Polymers and lubricating compositions containing the polymers

Abstract

To provide a polymer which can be used as an additive in a lubricating composition, and improves friction and reduces wear.SOLUTION: There is provided a polymer comprising a unit having the following structure in which x is 2 or 3, L is (CH2)y where y is an integer of 1 to 10 or L is CH(CH3)CH2S(CH2)z where z is an integer of 1 to 5, and [Q] is absent or a polymerization part composed of a unit having a certain structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to polymers, particularly amphiphilic polymers. The present invention also relates to lubricating compositions (lubricants) containing said polymers and to the use of said polymers as additives for lubricants. Lubricants of particular interest are lubricating oil compositions, such as those used to lubricate the crankcases of spark-ignition and compression-ignition internal combustion engines. The polymers impart wear and friction reducing properties to lubricants, such as lubricating oil compositions, thereby improving efficiency and aiding in wear reduction. [Background technology]

[0002] There is great interest in improving fuel economy in gasoline and diesel engines. This can be done with the lubricant engine oil by reducing friction either in the bulk fluid (by reducing the oil viscosity) or between contacting parts by the inclusion of friction modifying additives. There is also a continuing need to reduce the occurrence of wear in the engine. Summary of the Invention

[0003] In a first aspect, the present invention provides a polymer comprising units having the structure (I). [ka] (I) In the formula, x is 2 or 3, and L is an integer such that y is 1 to 10 (CH 2 ) y or L is CH(CH) where z is an integer from 1 to 12, preferably from 1 to 5. 3 )CH 2 S(CH 2 ) z It is. [Q] is absent or is a polymerized portion consisting of units having the structure (II). [ka] (II) wherein R is a hydrocarbyl group or a hydrocarbyl group containing one or more heteroatoms, R may be linear, branched or cyclic, saturated or unsaturated, and R has from 1 to 30 carbon atoms. [Q] consists of identical structural (II) units, or [Q] consists of more than one different structural (II) units having different R groups. X is a halogen or another chain terminating group. Preferably, the number of structure (I) units in the polymer is from 2 to 100, preferably from 2 to 50, for example from 5 to 30. In some embodiments, the polymer further comprises a unit having structure (III). [ka] (III) In the formula, R 1 is a straight or branched, saturated or unsaturated hydrocarbyl group having from 1 to 50, preferably from 2 to 24, for example from 2 to 18, carbon atoms; w is 2 or 3. In some embodiments, the polymer comprises units of Structure (I). In another embodiment, the polymer consists of Structure (I) units and Structure (III) units.

[0004] The polymers of the present invention are described in more detail below. The polymers of the present invention comprise units having the structure (I). [ka] (I) In some embodiments, all units of structure (I) have the same value of x; it is either 2 or 3. In alternative embodiments, in some units x is 2 and in others x is 3. The ratio of the number of units where x is 2 to the number of units where x is 3 can be any suitable ratio, but is preferably from 1:100 to 100:1. In one embodiment, the L group is (CH 2 ) yand y is an integer from 1 to 20. Preferably, y is an integer from 1 to 10, more preferably from 2 to 7, for example 5. In another embodiment, the L group is CH(CH 3 )CH 2 S(CH 2 ) z and z is an integer from 1 to 12, preferably from 1 to 5. In some embodiments, z is 2. In some embodiments, [Q] is absent. In an alternative embodiment, [Q] is a polymeric moiety comprised of units having structure (II). [ka] (II)

[0005] In the context of the present invention, it should be understood that polymerized moieties include moieties that can more precisely be called "oligomers." The number of units of structure (II) present need only be as few as two. Preferably, the number of units of structure (II) in [Q] is from 2 to 200, more preferably from 2 to 100, and even more preferably from 2 to 50. Preferably, the ratio of the number of units of Structure (I) in the polymer to the number of units of Structure (II) in the polymerized portion [Q] is in the range of 1:50 to 50:1, more preferably 1:20 to 20:1, even more preferably 1:10 to 10:1, such as 1:5 to 5:1, 1:2 to 2:1, for example 1:1.

[0006] The polymeric portion [Q] may be a homopolymer, in the sense that it is composed of a single type of structural (II) unit, in which case all R groups in [Q] are the same. In another embodiment, the polymeric portion [Q] may be a copolymer, and there are two or more different types of structural (II) units. These different types of structural (II) units are distinguished by different R groups. If [Q] is a copolymer, the different structural (II) units may be arranged as a statistical copolymer, and the polymerization follows known statistical laws, such as Bernoulli statistics or Markov statistics. Alternatively, the different structural (II) units may be arranged as a random copolymer. Furthermore, the different structural (II) units may be arranged in an order, resulting in an alternating copolymer, a periodic copolymer, or a block copolymer. In a particular embodiment, the two or more different types of structural (II) units form a block copolymer. If [Q] is a copolymer, there are different types of structural (II) units, which are distinguished by different R groups. The number of different types of structural (II) units present is not limited, but in a preferred embodiment, there are 2, 3, 4, 5 or more, for example up to 12 different types of structural (II) units, each distinguished by a different R group. In a particularly preferred embodiment, there are two different types of structural (II) units. There is no limit to the respective proportions of different types of structural (II) units present in [Q]. When [Q] is composed of two different types of structural (II) units, the ratio of the number of units of one type to the number of units of the other type is preferably in the range of 1:100 to 100:1, more preferably 1:50 to 50:1, even more preferably 1:20 to 20:1, for example 1:10 to 10:1. It will be understood that the polymerized portion [Q] may be composed of only one structural (II) unit of one type and one structural (II) unit or two or more structural (II) units of another type. For example, in certain embodiments, [Q] may consist of one type of structural (II) unit, preferably two or more structural (II) units, and another type of structural (II) unit attached to the end. The configuration is described below for the [Q] moiety having three structural (II) units carrying R groups and a terminal structural (II) unit carrying R' groups, where R and R' are different. [ka]

[0007] The R group is a hydrocarbyl group or a hydrocarbyl group containing one or more heteroatoms. As stated above, all R groups present in [Q] may be the same, i.e., each unit of structure (II) present is the same. Alternatively, two or more different units of structure (II) may be present, each with a different R group. Examples of hydrocarbyl groups suitable as R groups are straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and higher analogs. Also suitable are branched alkyl groups such as iso-propyl, iso-butyl, sec-butyl, tert-butyl, 2-methylpentyl, 2-propylheptyl, 2-butyloctyl, 2-ethylhexyl, iso-octyl, iso-nonyl, 2-tert-butylheptyl, 3-isopropylheptyl, 5-methylundecyl, 2-methyldodecyl, 5-methyltridecyl, 2-methylhexadecyl, 5-isopropylheptadecyl, 4-tert-butyloctadecyl, 5-ethyloctadecyl, 3-isopropyloctadecyl, and the like. Further examples of hydrocarbyl groups suitable as R groups include linear alkenyl groups and higher analogues such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, and the like. As is known in the art, an alkenyl group can contain a single carbon-carbon double bond that can be located at any point along the carbon chain. Thus, for example, a propenyl group can be prop-1-enyl or prop-2-enyl. Alternatively, an alkenyl group can contain more than one carbon-carbon double bond, an example being a "di-enyl" group that contains two carbon-carbon double bonds. In groups with multiple carbon-carbon double bonds, the double bonds may or may not be conjugated.

