Polymers and lubricating compositions containing polymers

Abstract

A polymer comprising units of the following formula I is presented: [Formula I] where x is 2 or 3; L is (CH2)y, where y is an integer from 1 to 10, or L is CH(CH3)CH2S(CH2)z, where z is an integer from 1 to 5; [Q] is absent or is a polymerized residue composed of units of the following formula II: [Formula II] [where R is a hydrocarbyl group or a hydrocarbyl group containing one or more heteroatoms, where R may be a straight-chain, branched-chain, or cyclic saturated or unsaturated hydrocarbyl group, and R has 1 to 30 carbon atoms]; [Q] is composed of units of the same formula II, or [Q] is composed of more than one different unit of formula II with different group R; and X is a halogen or another chain-terminating group. The polymer may be used as an additive in a lubricating composition by providing friction improvement and wear reduction.

Description

Technology Field

[0001] The present invention relates to polymers, in particular to amphiphilic polymers. The present invention also relates to lubricating compositions (lubricants) containing polymers, and to the use of 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. Polymers improve efficiency and aid in the reduction of wear by providing wear and friction-reducing properties to lubricants, such as lubricating oil compositions. Background Technology

[0002] There is significant interest in improving the fuel efficiency of gasoline and diesel engines. This can be achieved through engine lubricating oil by reducing the frictional contribution of the bulk fluid (by lowering oil viscosity) or by reducing friction between contact parts through the inclusion of friction modifier additives. There is also a continuing need to reduce the occurrence of wear in engines.

[0003] In a first aspect, the present invention provides a polymer comprising a unit of the following formula I:

[0004] [Chemical Formula I]

[0005]

[0006] In the above formula,

[0007] x is 2 or 3 and;

[0008] L is (CH2) y provided that y is an integer from 1 to 10, or L is CH(CH3)CH2S(CH2) z That is, z is an integer from 1 to 12, preferably an integer from 1 to 5;

[0009] [Q] is absent or is a polymerized residue consisting of a unit of the following chemical formula II:

[0010] [Chemical Formula II]

[0011]

[0012] [In the above formula,

[0013] R is a hydrocarbyl group, or a hydrocarbyl group containing one or more heteroatoms, wherein R may be a straight-chain, branched-chain, or cyclic saturated or unsaturated hydrocarbyl group, and R has 1 to 30 carbon atoms],

[0014] [Q] is composed of units of the same chemical formula II, or [Q] is composed of more than one different unit of chemical formula II with different group R;

[0015] X is a halogen or another chain termination group.

[0016] Preferably, the number of units of Formula I in the polymer is 2 to 100, preferably 2 to 50, for example 5 to 30.

[0017] In one embodiment, the polymer further comprises a unit of the following chemical formula III:

[0018] [Chemical Formula III]

[0019]

[0020] In the above formula,

[0021] R 1 It is a straight-chain or branched-chain saturated or unsaturated hydrocarbyl group having 1 to 50, preferably 2 to 24, for example 2 to 18 carbon atoms;

[0022] w is 2 or 3.

[0023] In one embodiment, the polymer consists of units of chemical formula I.

[0024] In another embodiment, the polymer consists of units of Formula I and units of Formula III.

[0025] The polymer of the present invention will be described in more detail below. Specific details for implementing the invention

[0026] The polymer of the present invention comprises a unit of the following chemical formula I;

[0027] [Chemical Formula I]

[0028] .

[0029] In one embodiment, all units of Formula I have an equal value of x of 2 or 3. In another embodiment, in some units, x is 2 and in other units, 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, preferably 1:100 to 100:1.

[0030] In one mode, L is (CH2) y However, y is an integer from 1 to 20. Preferably, y is an integer from 1 to 10, more preferably from 2 to 7, e.g., 5.

[0031] In another mode, L is CH(CH3)CH-2S(CH2) z However, z is an integer from 1 to 12, preferably an integer from 1 to 5. In one embodiment, z is 2.

[0032] In one mode, [Q] is absent.

[0033] In another embodiment, [Q] is a polymerized residue consisting of units of the following chemical formula II:

[0034] [Chemical Formula II]

[0035] .

[0036] In the context of the present invention, it should be understood that the polymerized residue includes, more strictly speaking, a residue referred to as an "oligomer." The number of units of Formula II may be as few as 2. In [Q], the number of units of Formula II is preferably 2 to 200, more preferably 2 to 100, and even more preferably 2 to 50.

[0037] The ratio of the number of units of Formula I in the polymer to the number of units of Formula II in the polymerized residue [Q] can be preferably 1:50 to 50:1, more preferably 1:20 to 20:1, even more preferably 1:10 to 10:1, e.g. 1:5 to 5:1, 1:2 to 2:1, e.g. 1:1.

[0038] The polymerized residue [Q] may be homopolymeric in that it consists of a single type of unit of Formula II. In this case, all groups R in [Q] are identical.

[0039] In another embodiment, the polymerized residue [Q] may be copolymerizable, in which two different types of units of Formula II are present. These different types of units of Formula II may be distinguished by different groups R. When [Q] is copolymerizable, the different units of Formula II may be arranged as a statistical copolymer formed such that the polymerization follows known statistical rules, e.g., Bernoulli statistics or Markovian statistics. Alternatively, the different units of Formula II may be arranged as a random copolymer. Even more alternatively, the different units of Formula II may be arranged in an ordered manner to provide an alternating copolymer, a periodic copolymer, or a block copolymer. In a specific embodiment, two or more different types of units of Formula II form a block copolymer.

[0040] When [Q] is copolymerized, there will be different types of units of Formula II distinguished by different group R. The number of different types of units of Formula II is not limited, but in a preferred embodiment, there will be 2, 3, 4, 5 or more, e.g., 12 or fewer different types of units of Formula II distinguished by different group R. In a particularly preferred embodiment, there will be two different types of units of Formula II. The ratio of each different type of unit of Formula II in [Q] is not limited. When [Q] is composed of two different types of compounds of Formula II, the ratio of the number of units of one type to the number of units of the other type is preferably 1:100 to 100:1, more preferably 1:50 to 50:1, even more preferably 1:20 to 20:1, e.g., 1:10 to 10. It will be understood that the polymerized residue [Q] may consist of only a single unit of one type of Formula II, or two or more units of another type of Formula II. For example, in a specific embodiment, [Q] may consist of one unit of one type, preferably two or more units of Formula II and a single unit of another type of Formula II attached as a terminal. Such an arrangement is exemplified in the following formula for a residue [Q] having three units of Formula II having a group R and terminal units of Formula II having R', where R and R' are different:

[0041] .

[0042] The group R is a hydrocarbyl group or a hydroxycarbyl group having one or more heteroatoms. As discussed above, all groups R present in [Q] can be identical, that is, each unit of Formula II will be identical. Alternatively, there may be two or more different units of Formula II, each with a different group R.

