim 1, wherein the arm comprises a block copolymer.   The lubricant according to any one of claims 1 to 6, wherein the number of arms bonded to the polyvalent organic moiety is 3 to 20, or 5 to 20, or 6 to 15, or 7 to 8. Composition.   The lubrication according to any of claims 1 to 7, wherein the number average molecular weight of the arms is from about 10,000 to about 200,000, or 20,000 to 100,000, or 35,000 to 50,000. Agent composition.   The lubricant composition according to any of claims 1 to 8, wherein one or more than one of the arms comprises units derived from an alkyl acrylate monomer.   The lubricant composition according to any one of claims 1 to 9, wherein the (meth) acrylate-containing polymer includes a star polymer in which a plurality of arms are connected to a core.   The lubricant composition of claim 10, wherein the core comprises a polymerized monomer of alkylene glycol dimethacrylate.   The lubricant composition of claim 1, wherein the arm comprises a hydrocarbyl group.   The lubricant composition according to any one of claims 1 to 12, wherein the (meth) acrylate-containing polymer includes a comb polymer.   14. The lubricant composition of claim 13, wherein the arm is a polymer entity comprising conjugated diene monomer units (optionally hydrogenated) or isobutylene monomer units.   The lubricant composition of claim 14, wherein the conjugated diene comprises butadiene or isoprene.   16. The amount of the (meth) acrylate containing polymer comprising a plurality of arms is present in an amount of about 0.1 to 2.5, or 0.25 to about 2.5 weight percent. The lubricant composition according to any one of the above.   The lubricant composition according to any of claims 1 to 16, wherein the ethylene / olefin copolymer comprises at least one of a propylene monomer unit or a butylene monomer unit.   The lubricant composition according to any of claims 1 to 17, wherein the ethylene / olefin copolymer comprises propylene monomer units.   The lubricant composition according to any of claims 1 to 18, wherein the ethylene / olefin copolymer comprises about 40 to about 50 weight percent ethylene monomer units and about 50 to about 60 weight percent propylene monomer units.   20. A lubricant composition according to any preceding claim, wherein the ethylene / olefin copolymer has a weight average molecular weight of about 20,000 to about 180,000.   The amount of said ethylene / olefin copolymer is from about 0.1 to about 10, or from about 0.1 to about 2.5, or from about 0.1 to about 1 weight percent. The lubricant composition as described.   At least a detergent, a dispersant, an antioxidant, an antiwear agent, a friction modifier, a pour point depressant, a corrosion inhibitor, and an antifoam agent, an anti-emulsifier, a metal deactivator, or a metal salt of a phosphorus acid The lubricant composition according to any of claims 1 to 21, further comprising one.   23. The method of any preceding claim, further comprising an overbased detergent in an amount of about 0.5 to about 2.0 weight percent and an ashless dispersant in an amount of about 0.5 to about 3 weight percent. Lubricant composition.   A lubricant composition suitable for lubricating motorcycle crankcases and wet clutches, comprising an overbased calcium detergent in an amount of 0.2 to 1.8 weight percent of said composition, an ashless dispersant. And further comprising a friction modifying additive in an amount of 0.8 to 3.2 weight percent of the composition and a friction modifier additive that increases static friction at the friction plate-steel interface in an amount of 0.05 to 1.85 weight percent of the composition. The lubricant composition according to any one of claims 1 to 23.   25. A method of lubricating a mechanical device comprising the step of supplying a lubricant composition according to any of claims 1 to 24 thereto.   26. The method of claim 25, wherein the mechanical device comprises a hydraulic system.   26. The method of claim 25, wherein the mechanical device comprises an internal combustion engine.   28. The method of claim 27, wherein the internal combustion engine is a passenger car engine.   29. A method according to claim 27 or claim 28, wherein the internal combustion engine is a spark ignition engine. 28. The method of claim 27, wherein the internal combustion engine comprises a motorcycle engine.