[0008] In some embodiments, the R group may be a linear alkenyl group derived from fatty acids of natural origin, such as vegetable oils, or from animal fats. Such fatty acids are mixtures of compounds with different carbon chain lengths, and therefore the R groups derived from them are mixed as well. Such groups are often represented as CX:Y, where X refers to the number of carbon atoms in the group and Y is the number of double bonds in the group. One example is the oleyl group (from oleic acid), represented as C18:1, which has 18 carbon atoms and a single carbon-carbon double bond. Mixtures rich in C18:1, C18:2, and C18:3 are suitable examples. As is known in the art, mixtures derived from natural fatty acids may usually contain small amounts of alkyl groups, such as stearyl groups (C18:0). Suitable branched alkenyl groups are the double bond-containing analogs of the branched alkyl groups described above. Triply unsaturated groups, i.e. alkynyl groups, are also suitable. An example is the propargyl group. As the hydrocarbyl group R, saturated and unsaturated cyclic groups, including polycyclic groups, are also suitable. Such groups may be substituted or unsubstituted. Examples of monocyclic saturated groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of polycyclic saturated groups include groups derived from decalin and the like. Examples of unsaturated groups are benzyl, naphthyl, and groups derived from anthracene, phenanthrene, phenalene, and the like. Substituted analogs of saturated and unsaturated cyclic groups, including polycyclic groups, can include groups substituted with a single alkyl or alkenyl group, or with more than one alkyl or alkenyl group, or mixtures thereof. The substituents can be straight or branched chain and can include the alkyl and alkenyl groups listed above.

[0009] Alternatively or additionally, the R group may be a hydrocarbyl group containing one or more heteroatoms. Heteroatoms include oxygen, sulfur, nitrogen, phosphorus and halogens. As known in the art, the heteroatoms may be located between saturated or unsaturated carbon-carbon bonds, such as those found in ethers or pyridines, or may be located in a substituent group attached to the hydrocarbyl group, such as a hydroxy or carboxylic acid group. Any of these types of groups are considered to be hydrocarbyl groups containing one or more heteroatoms, as groups having both one or more heteroatoms located between saturated or unsaturated carbon-carbon bonds and one or more heteroatoms located in a substituent group. An example of a hydrocarbyl group containing one or more heteroatoms is the structure -[(CR 2 H) a O] b OR 3 where a is an integer from 2 to 4, preferably 2, and b is an integer from 2 to 100, preferably from 2 to 20, for example from 2 to 10. 2 is hydrogen or CH 2 Or CH 2 CH 2 Preferably, R 2 is hydrogen. R 3 is hydrogen, an alkyl group such as methyl or ethyl, or an aryl group such as phenyl. 3 is a methyl group. Preferably, a is 2 and R is 1 so that this group is a polyethylene glycol group. 2 is hydrogen. In a preferred embodiment, R is a diethylene glycol group. 2 is hydrogen, a is 2, and b is 2. In another preferred embodiment, a is 2 and b is an average value of 7 to 8, such that the group is an oligoethylene glycol group. Further examples of hydrocarbyl groups containing one or more heteroatoms are groups bearing one or more hydroxyl groups. These include hydroxybenzyl groups and similar aromatic groups bearing one or more hydroxyl groups. Amino and silyl groups are also suitable.

[0010] In some embodiments, the polymer further comprises a unit having structure (III). [ka] (III) Hydrocarbyl Group R 1 is preferably a hydrocarbyl group as described above for the hydrocarbyl group R. In a preferred embodiment, R 1 The groups include linear alkenyl groups or mixtures of linear alkenyl groups derived from fatty acids of natural sources such as vegetable oils, or animal fats, which are described above in connection with the R group. Preferably, R 1 R comprises a mixture of linear alkenyl groups derived from fatty acids of natural sources such as vegetable oils or animal fats, at least 10% of which contain unsaturated hydrocarbyl groups having from 8 to 20 carbon atoms. More preferably, R 1 At least 20% or 30% or 40% or 50% of the groups contain unsaturated hydrocarbyl groups having from 8 to 20 carbon atoms. 1 At least 60% or 70% of the groups contain unsaturated hydrocarbyl groups having from 8 to 20 carbon atoms. 1 At least 10% of the groups contain unsaturated hydrocarbyl groups having from 15 to 20 carbon atoms. More preferably, R 1 At least 20% or 30% or 40% or 50% of the groups contain unsaturated hydrocarbyl groups having from 15 to 20 carbon atoms. 1 At least 60% or 70% of the groups contain unsaturated hydrocarbyl groups having from 15 to 20 carbon atoms. Preferably, R 1comprises a mixture of linear alkenyl groups, at least 5% of which contain unsaturated hydrocarbyl groups having 17 carbon atoms. More preferably, R 1 At least 10% or 20% or 30% or 40% or 50% or 60% of the groups contain unsaturated hydrocarbyl groups having 17 carbon atoms. Even more preferably, R 1 At least 70% of the groups contain unsaturated hydrocarbyl groups containing 17 carbon atoms. In a preferred embodiment, R 1 contains a mixture of linear alkenyl groups, at least 50% of which are mono-, di- or trivalently unsaturated C 17 More preferably, R 1 At least 60% of the groups are mono-, di- or trivalent unsaturated C 17 alkenyl groups or any mixture thereof. Even more preferably, R 1 At least 70% of the groups are mono-, di- or triunsaturated C 17 alkenyl groups or any mixture thereof. In a particularly preferred embodiment, R 1 The group is mono-, di- or tri-unsaturated C 17 The mixture of alkenyl groups includes mono- and di-unsaturated C 17 High in alkenyl groups. Such mixtures may contain small amounts of shorter and longer molecules.