[0043] Examples of hydrocarbyl groups suitable as group R are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and analogs with a larger number of carbon atoms. Branched-chain alkyl groups, such as isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylpentyl, 2-propylheptyl, 2-butyloctyl, 2-ethylhexyl, isooctyl, isononyl, 2-tert-butylheptyl, 3-isopropylheptyl, 5-methylundecyl, 2-methyldodecyl, 5-methyltridecyl, 2-methylhexadecyl, 5-isopropylheptadecyl, 4-tert-butyloctadecyl, 5-ethyloctadecyl, 3-isopropyloctadecyl, and analogs are also suitable.

[0044] Additional examples of hydrocarbyl groups suitable as group R are alkenyl groups, such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, and analogs of a greater number of carbons. As is known in the art, alkenyl groups may contain a single carbon-carbon double bond which may be at any position on the carbon chain. Thus, for example, the propenyl group may be prop-1-enyl or prop-2-enyl. Alkenyl groups may otherwise contain more than one carbon-carbon double bond, an example of which is a "di-enyl" group containing two carbon-carbon double bonds. In a group having multiple carbon-carbon double bonds, the double bonds may be conjugated or non-conjugated.

[0045] In one embodiment, the group R may be a straight-chain alkenyl group derived from a natural source of fatty acids, such as vegetable oil or animal fat. These fatty acids are a mixture of compounds with different carbon chain lengths, and accordingly, the group R derived therefrom is similarly mixed. Often, these groups are represented as CX:Y, where X is the number of carbon atoms in the group and T is the number of double bonds in the group. An example of this is the oleyl group (derived from oleic acid), represented as C18:1, which has 18 carbon atoms and one carbon-carbon double bond. Mixtures consisting mainly of C18:1, C18:2, and C18:3 are suitable examples. As is known in the art, mixtures derived from natural fatty acids may also typically contain small amounts of alkyl groups, such as stearyl (C18:0).

[0046] Suitable branched-chain alkenyl groups are analogs containing double bonds of the aforementioned branched-chain alkyl groups.

[0047] Alkenyl groups, which are triunsaturated groups, are also suitable. An example of this is the propargyl group.

[0048] Additionally, the hydrocarbyl group R is a saturated and unsaturated ring group, such as a polycyclic group. These 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 those derived from decalins and their analogs. Examples of unsaturated groups include those derived from benzyl and naphthyl, and anthracene, phenanthrene, phenalene, and their analogs.

[0049] Substituted analogs of saturated and unsaturated ring groups, such as polycyclic groups, may include those substituted with a single alkyl or alkenyl group, more than one alkyl or alkenyl group, or a mixture thereof. The substituted group may be straight or branched and may include the aforementioned alkyl and alkenyl groups.

[0050] Alternatively or additionally, the group R may be a hydrocarbyl group containing one or more heteroatoms. Heteroatoms include oxygen, sulfur, nitrogen, phosphorus, and halogens. As is known in the art, heteroatoms may be located between saturated or unsaturated carbon-carbon bonds, as found, for example, in ethers or pyridines, or on substituents attached to a hydrocarbyl group, such as a hydroxy or carboxylic acid group.

[0051] An example of a hydrocarbyl group containing one or more heteroatoms is the chemical formula -[(CR2H) a O] b OR3 is a polyalkylene glycol group (wherein a is an integer from 2 to 4, preferably 2; and b is an integer from 2 to 100, preferably an integer from 2 to 20, e.g., an integer from 2 to 10). R2 is hydrogen or an alkyl residue, e.g., CH2 or CH2CH2. Preferably, R2 is hydrogen. R3 is hydrogen, an alkyl group, e.g., methyl ethyl ethyl, or an aryl group, e.g., phenyl. Preferably, R3 is methyl. Preferably, since a is 2 and R2 is hydrogen, the group is a polyethylene glycol group. In a preferred embodiment, since R2 is hydrogen, a is 2, and b is 2, the group is a diethylene glycol group. In another preferred embodiment, since a is 2 and b is an average value of 7 to 8, the group is an oligoethylene glycol group. Further examples of hydrocarbyl groups containing one or more heteroatoms are groups having one or more hydrocarbyl groups. These include, for example, hydroxybenzyl groups and similar aromatic groups having one or more hydroxy groups. Amino and silyl groups are also suitable.

[0052] In one embodiment, the polymer further comprises a unit of the following chemical formula III:

[0053] [Chemical Formula III]

[0054] .

[0055] With respect to the hydrocarbyl group R, the hydrocarbyl group R such as the hydrocarbyl group described herein 1 This is desirable.

[0056] In a preferred embodiment, R 1 It comprises a mixture of straight-chain alkyl groups or straight-chain alkenyl groups derived from natural sources of fatty acids, such as vegetable oils or animal oils. This is described herein in relation to group R.

[0057] Preferably, R 1 It comprises a mixture of straight-chain alkenyl groups derived from natural sources of fatty acids, such as vegetable oils or animal oils, wherein at least 10% of said groups comprises unsaturated hydrocarbyl groups having 8 to 20 carbon atoms. More preferably, group R 1 At least 20%, 30%, 40%, or 50% of comprises unsaturated hydrocarbyl groups having 8 to 20 carbon atoms. Most preferably, group R 1 At least 60% or 70% of comprises unsaturated hydrocarbyl groups having 8 to 20 carbon atoms. Preferably, group R 1 At least 10% of comprises unsaturated hydrocarbyl groups having 15 to 20 carbon atoms. More preferably, group R 1 At least 20%, 30%, 40%, or 50% of comprises unsaturated hydrocarbyl groups having 15 to 20 carbon atoms. Most preferably, group R 1 At least 60% or 70% of it contains unsaturated hydrocarbyl groups having 15 to 20 carbon atoms.

[0058] Preferably, R 1 ... comprises a mixture of linear alkenyl groups, wherein at least 5% of the groups are unsaturated hydrocarbyl groups having 17 carbon atoms. More preferably, group R1 At least 10%, 20%, 30%, 40%, 50%, or 60% of comprises an unsaturated hydrocarbyl group having 17 carbon atoms. More preferably, R 1 At least 70% of it contains an unsaturated hydrocarbyl group having 17 carbon atoms.

[0059] In a preferred embodiment, R 1 It comprises a mixture of linear alkenyl groups, wherein at least 50% of the groups are single, double, or triple unsaturated C 17 It comprises an alkenyl group or any mixture thereof. More preferably, at least 60% of the group is a single, double, or triple unsaturated C 17 It comprises an alkenyl group or any mixture thereof. More preferably, at least 70% of the group is a single, double, or triple unsaturated C 17 It includes an alkeneyl group or any mixture thereof.