[0011] In one embodiment, for all units of Structure (III) present, w is 2. In another embodiment, for all units of Structure (III) present, w is 3. In yet another embodiment, the units of Structure (III) present are a mixture of moieties where w is 2 and moieties where w is 3. In this embodiment, the ratio of the number of Structure (III) units where w is 2 to the number of Structure (III) units where w is 3 can be any value, but is preferably in the range of 1:100 to 100:1, more preferably 1:50 to 50:1 or 1:20 to 20:1, for example 1:10 to 10:1. When the polymer of the present invention comprises or consists of structure (I) and structure (III) units, the units of structure (I) and (III) can be arranged as a statistical copolymer, the polymerization of which follows known statistical laws, such as Bernoulli statistics or Markov statistics. Alternatively, the units of structure (I) and (III) can be arranged as a random copolymer. Furthermore, the units of structure (I) and (III) can be arranged in an order, resulting in an alternating copolymer, a periodic copolymer, or a block copolymer. Preferably, when the polymer of the present invention comprises or consists of Structure (I) units and Structure (III) units, the ratio of the number of Structure (I) units to the number of Structure (III) units is from 1:100 to 100:1, more preferably from 1:50 to 50:1 or from 1:20 to 20:1, for example from 1:10 to 10:1.

[0012] In the polymers of the present invention, X is a halogen or a chain terminating group. Preferably, X is a halogen, and most preferably, X is bromine. As is known in the art, end group conversion reactions can be used to provide various types of chain terminating groups X. For example, X can be a hydroxy group, an azide group, an NH 2 It may be a thioether group or an ether group. The polymers of the invention may be of any molecular weight, but preferably have a number average molecular weight (Mn) of 500 to 500,000 g / mol, preferably 1,000 to 250,000 g / mol, more preferably 5,000 to 100,000 g / mol, e.g., 10,000 to 50,000 g / mol, as measured by gel permeation chromatography against linear, narrow molecular weight distribution poly(methyl methacrylate) standards in the range of 500 to 600,000 g / mol. Specific examples of polymers according to the invention include polymers having 10 structural (I) units, [Q] consisting of 20 structural (II) units, each R group being 2-ethylhexyl; polymers having 50 structural (I) units, [Q] consisting of 5 structural (II) units, each R group being 2-ethylhexyl; and polymers having 10 structural (I) units, [Q] consisting of 10 structural (II) units, each R group being 2-ethylhexyl. Other examples include polymers having 10 structural (I) units, [Q] consisting of 10 structural (II) units, each R group being 2-ethylhexyl, and a single terminal structural (II) unit in which R is a catechol group; and polymers having 10 structural (I) units, [Q] consisting of 10 structural (II) units, each R group being 2-ethylhexyl, and a random copolymer of 5 structural (II) units in which each R group is heptadecyl ethylene glycol methyl ether. In all cases, L is (CH 2 ) y or CH(CH 3 )CH 2 S(CH 2 ) z where y and z are as defined above.

[0013] A method for synthesizing the polymer of the present invention is described below. In the first step, the structure: [ka] is reacted with a mercaptoalcohol, such as 2-mercaptoethanol in this example, to give a compound of the structure: [ka] where p is 1 (2-isopropenyl-2-oxazoline) or 2 (2-isopropenyl-5,6-dihydro-4H-1,3-oxazine). It will be understood that the carbon chain between the sulfur atom and the terminal hydroxyl group is determined by the size of the mercaptoalcohol used. Although 2-mercaptoethanol is shown above, similar mercaptoalcohols having longer carbon chains are similarly suitable. The compound is then subjected to a Stecklich esterification reaction in which the compound is further reacted with a tertiary haloacid, such as α-bromoisobutyric acid, in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyl diimide, such as N,N'-diisopropylcarbodiimide, to give a compound of the structure: [ka] Compound A This forms a compound (compound A).

[0014] In another initial step, the lactone is first ring-opened by reaction with 2-amino-1-ethanol or 3-amino-1-propanol via nucleophilic attack of the nitrogen lone pair. For example, caprolactone ring-opened with 2-amino-1-ethanol has the structure: [ka] Generate. This compound is then reacted with a transition metal catalyst, e.g., Ti(OnBu). 4 The ring is closed by an organometallic catalyzed cyclocondensation reaction by heating in the presence of [ka] Form.

[0015] As described above, the compound may then be further reacted with a tertiary haloacid, such as α-bromoisobutyric acid, in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyl diimide, such as N,N'-diisopropylcarbodiimide, in a Stecklich esterification reaction to give the compound of the structure: [ka] Compound B This forms a compound (compound B). The same reaction replacing 2-amino-1-ethanol with 3-amino-1-propanol in the ring-opening reaction gives the compound of the structure: [ka] Compound B' It will be appreciated that a compound of the formula (Compound B') is prepared. It will also be understood that the length of the carbon chain between the oxygen atoms in the ring moiety and the chain is determined by the size of the lactone used in the ring-opening reaction. As is known in the art, lactones longer and shorter than caprolactone are available and suitable for use in the present invention.

[0016] Compounds A, B and B' or their analogs are used as monomers in polymerization reactions to form polymers according to the present invention. When compounds A, B and B' or analogs thereof are polymerized without the inclusion of other monomers, a polymer containing only structural (I) units without the presence of [Q] is produced. Or, [ka] By copolymerizing these mixtures with compounds A, B and B', or with their analogs, polymers having structure (I) units without [Q], and also structure (III) units are prepared. 1 is as defined above for structure (III). The polymerization can be carried out using cationic ring-opening polymerization (CROP). A suitable synthetic route involves heating a monomer or mixture of monomers in the presence of a tosylate, such as methyl tosylate, a triflate, a primary or secondary alkyl bromide or iodide, or a Lewis acid. The polymerized moiety [Q] can be introduced by reacting the polymer formed above with one or more acrylate monomers. This is conveniently carried out using Cu(0)-mediated reversible deactivation radical polymerization (RDRP) in which the initial polymer acts as an initiator. A deactivating agent (e.g., Cu 2Br) and ligands (e.g., Me 6 TREN) is used. When a single acrylate is used, [Q] consists of structural (II) units where all R groups are the same. Using a mixture of two or more different acrylate monomers results in a [Q] moiety with randomly arranged structural (II) units with different R groups. Alternatively, the reaction can be carried out in two or more stages, with the first stage producing structural (II) units with one type of R group, and then adding a different acrylate monomer to produce structural (II) units with different types of R groups. In this way, the [Q] moiety has a block copolymer structure where the size of each block can be controlled by controlling the amount of each acrylate monomer used.

[0017] Compounds A, B and B' and their analogs, and their synthesis, form another aspect of the present invention. Thus, in another aspect, the present invention provides a compound having the structure (IV): [ka] (IV) wherein p is 1 or 2 and q is an integer from 1 to 10, preferably from 1 to 5. In another embodiment, the present invention provides a compound having structure (V): [ka] (V) wherein p is 1 or 2 and r is an integer from 4 to 10, preferably from 2 to 5.

[0018] In another aspect, the present invention provides a method of synthesizing a compound of structure (IV), the method comprising: (a) reacting 2-isopropenyl-2-oxazoline, 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine or a mixture thereof with a mercaptoalcohol; (b) carrying out a Stecklich esterification reaction by reacting the product of step (a) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyldiimide, preferably N,N'-diisopropylcarbodiimide. In another aspect, the present invention provides a method of synthesizing a compound of structure (V), the method comprising: (a) ring-opening the lactone by reaction with 2-amino-1-ethanol, 3-amino-1-propanol, or a mixture thereof; (b) a transition metal catalyst, preferably Ti(OnBu) 4 ring-closing the product of step (a) by an organometallic catalyzed cyclization reaction by heating in the presence of (c) carrying out a Stecklich esterification reaction by reacting the product of step (b) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyldiimide, preferably N,N'-diisopropylcarbodiimide.

[0019] When used in this specification, the following words and expressions have the following meanings: "Active ingredient" or "(ai)" refers to an excipient that is not a diluent or solvent. The term "comprising" or any cognate word specifies the presence of a stated feature, step, or integer or ingredient, but does not exclude the presence or addition of one or more other features, steps, integers, ingredients, or groups thereof. The phrase "consisting of" or "consisting essentially of" or cognate words can be subsumed under "comprising" or any cognate word. The phrase "consisting essentially of" can include substances that do not materially affect the properties of the composition to which it is applied, and the phrase "consisting of" or cognate words means that only the recited feature, step, integer, ingredient, or group thereof to which the phrase refers is present. As used herein, "oil-soluble" or "oil-dispersible" or related terms do not necessarily mean that a compound or additive is soluble, dissolvable, miscible, or can be suspended in oil in all proportions. However, it does mean that the compound or additive is, for example, dissolved or stably dispersed to a sufficient degree to exert its intended effect in the environment in which the oil is utilized. Furthermore, for further incorporation of other additives, high concentrations of a particular additive can be incorporated if desired. "Ashless" with respect to an additive means that the additive is metal-free. "Ash-containing" with respect to an additive means that the additive contains a metal. "Major amount" means greater than 50% by weight of a composition or mixture. "Minor amount" means 50% by weight or less of a composition or mixture. An "effective amount" with respect to an additive means the amount of the additive (e.g., an additive concentrate) in a composition effective to provide a desired therapeutic effect, and the amount of the additive (e.g., an additive concentrate) in a composition that provides the desired therapeutic effect. "ppm" means parts per million by weight based on the total weight of the composition. The "metal content" of a composition or additive component, such as the molybdenum content or total metal content (ie, the sum of all individual metal contents) of an additive concentrate, is measured by ASTM D5185. "TBN" with respect to an additive component or "TBN" of a composition means Total Base Number (mg KOH / g) as determined by ASTM D2896. "K.V. 100 " means kinematic viscosity at 100°C as measured by ASTM D445. HTHS means High Temperature High Shear at 150° C. as measured by -CEC-L-36-A-90. "Phosphorus Content" is measured by ASTM D5185. "Sulfur Content" is measured by ASTM D2622. "Sulfated ash content" is measured by ASTM D874. Mn means number average molecular weight as determined by gel permeation chromatography against linear, narrow molecular weight distribution poly(methyl methacrylate) standards ranging from 550 to 600,000 g / mol. M w means weight average molecular weight as determined by gel permeation chromatography against linear, narrow molecular weight distribution poly(methyl methacrylate) standards ranging from 550 to 600,000 g / mol. "Dispersion" is M w / M n (denoted as D).

[0020] It will also be understood that the various components employed, as well as essential and preferred and conventional components, may react under conditions of formulation, storage and use, and the invention also provides products obtainable or obtainable by any such reactions. Moreover, it is understood that any high and low quality, range, or ratio limits set forth herein may be independently combined.

[0021] lubricating composition In a second aspect, the present invention provides a lubricating composition comprising a major amount, greater than 50 mass percent, based on the weight of the composition, of a base lubricant and a minor amount, less than 50 mass percent, based on the weight of the composition, of a polymer according to the first aspect of the present invention, which imparts friction reducing properties to the lubricant, and thus use of the lubricant to lubricate machines such as engines, transmissions, gears, etc. improves the efficiency of the machines and helps reduce wear of contacting mechanical parts. The base lubricant may be a lubricating oil, a grease or a fuel oil. In a preferred embodiment, the base lubricant is a lubricating oil such that the lubricating composition is a lubricating oil composition. The lubricating oil composition of the present invention may be a lubricant suitable for use as, for example, an automobile motor oil, and comprises a major amount of an oil of lubricating viscosity and a minor amount of the polymer according to the first aspect of the present invention. Typically, the lubricating oil composition also contains other performance enhancing additives (co-additives) in addition to the polymer. The lubricating oil composition may be in the form of an additive concentrate for blending with an oil of lubricating viscosity to make a finished lubricant. The lubricating oil compositions of the present invention preferably contain from 0.01 to 10 mass percent of the polymer of the present invention based on the weight of the composition, more preferably from 0.01 to 5 mass percent, for example 0.5, 1, 2, 3 or 4 mass percent, based on the weight of the composition. When in the form of an additive concentrate, the polymer is typically present in an oil of lubricating viscosity or other suitable carrier medium in an amount of from 0.07 to 70 mass percent based on the weight of the composition. Oils of lubricating viscosity (sometimes called "base stocks" or "base oils") are the primary liquid constituents of lubricants with which additives and possibly other oils are blended to make, for example, the finished lubricant (or lubricant composition). Base oils useful for making additive concentrates and lubricant compositions therefrom can be selected from natural oils (vegetable, animal, or mineral) and synthetic lubricating oils and mixtures thereof.

[0022] The definitions of base stocks and base oils in the present invention are the same as those described in the publication of the American Petroleum Institute (API), "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998, and classify base stocks as follows: a) Group I base stocks contain less than 90 percent saturates and / or more than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120, as determined by the test methods specified in Table E-1. b) Group II base stocks have a viscosity index greater than or equal to 80 and less than 120, as determined by the test methods specified in Table E-1. c) Group III base stocks have a viscosity index greater than or equal to 120, as determined by the test methods specified in Table E-1, and contain 90 percent or more saturates and 0.03 percent or less sulfur. d) Group IV base stocks are polyalphaolefins (PAOs). e) Group V base stocks include all other base stocks not included in Group I, II, III or IV.