[0060] In a particularly desirable embodiment, R 1 It is single, double, or triple unsaturated C 17 It includes a mixture of alkenyl groups, wherein the mixture is single, double, or triple unsaturated C 17 It forms the main structure of the alkenyl group. This mixture may contain small amounts of smaller or larger molecules.

[0061] In one embodiment, w is 2 in all units of Formula III present. In another embodiment, w is 3 in all units of Formula III present. In yet another embodiment, the units of Formula III are a mixture of residues, where w is 2 and 3. In the above embodiment, the ratio of the number of units of Formula III where w is 2 to the number of units of Formula III where w is 3 may be any suitable value, preferably 1:100 to 100:1, more preferably 1:50 to 50:1 or 1:20 to 20:1, e.g. 1:10 to 10:1.

[0062] In the polymer of the present invention, X is a halogen or a chain termination group. Preferably, X is a halogen, and most preferably, X is bromine. As is known in the art, a terminal group conversion reaction can be used to provide various types of chain termination groups X. For example, X may be a hydroxyl group, an azide group, an NH2 thioether group, or an ether group.

[0063] The polymer of the present invention may have any molecular weight, but preferably has 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, when measured by gel permeation chromatography with reference to a linear narrow poly(methyl methacrylate) standard of 500 to 600,000 g / mol.

[0064] Specific examples of polymers according to the present invention include: a polymer having 10 units of Formula I, each consisting of 20 units of Formula II, where each group R is 2-ethylhexyl; a polymer having 50 units of Formula I, where each group R is 2-ethylhexyl; and a polymer having 10 units of Formula I, where each group R is 2-ethylhexyl. Other examples include: a polymer having 10 units of Formula I, where each group R is 2-ethylhexyl and 1 terminal unit of Formula II, where R is a catechol group; and a polymer having 10 units of Formula I, where each group R is 2-ethylhexyl and 5 units of Formula II, where R is heptadecyleethylene glycol methyl ether. In all cases, L is (CH2) y or CH(CH3)CH2S(CH2) zIt may be, provided that y and z are as defined above.

[0065] A method for synthesizing a polymer according to the present invention is described below.

[0066] In the initial stage, a compound of the following chemical formula:

[0067]

[0068] [In the above formula, p is 1 (2-isoprofenyl-2-oxazoline) or 2 (2-isoprofenyl-5,6-dihydro-4H-1,3-oxazine)]

[0069] ...is reacted with a mercapto alcohol, e.g., 2-mercaptoethanol in this example, to produce a compound of the following chemical formula:

[0070] .

[0071] 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.

[0072] Unlike 2-mercaptoethanol as presented above, mercaptoalcohols with longer carbon chains are also suitable.

[0073] Subsequently, a Steglich esterification reaction is carried out so that the compound further reacts with a tertiary halogen acid, such as α-bromoisobutyric acid, in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide, such as N,N'-diisopropylcarbodiimide, to produce a compound of the following chemical formula (Compound A):

[0074] .

[0075] In the initial stage of the alternative, the lactone is first ring-opened by reacting with 2-amino-1-ethanol or 3-amino-1-propanol through nucleophilic attack by a lone pair of nitrogen electrons. For example, a ring-opened caprolactone using 2-amino-1-ethanol produces a compound of the following chemical formula:

[0076] .

[0077] Subsequently, the above compound is a transition metal catalyst, such as Ti(O₂). n A compound of the following chemical formula is formed by ring closure via an organometal-catalyzed condensation-cyclization reaction by heating in the presence of Bu)4:

[0078] .

[0079] As described above, subsequently, a Steglych esterification reaction is carried out so that the compound further reacts with a tertiary halogen acid, such as α-bromoisobutyric acid, in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide, such as N,N'-diisopropylcarbodiimide, to produce a compound of the following chemical formula (compound B):

[0080] .

[0081] It will be understood that in a ring-opening reaction, 2-amino-1-ethanol is replaced with 3-amino-1-propanol to produce a compound of the following chemical formula (compound B');

[0082] .

[0083] In addition, it will be understood that the length of the carbon chain between the ring residue and the intrachain oxygen atom is determined by the size of the lactone used in the ring-opening reaction. As is known in the art, both lactones larger and smaller than caprolactone are suitable for use in the present invention.

[0084] Compounds A, B and B', or analogs thereof, are used as monomers in polymerization to produce a polymer according to the present invention.

[0085] The polymerization of compounds A, B, and B', or analogs thereof, in the absence of other monomers, produces a polymer having only the unit of Formula I in the absence of [Q].

[0086] Alternatively, copolymerization of compounds A, B and B', or analogs thereof, with a compound of the following formula produces a polymer having units of formula I and units of formula III in which [Q] is absent:

[0087]

[0088] In the above formula, R1 is as defined above for Formula III. Polymerization can be achieved using a cationic ring-opening reaction (CROP). A suitable synthesis route involves heating a monomer or a mixture of monomers in the presence of a tosylate, e.g., methyl tosylate, triplate, primary or tertiary alkyl bromide or iodide, or a Lewis acid.

[0089] The polymerized residue [Q] can be introduced by reacting the polymer produced as described above with one or more acrylate monomers. This is appropriately achieved using Cu(0)-mediated reversible-inert radical polymerization (RDRP), where the initial polymer acts as an initiator. An inert agent (e.g., Cu2Br) and a ligand (e.g., Me6TREN) are used. When a single acrylate is used, [Q] consists of units of Formula II in which all groups R are the same. Using a mixture of two or more different acrylate monomers results in residue [Q] in which different groups R are randomly aligned. Alternatively, the reaction can be carried out in two or more steps, in which units of Formula II with one type of group R are produced in the first step, and then units of Formula II with different types of group R are produced by the subsequent addition of different acrylate monomers. In this manner, residue [Q] has a block copolymer structure in which the size of each block can be controlled by adjusting the amount of each acrylate monomer used.

[0090] Compounds A, B, B', and analogs thereof, and synthesis thereof form another aspect of the present invention, and in yet another aspect, the present invention presents a compound of the following formula IV:

[0091] [Chemical Formula IV]

[0092]

[0093] In the above formula, p is 1 or 2, and q is an integer from 1 to 10, preferably an integer from 1 to 5.

[0094] In another aspect, the present invention presents a compound of the following formula V:

[0095] [Chemical Formula V]

[0096]

[0097] In the above formula, p is 1 or 2, and r is an integer from 4 to 10, preferably an integer from 2 to 5.

[0098] In another aspect, the present invention

[0099] (a) reacting 2-isoprofenyl-2-oxazoline, 2-isoprofenyl-5,6-dihydro-4H-1,3-oxazine, or a mixture thereof with mercapto alcohol; and

[0100] (b) a step of performing a Steglych esterification reaction by reacting the product of step (a) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide, preferably N,N'-diisopropylcarbodiimide.