[0023] Typically, the base stock has a melting point of preferably 3 to 12 mm at 100°C. 2 / s, more preferably 4 to 10 mm 2 / s, most preferably 4.5-8 mm 2 / s viscosity. [Table 1]

[0024] Preferably, the oil of lubricating viscosity comprises at least 10 mass %, more preferably at least 20 mass %, even more preferably at least 25 mass %, even more preferably at least 30 mass %, even more preferably at least 40 mass %, even more preferably at least 45 mass % of Group II or Group III base stock, based on the total mass of the oil of lubricating viscosity. Even more preferably, the oil of lubricating viscosity comprises more than 50 mass %, preferably at least 60 mass %, more preferably at least 70 mass %, even more preferably at least 80 mass %, even more preferably at least 90 mass % of Group II or Group III base stock, based on the total mass of the oil of lubricating viscosity. Most preferably, the oil of lubricating viscosity consists essentially of Group II and / or Group III base stock. In some embodiments, the oil of lubricating viscosity consists solely of Group II and / or Group III base stock. In the latter case, it is recognized that the additives included in the lubricating oil composition can include a carrier oil that is not a Group II or Group III base stock.

[0025] Other oils of lubricating viscosity that can be included in the lubricating oil composition are detailed below. Natural oils include animal and vegetable oils (e.g., castor oil and lard oil), liquid petroleum oils, and hydrorefined and solvent treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic / naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene)); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs and congeners. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. Esters useful as synthetic lubricants include C 5 From C 12 Also included are esters made from monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0026] Unrefined, refined and re-refined oils can be used in the compositions of the present invention. Unrefined oils are oils obtained directly from natural or synthetic sources without further refining treatment. For example, shale oil obtained directly from retorting operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from esterification process and used without further treatment are unrefined oils. Refined oils are similar to unrefined oils, except that they are further processed in one or more refining steps to improve one or more properties. Many refining techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation. Re-refined oils are obtained by applying processes similar to those used to obtain refined oils to refined oils that have already been used. Such re-refined oils are also known as reclaimed or reprocessed oils, and are often further processed by techniques that handle used additives and oil breakdown products.

[0027] Other examples of base oils are Gas-to-Liquid ("GTL") base oils, i.e. base oils that have been purified using a Fischer-Tropsch catalyst. 2 The base oil may be derived from Fischer-Tropsch synthetic hydrocarbons made from synthesis gas containing CO and CO. These hydrocarbons usually require further processing to be useful as base oils. For example, they may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods known in the art. The oil of lubricating viscosity may comprise a Group I, Group IV or Group V base stock, or base oil blends of the above base stocks. The lubricating compositions of the present invention preferably comprise at least 60 mass %, such as 70 mass % or more of an oil of lubricating viscosity based on the mass of the composition.

[0028] Co-additives The lubricating compositions of the present invention, particularly lubricating oil compositions, may further comprise, in a form different from the polymer of the present invention, one or more phosphorus-containing compounds, antioxidants or antioxidants, dispersants, metal detergents, antiwear agents, friction modifiers, viscosity modifiers and other co-additives, which are described in more detail below. Suitable phosphorus-containing compounds include metal dihydrocarbyl dithiophosphates, which are often used as antiwear and antioxidant agents. The metal is preferably zinc, but may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. Most commonly, zinc salts are used in lubricating oils in amounts of 0.1 to 10 mass %, preferably 0.2 to 2 mass %, based on the total mass of the lubricating oil composition. These may be prepared according to known techniques, usually by first mixing one or more alcohols or phenols with P. 2 S 5 The dihydrocarbyl dithiophosphoric acid (DDPA) is formed by reacting with a zinc compound, and the DDPA formed is then neutralized with a zinc compound. For example, a dithiophosphoric acid can be made by reacting a mixture of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one dithiophosphoric acid are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. Any basic or neutral zinc compound can be used to make the zinc salt, although oxides, hydroxides and carbonates are most commonly used. Commercially available additives often contain an excess of zinc because an excess of basic zinc compound is used in the neutralization reaction. The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphates and can be represented by the formula: [ka] In the formula, R and R' have 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms, and may be the same or different hydrocarbyl radicals, including alkyl, alkenyl, aryl, arylalkyl, alkaryl, and alicyclic radicals. Particularly preferred as R and R' groups are alkyl groups having 2 to 8 carbon atoms. Thus, the radicals may be, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, and butenyl. To achieve oil solubility, the total number of carbon atoms (i.e., R and R') in the dithiophosphoric acid is generally 5 or more. Thus, the zinc dihydrocarbyl dithiophosphate (ZDDP) may include zinc dialkyl dithiophosphate. Suitably, the lubricating oil compositions of the present invention may have a phosphorus content of about 0.08 wt. % (800 ppm) or less. Preferably, in the practice of the present invention, ZDDP is used in an amount approaching or equal to the maximum allowable amount. Preferably, it is used in an amount that results in a phosphorus content not exceeding 100 ppm, which is the maximum allowable amount for phosphorus. Thus, the lubricating oil compositions useful in the practice of the present invention preferably contain ZDDP or other zinc-phosphorus compound in an amount that introduces 0.01 to 0.08 wt. % phosphorus, such as 0.04 to 0.08 wt. %, preferably 0.05 to 0.08 wt. % phosphorus, based on the total weight of the lubricating oil composition.

[0029] Antioxidants or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on metal surfaces, and viscosity increase. Such antioxidants include hindered phenols, preferably C 5 From C 12Included are alkaline earth metal salts of alkylphenol thioesters having alkyl side chains, calcium nonylphenol sulfide, oil-soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons or esters, phosphites, metal thiocarbamates, the oil-soluble copper compounds described in U.S. Pat. No. 4,867,890, and molybdenum-containing compounds. Aromatic amines with at least two aromatic groups directly attached to the nitrogen constitute another class of compounds frequently used for antioxidant purposes. Typical oil-soluble aromatic amines with at least two aromatic groups directly attached to one amine nitrogen contain 6 to 16 carbon atoms. These amines may contain more than two aromatic groups. With a total of at least three aromatic groups, two aromatic groups are connected by a covalent bond or an atom or group (e.g., oxygen or sulfur atom, or -CO-, -SO 2 Compounds in which at least two aromatic groups are linked by an alkylene group (or an alkylene group), two of which are attached directly to an amine nitrogen, are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen. Typically, the aromatic ring is substituted with one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups. The amount of any such oil-soluble aromatic amine having at least two aromatic groups attached directly to an amine nitrogen preferably does not exceed 0.4 wt.%.

[0030] Dispersants are additives whose primary function is to keep a mixture of solids and liquids in suspension, thereby passivating the mixture and reducing sludge settling as well as engine deposits. For example, dispersants keep in suspension oil-insoluble substances that are produced by oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or settling on metal parts of the engine. Dispersants in the present invention are preferably "ashless" as described above, being non-metallic organic materials that do not form substantially ash on combustion, as opposed to metal-containing, i.e. ash-forming, materials. They comprise long hydrocarbon chains with polar heads, the polarity arising from the inclusion of, for example, O, P or N atoms. The hydrocarbons may have, for example, from 40 to 500 carbon atoms, and are oleophilic groups that provide oil solubility. Thus, ashless dispersants may comprise an oil-soluble polymer backbone. A preferred class of olefin polymers is constituted by polybutenes, specifically polyisobutene (PIB) or poly-n-butenes, such as C 4 It can be prepared by polymerization of refinery streams. Dispersants include, for example, derivatives of long-chain hydrocarbon-substituted carboxylic acids, such as derivatives of high molecular weight hydrocarbyl-substituted succinic acids.A notable group of dispersants is constituted by hydrocarbon-substituted succinimides, for example, prepared by reacting the above acids (or derivatives) with nitrogen-containing compounds, advantageously polyalkylene polyamines, such as polyethylene polyamines.Particularly preferred are the reaction products of polyalkylene polyamines with alkenyl succinic anhydrides, as described, for example, in U.S. Pat. Nos. 3,202,678; 3,154,560; 3,172,892; 3,024,195; 3,024,237; 3,219,666; and 3,216,936, which can be post-treated to improve their properties, such as boration (described in U.S. Pat. Nos. 3,087,936 and 3,254,025), fluorination or oxylation. For example, boration may be carried out by treating the acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and boron acid esters. Preferably, if present, the dispersant is a succinimide dispersant derived from moderately functional polyisobutene having a number average molecular weight in the range of 1000 to 3000, preferably 1500 to 2500. The succinimide is preferably derived from a highly reactive polyisobutene. Other examples of dispersant types that can be used are linked aromatic compounds, such as those described in EP-A-2090642.

[0031] Detergents are additives that reduce the formation of piston deposits in engines, such as high-temperature varnish and lacquer deposits; they usually have acid-neutralizing properties and are capable of maintaining finely divided solids in suspension. Many detergents are based on metal "soaps", that is, metal salts of acid-organic compounds. Generally, detergents contain a polar head with a long hydrophobic tail, which comprises a metal salt of an acidic organic compound. The salt is usually described as a normal or neutral salt, and can have a substantially stoichiometric amount of metal, typically with 100% active mass and a Total Base Number, or TBN, of 0 to 80 (as can be measured by ASTM D2896). Large amounts of metal base can be included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acid gas, such as carbon dioxide. The resulting overbased detergent contains neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle. Such overbased detergents may have a TBN at 100% effective mass of 150 or more, typically 200 to 500 or more. Detergents that can be suitably used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates, and other oil-soluble metal carboxylates, the metals being in particular alkali metals or alkaline earth metals, such as Na, K, Li, Ca and Mg.The most commonly used metals are Ca and Mg, and mixtures of Ca and / or Mg with Na, which can be present in detergents used in the lubricating composition.Detergents can be used in various combinations.

[0032] Additional additives can be incorporated into the compositions of the present invention to meet specific performance requirements. Examples of additives that may be included in the lubricating oil compositions of the present invention are metal rust inhibitors, viscosity index improvers, corrosion inhibitors, antioxidants, other friction modifiers, antifoam agents, antiwear agents, and pour point depressants, some of which are described in more detail below. Friction modifiers and fuel economy agents compatible with the other components of the final oil may also be included. Examples of such materials include glyceryl monoesters of higher fatty acids, such as glyceryl monooleate; esters of long chain polycarboxylic acids and diols, such as butanediol esters of dimerized unsaturated fatty acids; and alkoxylated alkyl substituted monoamines, diamines and alkyl ether amines, such as ethoxylated tallow amine and ethoxylated tallow ether amine. Other known friction modifiers include oil-soluble organomolybdenum compounds. These organomolybdenum friction modifiers also provide antioxidant and antiwear properties to lubricating oil compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyl dithiophosphates, alkyl xanthates, and alkyl thioxanthates. Additionally, the molybdenum compound may be an acidic molybdenum compound, which reacts with basic nitrogen compounds, typically hexavalent, as determined by ASTM test D-664 or D-2896 titration. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds. Molybdenum compounds useful in the compositions of the present invention include those having the formula: Mo(R''OCS 2 ) 4 and Mo(R''SCS 2 ) 4 where R″ is an organic radical selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl, generally having from 1 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and most preferably alkyl having from 2 to 12 carbon atoms. Particularly preferred are the dialkyldithiocarbamates of molybdenum. Another group of organo-molybdenum compounds useful in the lubricating compositions of the present invention are the trinuclear molybdenum compounds, particularly those of the formula Mo 3 S k A n D z and mixtures thereof, where A is independently selected from ligands bearing organic groups having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, D is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. At least 21 carbon atoms should be present in all of the organic groups of the ligand, e.g., at least 25, at least 30, or at least 35 carbon atoms. Lubricating oil compositions useful in all aspects of the invention preferably contain at least 10 ppm, at least 30 ppm, at least 40 ppm, more preferably at least 50 ppm molybdenum. Lubricating oil compositions useful in all aspects of the invention suitably contain no more than 1000 ppm, no more than 750 ppm or no more than 500 ppm molybdenum. Lubricating oil compositions useful in all aspects of the invention preferably contain from 10 to 10000 ppm molybdenum, for example from 30 to 750 or from 40 to 500 ppm (measured as molybdenum atoms).