[0101] A method for synthesizing a compound of chemical formula IV containing is presented.

[0102] In another aspect, the present invention

[0103] (a) A step of ring-opening a lactone through reaction with 2-amino-1-ethanol, 3-amino-1-propanol, or a mixture thereof;

[0104] (b) the product of step (a) above, a transition metal catalyst, preferably Ti(O₂) n A step of ring-closing through an organometal-catalyzed condensation-cyclization reaction by heating in the presence of Bu)4; and

[0105] (c) a step of performing a Steglych esterification reaction by reacting the product of step (b) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide, preferably N,N'-diisopropylcarbodiimide.

[0106] A method for synthesizing a compound of chemical formula V containing [ ] is presented.

[0107] "Active ingredient" or "(ai)" refers to an additive substance that is not a diluent or solvent.

[0108] "Comprising" or any cognate word specifies the presence of the mentioned feature, step, integer, or component, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. Expressions "consisting of" or "consisting essentially of" or cognate expressions may be included within "comprising" or any cognate word. The expression "consisting essentially of" allows for the inclusion of a substance that does not substantially affect the properties of the composition to which it applies. Expressions "consisting of" or cognate expressions mean that only the mentioned feature, step, integer, component, or group thereof designated by such expression is present.

[0109] As used herein, "oil-soluble," "oil-dispersible," or similar terms do not necessarily indicate that a compound or additive can be soluble, soluble, miscible, or suspended in oil in all proportions. However, they imply that, for example, it can be soluble or stably dispersed in oil to a sufficient degree to produce the intended effect in the environment in which the oil is used. Furthermore, the additional incorporation of other additives may also allow for higher levels of the specific additive, if desirable.

[0110] In relation to additives, "ashless" means that the additive does not contain metal.

[0111] In relation to additives, "metal-containing" means that the additive contains metal.

[0112] "Major amount" means more than 50 mass% of the composition or mixture.

[0113] "Minor amount" means 50 mass% or less of the composition or mixture.

[0114] With respect to additives, "effective amount" refers to the amount of an additive (e.g., additive concentrate) in a composition that is effective in providing the desired technical effect and provides it.

[0115] "ppm" means parts per million mass based on the total mass of the composition.

[0116] The "metal content" of a composition or additive component, for example, the molybdenum content of an additive concentrate or the total metal content (i.e., the sum of all individual metal contents), is measured by ASTM D5185.

[0117] In relation to additive components or compositions, "TBN" refers to the total base content (mg KOH / g) measured by ASTM D2896.

[0118] "KV 100" refers to the kinematic viscosity at 100°C as measured by ASTM D445.

[0119] HTHS means high temperature and high shear at 150°C as measured by -CEC-L-36-A-90.

[0120] "Phosphorus content" is measured by ASTM D5185.

[0121] "Sulfur content" is measured by ASTM D2622.

[0122] "Sulfurized ash content" is measured by ASTM D874.

[0123] Mn refers to the number average molecular weight measured by gel permeation chromatography with reference to a linear, narrow poly(methyl methacrylate) standard in the range of 550 to 600,000 g / mol.

[0124] Mw refers to the weight-average molecular weight measured by gel permeation chromatography with reference to a linear, narrow poly(methyl methacrylate) standard in the range of 550 to 600,000 g / mol.

[0125] "Dispersion" refers to Mw / Mn (denoted as Ð).

[0126] Furthermore, it will be understood that various ingredients used, which are not only optimal and conventional but also essential, may react under the conditions of formulation, storage, and use, and that the present invention also provides products obtainable or obtained by any such reaction.

[0127] In addition, it is understood that the upper and lower limits of any quality, range, or ratio described herein may be combined independently.

[0128] lubricating composition

[0129] In a second aspect, the present invention provides a lubricating composition comprising a large amount of base lubricant exceeding 50 mass% based on the mass of the lubricating composition and a small amount of polymer according to the first aspect of the present invention less than 50 mass% based on the mass of the lubricating composition. The polymer provides friction-reducing properties to the lubricant. Therefore, using such a lubricant to lubricate machinery such as engines, transmissions, gears, etc. improves the efficiency of the machinery and helps reduce wear on contacting machinery parts.

[0130] The base lubricant may be a lubricating oil, grease, or fuel oil. In a preferred embodiment, the base lubricant is a lubricating oil such that the lubricating composition becomes a lubricating oil composition.

[0131] The lubricating oil composition of the present invention may be a lubricant suitable for use, for example, as an automotive motor oil, and comprises a large amount of oil of lubricating viscosity and a small amount of a polymer according to the first aspect of the present invention. Typically, the lubricating oil composition will also contain other performance-enhancing additives (auxiliary additives) in addition to the polymer. The lubricating composition may also be in the form of an additive concentrate for blending with the oil of lubricating viscosity to produce a final lubricant.

[0132] The lubricating oil composition of the present invention will preferably contain 0.01 to 10 mass%, more preferably 0.01 to 5, for example, up to 0.5, 1, 2, 3, or 4 mass% based on the mass of the composition of the polymer of the present invention. In the case of an additive concentrate, the polymer will typically be present in an amount of 0.07 to 70 mass% based on the mass of the composition in an oil of lubricating viscosity or other suitable carrier fluid.

[0133] Lubricating oil (sometimes referred to as "base stock" or "base oil") is the main liquid component of a lubricant, to which additives and possibly other oils are blended to produce, for example, a final lubricant (or lubricant composition). Base oils useful for the preparation of additive concentrates, as well as for the preparation of lubricant compositions therefrom, can be selected from natural oils (vegetable, animal, or mineral), synthetic lubricants, and mixtures thereof.

[0134] The definitions of base stock and base oil in the present invention are the same as those found in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System” Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998, which classifies base stock as follows.

[0135] a) Group I base stock contains less than 90% saturate and / or more than 0.03% sulfur and has a viscosity index of 80 or higher and less than 120 when using the test method specified in Table E-1.

[0136] b) Group II base stock contains more than 90% saturation and less than 0.03% sulfur and has a viscosity index of 80 or more and less than 120 when using the test method specified in Table E-1.

[0137] c) Group III base stock contains more than 90% saturation and less than 0.03% sulfur and has a viscosity index of 120 or higher when using the test method specified in Table E-1.

[0138] d) Group IV base stock is polyalphaolefin (PAO).

[0139] e) Group V base stock includes all other base stocks not included in Groups I, II, III, or IV.

[0140] Typically, the base stock is preferably 3 to 12, more preferably 4 to 10, and most preferably 4.5 to 8 mm at 100°C. 2 It has a viscosity of / s.