[0033] The viscosity index of a base stock is increased or improved by the incorporation of certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII). Generally, polymeric materials useful as viscosity modifiers have a number average molecular weight (Mn) of 5,000 to 250,000, preferably 15,000 to 200,000, more preferably 20,000 to 150,000. These viscosity modifiers can be grafted with grafting materials such as maleic anhydride, and the grafted materials can be reacted with amines, amides, nitrogen-containing heterocycles, or alcohols to form multifunctional viscosity modifiers (dispersant-viscosity modifiers). Polymers prepared using diolefins contain ethylenic unsaturation, and such polymers are preferably hydrogenated. When the polymer is hydrogenated, the hydrogenation can be carried out using any of the techniques known in the art. For example, the hydrogenation can be carried out so that the ethylene and aromatic unsaturation are converted (saturated), for example, using methods such as those taught in U.S. Pat. Nos. 3,113,986 and 3,700,633. Or the hydrogenation can be carried out selectively, so that a significant portion of the ethylenic unsaturation is converted, while most of the aromatic unsaturation is not converted, as taught in U.S. Pat. Nos. 3,634,595; 3,670,054; 3,700,633 and Re27,145. Any of these methods can also be used to hydrate polymers that contain only ethylenic unsaturation and no aromatic unsaturation.

[0034] Pour point depressants (PPDs), also known as lube oil flow improvers (LOFIs), lower the minimum temperature at which a lubricant will flow. Compared to VMs, LOFIs generally have a lower number average molecular weight. Like VMs, LOFIs can be grafted with grafting materials such as maleic anhydride, and the grafted materials can be reacted with amines, amides, nitrogen-containing heterocycles, or alcohols to form multifunctional additives.

[0035] When a lubricating composition contains one or more of the above additives, each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function. Listed below are representative effective amounts of such additives when used in crankcase lubricants. All values ​​listed (except for those for detergents, since the detergents are used in the oil in the form of colloidal dispersants) are given as mass percent active ingredient (AI). [Table 2]

[0036] Preferably, the Noack volatility of the fully formulated lubricating oil composition (oil of lubricating viscosity with all additives) is 18 mass % or less, such as 14 mass % or less, preferably 10 mass % or less.Lubricating oil compositions useful in the practice of the present invention may have a total sulphurized ash content of 0.5 to 2.0 mass %, such as 0.7 to 1.4 mass %, preferably 0.6 to 1.2 mass %. Although not required, it may be desirable to prepare one or more additive concentrates (the concentrates are sometimes referred to as additive packages) containing the additives so that multiple additives can be added simultaneously to the oil to form the lubricating oil composition.

[0037] In another aspect, the invention provides a method of reducing friction and / or wear between contacting surfaces of a mechanical device, the method comprising lubricating the surfaces with the lubricating composition of the second aspect. Preferably, the mechanical device is a spark ignition or compression ignition internal combustion engine. In another aspect, the present invention provides the use of a polymer according to the first aspect as an additive in a lubricating composition to reduce friction and / or wear between contacting surfaces of a mechanical device lubricated by the composition. Preferably, the lubricating composition is a lubricating oil composition. Preferably, the mechanical device is a spark ignition or compression ignition internal combustion engine. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] Working Example Synthesis examples of polymers according to the present invention In the first step, 2-isopropenyl-2-oxazoline (5.06 g, 44.09 mmol) and 2-mercaptoethanol (3.2 ml, 44.99 mmol) were stirred in a round bottom flask under inert atmosphere for 15 minutes. The reaction mixture was then diluted with anhydrous dichloromethane, followed by the addition of 4-(dimethylamino)pyridine (DMAP, 5.54 g, 0.45 mmol) and α-bromoisobutyric acid (7.50 g, 44.99 mmol). The solution was then cooled in an ice bath, N,N'-diisopropylcarbodiimide (6.97 ml, 44.99 mmol) was slowly added dropwise, and the mixture was stirred overnight. After filtration, washing and solvent removal, and purification by flash chromatography, a colorless oil was obtained (6.67 g, 43.8% yield). For the second step, the product from the first step was combined with p-toluenesulfonic acid, sealed in a microwave vial and purged with nitrogen. Dry acetonitrile was then added to the mixture to produce a 4M solution and the vial was resealed. The mixture was heated to 60° C. and stirred until complete conversion, and analyzed by GPC and 1 Confirmed by 1 H NMR. As the final step, the product of the second step was treated with 2-ethylhexyl acrylate, a deactivator (Cu 2 Br) and ligand (Me 6 The mixture was combined with isopropanol (50% by weight) and the resulting solution was purged under an inert atmosphere for 30 minutes. A pre-activated copper wire wrapped around a magnetic stirrer was added to the reaction vessel. The reaction vessel was placed in a 25°C water bath and stirred until complete conversion.

[0039] Test Data Polymers having the general structure shown below were prepared as described above: The reactant ratios were varied to obtain the desired values ​​of n and m. [ka] The polymer details are given in the table below. [Table 3] "2EH" represents a 2-ethylhexyl group.

[0040] 1 g of each polymer was added to 99 g of API Group I mineral oil. These samples were subjected to traction and wear tests along with samples of the same mineral oil without any added polymer. Each oil was tested using a High Frequency Reciprocating Rig (HFRR) available from PCS Instruments, London, UK. This machine uses a 6mm diameter ball as the upper specimen which reciprocates under load against a disc-shaped lower specimen. The ball and disc are made of AISI 52100 polished steel. The test conditions are given in the table below. [Table 4] The wear scar formed on the lower disk specimens was analyzed using a Zemetrics ZeScope 3D optical profilometer using non-contact interferometric focal scanning. The amount of wear can be measured by measuring the disk material lost during the test. 3 The wear results were reported as wear scar volume (WSV) in units of 10 ... [Table 5] It is clear that the polymers of the present invention significantly reduce the amount of wear measured on the test samples compared to the base oil alone. These data confirm that the polymers are effective antiwear agents. The friction data are indicative of the wear protection mechanism provided by the polymers of the present invention: in all cases, the presence of the polymer significantly reduced the recorded friction, indicating greater separation of the contacting surfaces.