[0141] [Table E-1]

[0142] Analysis method for base stock

[0143]

[0144] Preferably, the lubricating viscosity oil comprises a Group II or Group III base stock in a mass% or greater of 10, more preferably 20, even more preferably 25, even more preferably 30, even more preferably 40, and even more preferably 45, based on the total mass of the lubricating viscosity oil. More preferably, the lubricating viscosity oil comprises a Group II or Group III base stock in a mass% or greater of 50, preferably 60, even more preferably 70, even more preferably 80, and even more preferably 90, based on the total mass of the lubricating viscosity oil. Most preferably, the lubricating viscosity oil is essentially composed of a Group II and / or Group III base stock. In some embodiments, the lubricating viscosity oil is composed solely of a Group II and / or Group III base stock. In the latter case, it is acknowledged that the additives included in the lubricating oil composition may comprise a carrier oil that is not a Group II or Group III base stock.

[0145] Oils of different lubricating viscosities that may be included in the lubricating oil composition are listed as follows:

[0146] Natural oils include animal and vegetable oils (e.g., castor and lard oils), liquid petroleum oils, and hydro-refined and solvent-treated mineral lubricants of the paraffin, naphthenic, and mixed paraffin-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

[0147] Synthetic lubricating oils comprise hydrocarbon oils, such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene)); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g., biphenyl, terphenyl, alkylated polyphenol); and alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues thereof.

[0148] Other suitable classes of synthetic lubricants include esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, souveric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid) and 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, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by the reaction of 1 mole of sebaxane with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0149] Esters useful as synthetic oils are also C5 to C 12It includes monocarboxylic acids and polyols, and polyol ethers, such as neopentyl glycol, dimethylolpropane, pentaerythritol, dipentaerythritol, and those prepared from dipentaerythritol.

[0150] Unrefined, refined, and re-refined oils may be used in the compositions of the present invention. Unrefined oil is obtained directly from natural or synthetic sources without further refining treatment. For example, shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil. Refined oil is similar to unrefined oil except that it is further processed in one or more refining steps to improve one or more properties. Many such refining techniques, such as distillation, solvent extraction, acid or base extraction, filtration, and osmosis, are known to those skilled in the art. Re-refined oil is obtained by a process similar to that used to obtain refined oil, which is applied to refined oil that has already been in service. Such re-refined oil is also known as regenerated or reprocessed oil and is often further treated by techniques for processing used additives and oil cracking products.

[0151] Another example of a base oil is a gas-to-liquid ("GTL") base oil, that is, the base oil may be an oil derived from Fischer-Tropsch synthetic hydrocarbons produced from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require additional processing to be useful as a base oil. For example, they may be hydrogenated isomerized; hydrocracking and hydrogenated isomerized; dewaxed; or hydrogenated isomerized and dewaxed by methods known in the art.

[0152] The oil of lubricating viscosity may also include a Group I, Group IV, or Group V base stock or base oil blend of the aforementioned base stock.

[0153] The lubricating composition of the present invention preferably comprises an oil with a lubricating viscosity of 60% or more, for example 70% or more, based on the weight of the composition.

[0154] auxiliary-additive

[0155] The lubricating composition of the present invention, in particular the lubricating oil composition, may further comprise one or more phosphorus-containing compounds; oxidation inhibitors or antioxidants; dispersants; metal detergents; anti-wear agents; friction modifiers, viscosity modifiers and other auxiliary additives, provided that they differ from the polymer of the present invention. These will be discussed in more detail below.

[0156] Suitable phosphorus-containing compounds include metal salts of dihydrocarbyl dithiophosphate, which are frequently used as anti-wear agents and antioxidants. The metal is preferably zinc, but may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, or copper. Zinc salts are most commonly used in lubricants in an amount of 0.1 to 10, preferably 0.2 to 2 mass%, based on the total weight of the lubricant composition. They can be prepared according to known techniques by first forming dihydrocarbyl dithiophosphate (DDPA) by reacting P2S5 with usually one or more alcohols or phenols, and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphate can be prepared by reacting a mixture of primary and secondary alcohols. Alternatively, polythiophosphate can be prepared, wherein the hydrocarbyl group of one phase is entirely secondary by nature and the hydrocarbyl group of the other phase is entirely primary by nature. To produce zinc salts, any basic or neutral zinc compound may be used, but oxides, hydroxides, and carbonates are most commonly used. Commercial additives often contain excess zinc due to the use of an excess of basic zinc compounds in the neutralization reaction.

[0157] The preferred zinc dihydrocarbyl dithiophosphate is an oil-soluble salt of dihydrocarbyl dithiophosphate and can be represented by the following chemical formula:

[0158]

[0159] In the above, R and R' may be the same or different hydrocarbyl radicals containing 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkalyl, and alicyclic radicals. Particularly preferred as the 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, butenyl. To obtain oil solubility, the total number of carbon atoms (i.e., R and R') in the dithiophosphoric acid will generally be 5 or more. Accordingly, zinc dihydrocarbyl dithiophosphate (ZDDP) may include zinc dialkyl dithiophosphate. The lubricating oil composition of the present invention may suitably have a phosphorus content of about 0.08 mass% (800 ppm) or less. Preferably, in the practice of the present invention, ZDDP is used in an amount close to or equal to the maximum allowable amount, preferably in an amount providing a phosphorus content within 100 ppm of the maximum allowable amount of phosphorus. Accordingly, a lubricating oil composition useful in the practice of the present invention preferably contains ZDDP or other zinc-phosphorus compounds in an amount that introduces 0.01 to 0.08 mass% of phosphorus, e.g. 0.04 to 0.08 mass% of phosphorus, preferably 0.05 to 0.08 mass% of phosphorus, based on the total mass of the lubricating oil composition.

[0160] Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate during use. Oxidative deterioration can be demonstrated by sludge in the lubricant, varnish-like deposits on metal surfaces, and an increase in viscosity. Such oxidation inhibitors are hindered phenols, preferably C5 to C 12Alkaline earth metal salts of alkylphenolthioesters having alkyl side chains, calcium nonylphenol sulfide, oil-soluble phenates and sulfated phenates, phosphosulfated or sulfated hydrocarbons or esters, phosphorus esters, metal thiocarbamates, oil-soluble copper compounds described in U.S. Patent No. 4,867,890, and molybdenum-containing compounds.

[0161] Aromatic amines having two or more aromatic groups directly attached to nitrogen constitute another class of compounds frequently used for antioxidant purposes. A typical oil-soluble aromatic amine having two or more aromatic groups directly attached to a single amine nitrogen contains 6 to 16 carbon atoms. Amines may contain more than two aromatic groups. A compound having a total of three or more aromatic groups, wherein two aromatic groups are connected by covalent bonds or by atoms or groups (e.g., oxygen or sulfur atoms, or -CO-, -SO2-, or alkylene groups) and two are directly attached to a single amine nitrogen, is also considered an aromatic amine having two or more aromatic groups directly attached to nitrogen. The aromatic ring is typically 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 two or more aromatic groups directly attached to one amine nitrogen should preferably not exceed 0.4 mass%.