[0041] Further synthesis examples of polymers according to the invention Synthesis of caprolactone-derived hydroxyl oxazoline: ε-caprolactone (30.01 g, 262.84 mmol) was added to a flask and heated to 80 °C under inert conditions. Ethanolamine (17.45 mL, 262.84 mmol) was then added to the flask, followed by heating at 120 °C for 2 h. Titanium(IV) butoxide (0.5 mL) was then added to the reaction mixture, followed by heating at 230 °C for 2 h. The reaction mixture was then distilled under reduced pressure to give ε-hydroxypentyl oxazoline as a clear yellow oil (7.53 g, 18.2%). Synthesis of inimer: ε-Hydroxypentyloxazoline (5.50 g, 35.00 mmol) was charged into a round bottom flask with DCM. To this mixture, 4-(dimethylamino)pyridine (DMAP, 0.44 g, 3.50 mmol) and α-bromoisobutyric acid (5.89 g, 35.00 mmol) were added. The solution was then cooled in an ice bath and N,N'-diisopropylcarbodiimide (5.5 mL, 35.00 mmol) was slowly added dropwise and stirred overnight. The urea by-product was then filtered off and the crude product was purified by filtration with saturated NaHCO 3 The solvent was then removed under reduced pressure and the product was purified by flash chromatography (silica gel, EA, TEA 2%) to give the inimer as a colorless oil (6.74 g, 62.9%). General procedure for cationic ring-opening polymerization (CROP): Monomer, p-toluenesulfonic acid (appropriate molar ratio) are sealed in a microwave vial and heated under N for several minutes. 2 Dry acetonitrile was then added to the reaction mixture to make a 4 M solution and the vial was resealed. The reaction mixture was then stirred at 60° C. until complete or near complete conversion, and the reaction mixture was analyzed by GPC and 1 Confirmed by 1 H NMR. A general procedure for the synthesis of brush polymers by Cu(0)-RDRP with chain extension: acrylate monomer, brush initiator, deactivator (Cu 2 Br), ligand (Me 6TREN (in a ratio of [monomer: 1:0.05:0.18]) and solvent (isopropanol, 50% by mass) were placed in a Schlenk flask in the following order: deactivator, ligand, initiator, monomer, and solvent. After sealing with a rubber septum and purging under an inert atmosphere for at least 30 min, 5 cm of preactivated Cu wire (0.25 mm) wound on a magnetic stirrer was added. The reaction mixture was then placed in a 25 °C oil bath and stirred until complete conversion. 1 Conversion was determined by H NMR spectroscopy. SEC analysis was performed on a sample diluted in THF, which was filtered through basic alumina to remove residual copper species prior to analysis.

[0042] Test Data Polymers having the general structure shown below were prepared as described above: The reactant ratios were varied to obtain the desired values ​​of p and r, and the monomer selection was varied to obtain the desired value of q. The polymer details are given in the table below. [ka] [Table 6]

[0043] 1 g of each polymer was added to 99 g of API Group I mineral oil. These samples were subjected to traction testing against samples of the same mineral oil without any added polymer. Each oil was tested using a Mini Traction Tester (MTM) available from PCS Instruments, London, UK. This machine uses a 19.05 millimeter (3 / 4 inch) diameter ball as the upper specimen, which moves under load against a disk-shaped lower specimen. The ball and disk are independently driven to provide a range of slide-to-roll ratios. The ball and disk are made of AISI 52100 polished steel. The test conditions are shown in the table below. [Table 7] [Table 8] The MTM machine is equipped with a piezoelectric transducer that measures the average coefficient of friction between the ball and disc. The friction results are shown in the table below. Each value is the average of at least two tests with each test oil. Data reported are data points at 20 mm / s for the 100° C. Stribeck process (step 7). [Table 9] It is clear that the polymers of the present invention significantly reduced the coefficient of friction measured on the test samples, and demonstrated greater separation of the contacting surfaces, as compared to the base oil alone.

Claims

1. Structure (I): 【Chemistry 1】 (I) A polymer comprising a unit having the formula: In the formula, x is 2 or 3, and L is an integer such that y is 1 to 10 (CH 2 ) y or L is CH(CH) where z is an integer from 1 to 5. 3 ) CH 2 S (CH 2 ) z and [Q] is absent or has the structure (II): 【Chemistry 2】 (II) is a polymerized portion consisting of units having the formula: wherein R is a hydrocarbyl group or a hydrocarbyl group containing one or more heteroatoms, R may be linear, branched or cyclic, saturated or unsaturated, and R has from 1 to 30 carbon atoms; [Q] consists of identical structural (II) units or [Q] consists of more than one different structural (II) units having different R groups; A polymer wherein X is a halogen, a hydroxy group, an azide group, an NH2 thioether group, or an ether group.

2. The polymer according to claim 1, wherein the number of units (II) in [Q] is 2 to 200.

3. Structure (III): 【Chemistry 3】 (III) 3. The polymer of claim 1 or claim 2, further comprising a unit having the formula: In the formula, R 1 is a straight or branched, saturated or unsaturated hydrocarbyl group having from 2 to 24 carbon atoms; and w is 2 or 3.

4. 4. The polymer of claim 3, wherein the ratio of the number of Structure (I) units to the number of Structure (III) units in the polymer is from 1:100 to 100:

1.

5. 3. The polymer according to claim 1 or 2, which comprises a unit of structure (I).

6. The polymer according to claim 3 or 4, which consists of a unit of structure (I) and a unit of structure (III).

7. 7. The polymer of claim 1, wherein X is a bromine atom.

8. 8. The polymer of claim 1 having a number average molecular weight of 500 to 500,000 g / mol as measured by gel permeation chromatography against linear, narrow molecular weight distribution poly(methyl methacrylate) standards ranging from 550 to 600,000 g / mol.

9. 9. A lubricating composition comprising a major amount of a base lubricant, greater than 50 mass percent, based on the weight of the composition, and a minor amount, less than 50 mass percent, of the polymer of any one of claims 1 to 8, based on the weight of the composition.

10. 10. The lubricating composition of claim 9 which is a lubricating oil composition, wherein the base lubricant is an oil of lubricating viscosity.

11. 11. A method of reducing friction and / or wear between contacting surfaces in a mechanical device, comprising lubricating said surfaces with a lubricating composition according to claim 9 or claim 10.

12. 9. Use of a polymer according to any one of claims 1 to 8 as an additive in a lubricating composition to reduce friction and / or wear between the contacting surfaces of a mechanical device lubricated by said composition.

13. Structure (IV): 【Chemistry 4】 (IV) A compound of the formula: A compound of the formula: wherein p is 1 or 2, and q is an integer from 1 to 10.

14. Structure (V): 【Chemistry 5】 (V) A compound of the formula: A compound of the formula: wherein p is 1 or 2, and r is an integer from 4 to 10.

15. 14. A method for synthesizing a compound of structure (IV) as shown in claim 13, comprising: (a) reacting 2-isopropenyl-2-oxazoline, 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine, or a mixture thereof, with a mercaptoalcohol; (b) carrying out a Steglich esterification reaction by reacting the product of step (a) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyldiimide.

16. 15. A method for synthesizing a compound of structure (V) as set forth in claim 14, comprising: (a) ring-opening the lactone by reaction with 2-amino-1-ethanol, 3-amino-1-propanol, or a mixture thereof; (b) ring closing the product of step (a) by an organometallic catalyzed cyclocondensation reaction by heating in the presence of a transition metal catalyst; (c) carrying out a Steaglich esterification reaction by reacting the product of step (b) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and a dihydrocarbyldiimide.

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