[0162] Dispersants are additives whose primary function is to passivate solid and liquid contaminants by retaining them in a suspension, thereby reducing sludge deposits and simultaneously reducing engine deposits. For example, dispersants retain oil-insoluble substances resulting from oxidation during the use of lubricants in the suspension, thereby preventing sludge aggregation and precipitation or deposition on metal parts of the engine.

[0163] In the present invention, the dispersant is preferably an "ash-free" non-metallic organic material that does not substantially form ash upon combustion, in contrast to the metal-containing and consequently ash-forming material described above. These comprise long hydrocarbon chains having polar heads, the polarity of which is derived, for example, by the inclusion of O, P, or N atoms. The hydrocarbon is a lipophilic group imparting oil solubility, for example, having 40 to 500 carbon atoms. Thus, the ash-free dispersant may comprise an oil-soluble polymer backbone.

[0164] A preferred class of olefin polymers consists of polybutene, in particular polyisobutene (PIB) or poly-n-butene, and can be produced, for example, by polymerization of a C4 purified stream.

[0165] The dispersants comprise, for example, derivatives of long-chain hydrocarbon-substituted carboxylic acids, examples of which are derivatives of high molecular weight hydrocarbyl-substituted succinic acid. A notable group of dispersants consists of hydrocarbon-substituted succinims prepared, for example, by reacting the said acid (or derivative) with a nitrogen-containing compound, advantageously polyalkylene polyamines, such as polyethylene polyamines. Particularly preferred are US-A-3,202,678; -3,154,560; -3,172,892; -3,024,195; -3,024,237, -3,219,666; It is a reaction product of an alkenyl succinic anhydride and a polyalkylene polyamine as described in -3,216,936, which may be post-treated, for example borication (as described in US-A-3,087,936 and -3,254,025), fluorination, or oxylation to improve its properties. For example, borication may be achieved by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxides, boron halides, boron acids, and esters of boron acids.

[0166] Preferably, the dispersant is a succinimide-dispersant derived from polyisobutene having a number average molecular weight of 1,000 to 3,000, preferably 1,500 to 2,500, and suitable functionality, where present. The succinimide is preferably derived from highly reactive polyisobutene.

[0167] Another example of a type of dispersant that can be used is a linked aromatic compound as described in EP-A-2 090 642.

[0168] Detergents are additives that reduce the formation of piston deposits, such as high-temperature varnish and lacquer deposits in engines; they generally possess acid-neutralizing properties and can retain fine solids in a suspension. Most detergents are based on metal "soaps," that is, metal salts of acidic organic compounds.

[0169] The detergent generally comprises a polar head having a long hydrophobic tail, and the polar head comprises a metal salt of an acidic organic compound. The salt may contain a substantially stoichiometric amount of metal when generally described as a normal or neutral salt, and typically the total number of bases or TBN (which can be measured by ASTM D2896) at 100% active mass will be 0 to 80. A large amount of metal base may be included by reacting an excess amount of metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.

[0170] The resulting superbasic detergent comprises a neutralized detergent as an outer layer of metal base (e.g., carbonate) micelles. This superbasic detergent may have a TBN of 150 or more in 100% active mass, typically 200 to 500 or more.

[0171] Suitablely, detergents that may be used include oil-soluble neutral and perbasic sulfonates, phenates, sulfide phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of metals, particularly alkali metals or alkaline earth metals, e.g., Na, K, Li, Ca, and Mg. The most commonly used metals are Ca and Mg (both of which may be present in detergents used in lubricating compositions), and mixtures of Ca and / or Mg with Na. Detergents may be used in various combinations.

[0172] Additional additives may be incorporated into the composition of the present invention to ensure that specific performance requirements are met. Examples of such additives that may be included in the lubricating oil composition of the present invention are metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, other friction modifiers, antifoaming agents, anti-wear agents, and pour point depressants. Some are discussed in more detail below.

[0173] Friction modifiers and fuel-efficient agents compatible with other components of the final oil may also be included. Examples of such substances include glyceryl monoesters of higher fatty acids, e.g., glyceryl mono-oleates; esters of long-chain polycarboxylic acids and diols, e.g., butanediol esters of dimerized unsaturated fatty acids; and alkoxylated alkyl-substituted monoamines, diamines, and alkyl ether amines, e.g., ethoxylated tallow amines and ethoxylated tallow ether amines.

[0174] Other known friction modifiers include oil-soluble organic-molybdenum compounds. These organic-molybdenum friction modifiers also provide antioxidant and wear-resistant properties to lubricant compositions. Examples of these oil-soluble organic-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanates, sulfides, and mixtures thereof. Molybdenum dithiocarbamates, dialkyl dithiophosphates, alkyl xanthates, and alkyl thioxanates are particularly preferred.

[0175] Additionally, molybdenum compounds may be acidic molybdenum compounds. These compounds will react with basic nitrogen compounds when measured by the ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, e.g., sodium molybdate hydrogen, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds.

[0176] Among the molybdenum compounds useful in the composition of the present invention are organic-molybdenum compounds of the following chemical formula:

[0177] Mo(R"OCS2)4 and

[0178] Mo(R"SCS2)4

[0179] In the above, “R” is generally an organic group selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl groups having 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms, most preferably alkyl groups having 2 to 12 carbon atoms. A dialkyl dithiocarbamate of molybdenum is particularly preferred.

[0180] Another group of organic molybdenum compounds useful in the lubricating composition of the present invention is trinuclear molybdenum compounds, particularly those with the formula Mo3S k An D z Compounds and mixtures thereof, wherein A is an independently selected ligand having an organic group having a sufficient number of carbon atoms to impart solubility or dispersibility in oil to the compound, n is 1 to 4, k is 4 to 7, D is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5 and includes non-stoichiometric values. Among all ligand organic groups, at least 21 carbon atoms, e.g., at least 25, at least 30, or at least 35 carbon atoms must be present.

[0181] In all embodiments of the present invention, a useful lubricating oil composition preferably contains molybdenum of 10 ppm or more, 30 ppm or more, 40 ppm or more, and more preferably 50 ppm or more. Suitably, in all embodiments of the present invention, a useful lubricating oil composition contains molybdenum of 1000 ppm or less, 750 ppm or less, or 500 ppm or less. In all embodiments of the present invention, a useful lubricating oil composition preferably contains 10 to 1000, e.g., 30 to 750 or 40 to 500 ppm of molybdenum (measured in molybdenum atoms).

[0182] The viscosity index of the base stock is increased or improved by incorporating a specific polymeric material that functions as a viscosity modifier (VM) or a viscosity index improver (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. Such viscosity modifiers can be grafted with a grafting material, such as maleic anhydride, for example, and the grafted material can react with, for example, an amine, amide, a nitrogen-containing heterocyclic compound, or an alcohol to form a multifunctional viscosity modifier (dispersant-viscosity modifier).

[0183] Polymers prepared from diolefins will contain ethylenically unsaturated polymers, and such polymers are preferably hydrogenated. When the polymer is hydrogenated, hydrogenation may be achieved using any technique known in the prior art. For example, hydrogenation may be achieved such that both ethylenically unsaturated and aromatically unsaturated polymers are converted (saturated) using a method such as that taught, for example, in U.S. Patents No. 3,113,986 and No. 3,700,633, or hydrogenation may be achieved selectively such that a substantial portion of the ethylenically unsaturated polymers are converted while the aromatically unsaturated polymers are converted little or nothing, as taught, for example, in U.S. Patents No. 3,634,595; 3,670,054; 3,700,633 and Re 27,145. Any of these methods may also be used to hydrogenate a polymer containing only ethylenically unsaturated polymers and not aromatically unsaturated polymers.

[0184] Pour point depressants (PPDs), also known as lubricant flow improvers (LOFIs), lower the lowest temperature at which lubricating oil flows. 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 react with, for example, amines, amides, nitrogen-containing heterocyclic compounds, or alcohols to form multifunctional additives.

[0185] If the lubricating composition contains one or more of the aforementioned additives, each additive is typically blended into the base oil in an amount that enables the additive to provide the desired function. Typical effective amounts of such additives when used in crankcase lubricants are listed below. All listed values ​​(excluding detergent values, as detergents are used in the oil in the form of colloidal dispersants) are referred to as mass % active ingredient (AI).

[0186]

[0187] Preferably, the Noack volatility of the fully formulated lubricating oil composition (oil of lubricating viscosity + all additives) is 18 or less, e.g. 14 or less, preferably 10 or less by mass%. A lubricating oil composition useful for the practice of the present invention may have a total sulfated ash content of 0.5 to 2.0, e.g. 0.7 to 1.4, preferably 0.6 to 1.2 by mass%. Although not essential, it may be desirable to prepare one or more additive concentrates containing additives (concentrates sometimes referred to as additive packages) and to simultaneously add several additives to the oil to form the lubricating oil composition.

[0188] In another aspect, the present invention provides a method for reducing friction and / or wear between contact surfaces of a mechanical device, comprising lubricating the surface with a lubricating composition of the second aspect. Preferably, the mechanical device is a spark-ignition or compression-ignition internal combustion engine.

[0189] In another aspect, the present invention provides a use of a polymer according to the first aspect as an additive in a lubricating composition to reduce friction and / or wear between contact 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.

[0190] Examples

[0191] Exemplary synthesis of a polymer according to the present invention

[0192] In the first step, 2-propenyl-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 an inert atmosphere for 15 minutes. Subsequently, the reaction mixture was diluted with anhydrous dichloromethane, and then 4-(dimethylamino)pyridine (DMAP, 5.54 g, 0.45 mmol) and α-bromoisobutyric acid (7.50 g, 44.99 mmol) were added. Subsequently, the solution was 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, colorless oil was obtained by purification by rapid chromatography (6.67 g, 43.8% yield).

[0193] In the second step, the product obtained from the first step was combined with p-toluenesulfonic acid, placed in a microwave vial, sealed, and purged with nitrogen. Subsequently, dry acetonitrile was added to the mixture to form a 4 M solution, and the vial was resealed. The mixture was heated to 60°C and stirred until complete conversion (GPC and 1 (Confirmed by H NMR).

[0194] In the final step, the product of the second step was combined with the desired ratio of 2-ethylhexyl acrylate, an inactivator (Cu2Br), and a ligand (Me6TREN). The mixture was combined with isopropanol (50 wt%), and the resulting solution was purified under an inert atmosphere for 30 minutes. A circular magnetic stirrer wound with a pre-activated copper wire was added to the reaction vessel. The reaction vessel was placed in an oil bath at 25°C and stirred until complete conversion.

[0195] Test data

[0196] A polymer having the chemical formula presented below was prepared by varying the reactant ratios to obtain the desired values ​​of n and m, as described above.

[0197]

[0198] Details of the polymer are presented in the table below.

[0199]

[0200] 1 g of each polymer was added to 99 g of API Group I mineral oil. The samples were subjected to traction and wear tests along with samples of the same mineral oil without any polymer addition.

[0201] Each oil was tested using a High Frequency Reciprocating Rig (HFRR) available from PCS Instruments, London, UK. The device uses a 6 mm diameter ball as the upper specimen that reciprocates under an applied load against a disc-shaped lower specimen. The test conditions are presented in the table below.

[0202]

[0203] The wear scar formed on the lower disk specimen was analyzed using a Zemetrix Zescope 3D optical profilometer employing non-contact interference focus scanning. This measures the amount of wear by measuring the material lost from the disk during the test. This is in μm 3 It was reported as the volume of wear marks (WSV) in units. A piezoelectric transducer was fitted to the HFRR device to measure the average coefficient of friction between the ball and the disc. The wear results are shown in the table below, where each value is the average of three tests using each test oil.

[0204]

[0205] It is clear that the polymer of the present invention significantly reduced the amount of measured friction on the test sample compared to the base oil alone. The data demonstrate that the polymer is an effective anti-wear agent.

[0206] The wear data provides an indicator of the mechanism of wear protection provided by the polymer of the present invention. In all cases, the presence of the polymer causes a significant increase in recorded wear by indicating a greater separation of the contact surfaces.

[0207] Further exemplary synthesis of the polymer according to the present invention

[0208] Hydroxy from oxazoline Induced Caprolactone synthesis: ε-caprolactone (30.01 g, 262.84 mmol) was added to a flask and heated to 80°C under inert conditions. Subsequently, ethanolamine (17.45 mL, 262.84 mmol) was added to the flask and heated at 120°C for 2 hours. Then, titanium(IV) butoxide (0.5 mL) was added to the reaction mixture and heated at 230°C for 2 hours. Subsequently, the reaction mixture was distilled under vacuum to obtain ε-hydroxy-pentyl oxazoline as a clear yellow oil (7.53 g, 18.2%).

[0209] Synthesis of inimers : ε-hydroxy-pentyl oxazoline (5.50 g, 35.00 mmol) was placed in a round-bottom flask with DCM. To the mixture, 4-(dimethylamino)pyridine (DMAP, 0.44 g, 3.50 mmol) and α-bromoisobutyric acid (5.89 g, 35.00 mmol) were added. Subsequently, the solution was cooled in an ice bath, N,N'-diisopropylcarbodiimide (5.5 mL, 35.00 mmol) was slowly added dropwise, and the mixture was stirred overnight. Subsequently, the urea byproduct was filtered out, and the unpurified material was washed with saturated NaHCO3 and brine. Subsequently, the solution was removed under vacuum, and the product was purified by rapid chromatography (silica gel, EA, TEA 2%) to obtain the inimer as a colorless oil (6.74 g, 62.9%).

[0210] General Procedure for Cationic Ring-Opening Polymerization : The monomer p-toluenesulfonic acid (in an appropriate molar ratio) was placed in a microwave vial, sealed, and purified with N2 for a few minutes. Subsequently, dry acetonitrile was added to the reaction mixture to produce a 4 M solution, and the vial was opened. Subsequently, the reaction mixture was subjected to GPC and 1 The mixture was stirred at 60°C until complete or near-complete conversion was confirmed by H NMR.

[0211] General procedure for the synthesis of brush polymers via Cu(0)-RDRP by chain extension: An acrylate monomer brush initiator, an inactivator (Cu2Br), a ligand (Me6TREN) (ratio of [monomer:1:0.05:0.18]), and a solvent (isopropanol, 50 wt%) were added to a Schlenk tube in the following order: inactivator, ligand, initiator, monomer, solvent. The mixture was sealed with a rubber septum and purified under an inert atmosphere for at least 30 minutes, after which a 5 cm length of pre-activated Cu wire (0.25 mm) wound around a magnetic stirrer was added. Subsequently, the reaction mixture was placed in an oil bath set at 25°C and stirred until complete conversion. The conversion 1 Measurements were performed by H NMR spectroscopy, and SEC analysis was carried out using a sample diluted in THF from which residual copper paper had been removed by filtering with basic alumina prior to the analysis.

[0212] Test data

[0213] A polymer having the chemical formula presented below was prepared by varying the reactant ratios to obtain the desired values ​​of p and r, and by varying the monomers to obtain the desired value of q, as described above.

[0214] Details of the polymer are presented in the table below.

[0215]

[0216]

[0217] 1 g of each polymer was added to 99 g of API Group I mineral oil. The sample was subjected to a traction test with a sample of the same mineral oil without any polymer addition.

[0218] Each oil was tested using a Mini Traction Machine (MTM) available from PCS Instruments, London, UK. The machine uses a 3 / 4 mm diameter ball as the upper specimen, which moves under an applied load on a disc-shaped lower specimen. Both the ball and the disc are driven independently to achieve a certain range of slide-to-roll ratios. The ball and the disc are made of AISI 52100 ground steel. The test conditions are presented in the table below.

[0219]

[0220]

[0221] A piezoelectric transducer was equipped on the MTM device to measure the average coefficient of friction between the ball and the disc. The wear results are shown in the table below, where each value is the average of two or more tests using each test oil. The reported data is a 20 mm / s data point from the 100°C Stribeck stage (Stage 7).

[0222]

[0223] It is clear that the polymer of the present invention causes a significant reduction in the coefficient of friction measured in the test sample compared to the base oil alone by exhibiting a larger separation of the contact surfaces.

Claims

Claim 1 Polymer containing units of the following chemical formula I: [Chemical Formula I] In the above formula, x is 2 or 3 and L is (CH2) y provided that y is an integer from 1 to 10, or L is CH(CH3)CH2S(CH2) z That is, z is an integer from 1 to 5; and [Q] is absent or a polymerized residue composed of a unit of the following chemical formula II: [Chemical Formula II] [In the above formula, R is a hydrocarbyl group or a hydrocarbyl group containing one or more heteroatoms, R may be a straight-chain, branched-chain, or cyclic saturated or unsaturated hydrocarbyl group, and R has 1 to 30 carbon atoms], [Q] is composed of units of the same formula II, or [Q] is composed of more than one different unit of formula II with different group R; X is a halogen; the number of units of formula I in the polymer is 2 to 100; and the number of units of formula II in [Q] is 2 to 200. Claim 2 delete Claim 3 In claim 1, the polymer further comprising a unit of the following chemical formula III: [Chemical Formula III] In the above formula, R 1 is a straight or branched saturated or unsaturated hydrocarbyl group having 2 to 24 carbon atoms; w is 2 or 3. Claim 4 A polymer according to claim 3, wherein the ratio of the number of units of Formula I to the number of units of Formula III in the polymer is 1:100 to 100:

1. Claim 5 In claim 1, a polymer composed of units of chemical formula I. Claim 6 In paragraph 3, a polymer composed of units of chemical formula I and units of chemical formula III. Claim 7 A polymer in which X is a bromine atom, in paragraph 1. Claim 8 A polymer having a number average molecular weight of 500 to 500,000 g / mol when measured by gel permeation chromatography with reference to a linear narrow poly(methyl methacrylate) standard of 550 to 600,000 g / mol. Claim 9 A lubricating composition comprising: a large amount of base lubricant exceeding 50 mass% based on the mass of the composition; and a small amount of a polymer according to any one of claims 1 and 3 to 8, less than 50 mass% based on the mass of the composition. Claim 10 In claim 9, a lubricating composition in which the base lubricant is an oil of lubricating viscosity. Claim 11 A method for reducing friction and / or wear between contact surfaces of a mechanical device, comprising lubricating the surfaces with a lubricating composition according to claim 9. Claim 12 A use as an additive in a lubricating composition for reducing friction and / or wear between contact surfaces of a mechanical device, wherein the mechanical device is lubricated by said composition, of a polymer according to any one of claims 1 and 3 to 8. Claim 13 Compound of Chemical Formula IV below: [Chemical Formula IV] In the above formula, p is 1 or 2; and q is an integer from 1 to 10. Claim 14 Compound of the following chemical formula V: [Chemical Formula V] In the above formula, p is 1 or 2; r is an integer from 4 to 10. Claim 15 A method for synthesizing a compound of Formula IV according to claim 13, comprising: (a) reacting 2-isoprofenyl-2-oxazoline, 2-isoprofenyl-5,6-dihydro-4H-1,3-oxazine, or a mixture thereof with a mercapto alcohol; and (b) performing a Steglich esterification reaction by reacting the product of step (a) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide. Claim 16 A method for synthesizing a compound of Formula V according to claim 14, comprising: (a) a step of ring-opening a lactone by reacting it with 2-amino-1-ethanol, 3-amino-1-propanol, or a mixture thereof; (b) a step of ring-closing the product of step (a) by heating it in the presence of a transition metal catalyst through an organometallic-catalyzed condensation-cyclization reaction; and (c) a step of performing a Steglych esterification reaction by reacting the product of step (b) with α-bromoisobutyric acid in the presence of 4-N,N-dimethylaminopyridine and dihydrocarbyldiimide.

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