TW201443209A - Viscosity index improver, method for producing same, and oil composition - Google Patents

Abstract

The present invention provides: a viscosity index improver having an excellent effect of improving a viscosity index and a high-temperature high-shear viscosity of an oil; and others. The viscosity index improver according to the present invention comprises a hydrogenation product of a copolymer which contains (a) a structural unit derived from an aromatic vinyl compound and (b) a structural unit derived from a conjugated diene, wherein (b1) a farnesene-derived structural unit is contained in an amount of 1 to 100 mass% and (b2) a structural unit derived from a conjugated diene other than farnesene is contained in an amount of 0 to 99 mass% both relative to the total amount of (b) the structural unit derived from a conjugated diene, and 50 mol% or more of carbon-carbon double bonds in (b) the structural unit derived from a conjugated diene are hydrogenated.

Description

Viscosity index upward agent, its manufacturing method and oil composition

The present invention relates to a viscosity index upward agent, a method for producing the same, and an oil composition, the viscosity index upward agent comprising a hydride containing a copolymer derived from a structural unit of bacteriocin, and the oil composition comprising the viscosity index Upward agent and base oil.

A hydride of a block copolymer comprising a polymer block derived from a structural unit derived from an aromatic vinyl compound and a polymer block derived from a structural unit derived from a conjugated diene, thereby eliminating the need for It is used for daily groceries, automotive parts, various industrial products, etc., because it exhibits the same characteristics as vulcanized rubber and is excellent in damping properties, flexibility, rubber elasticity, and weather resistance. Wide range.

The hydrogenated product of such a block copolymer is obtained by, for example, hydrogenating a block copolymer obtained by sequentially polymerizing an aromatic vinyl compound and a conjugated diene such as isoprene or butadiene (see, for example, Patent Document 1). ,2).

Further, Patent Document 3 discloses a hydrogenated product of a block copolymer as a viscosity index upward agent for a lubricating oil, and a hydrogenated product of the block copolymer is obtained by polymerization comprising a structural unit derived from an aromatic vinyl compound. The block is composed of a polymer block comprising a structural unit derived from a conjugated diene.

Further, in Patent Documents 4 and 5, a polymer of β-bacteria green is described, but practical physical properties have not been sufficiently studied.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent No. 2777239

Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-090267

Patent Document 3 Japanese Patent Publication No. 2009-532513

Patent Document 4 Japanese Special Table 2012-502135

Patent Document 5 Japanese Special Table 2012-502136

The viscosity index upward agent disclosed in Patent Document 3 is excellent in the effect of improving the viscosity index of the lubricating oil and the high-temperature high-shear viscosity, but it is preferable to develop different kinds of viscosity index upward agents excellent in the effect.

The object of the present invention is to provide a viscosity index upward agent, a method for producing the same, and an oil composition, the viscosity index upper agent improving the oil viscosity index and the high temperature high shear viscosity, and the oil composition has a viscosity index and a high temperature. High shear viscosity is high.

The present invention relates to the following [1] to [3].

[1] A viscosity index upward agent comprising a viscosity index upward agent comprising a hydride of a copolymer derived from a structural unit (a) of an aromatic vinyl compound and a structural unit (b) derived from a conjugated diene, In the total amount of the structural unit (b) derived from the conjugated diene, the content of the structural unit (b1) derived from the phycochloroene is from 1 to 100% by mass, and the structural unit derived from the conjugated diene other than the bacteriocin ( The content of b2) is from 0 to 99% by mass, and the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene is hydrogenated at 50 mol% or more.

[2] An oil composition comprising a base oil and a viscosity index upward agent of the above [1].

[3] A method for producing a viscosity index upward agent according to the above [1], which comprises obtaining a structural unit (a) derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene by anionic polymerization (b) a polymerization step of the copolymer; and a step of hydrogenating 50 mol% or more of the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene.

According to the present invention, there is provided a viscosity index upward agent, a method for producing the same, and an oil composition, the viscosity index upper agent having excellent effects of improving oil viscosity index and high temperature high shear viscosity, and the oil composition has a viscosity index and a high temperature. The shear viscosity is high.

[viscosity index up agent]

The viscosity index upward agent of the present invention comprises a hydride containing a copolymer derived from an aromatic vinyl compound (a) and a structural unit (b) derived from a conjugated diene (hereinafter referred to as "copolymer") (hereinafter referred to as "copolymer") Hereinafter, the viscosity index of the "hydrogenated copolymer" is an upward agent. In the total amount of the structural unit (b) derived from the conjugated diene, the content of the structural unit (b1) derived from the phycochloroene is from 1 to 100% by mass, and the structural unit derived from the conjugated diene other than the bacteriocin ( The content of b2) is from 0 to 99% by mass, and the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene is hydrogenated by hydrogenation of 50 mol% or more.

The hydrogenated copolymer constituting the viscosity index upward agent of the present invention may be either a hydride of a block copolymer or a hydride of a random copolymer.

That is, the viscosity index upward agent of the present invention may further comprise a polymer block (A) mainly composed of the structural unit (a) derived from the aromatic vinyl compound, and a structural unit derived from the conjugated diene (b) A hydrogenated product of a block copolymer of the main polymer block (B) (hereinafter referred to as "hydrogenated block copolymer").

Further, the viscosity index upward agent of the present invention may comprise a random polymerization of the structural unit (a) derived from the aromatic vinyl compound, the structural unit (b1) derived from the chlorophyll, and the conjugated diene other than the bacteriochlorene. A hydride of a random copolymer formed by the structural unit (b2) (hereinafter referred to as "hydrogenated random copolymer").

<Structural unit derived from aromatic vinyl compound (a)>

The above copolymer contains a structural unit (a) derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 4-propylstyrene. 4-tertiary butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2,4-dimethyl styrene, 2,4-diisopropyl styrene, 2,4,6 -trimethylstyrene, 2-ethyl-4-benzylbenzene Ethylene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinyl fluorene, N,N-diethyl-4-amineethylstyrene, vinylpyridine, 4-methoxy Styrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, 4-methylstyrene, and more preferably styrene are preferable from the viewpoint of improving the oil viscosity index and the high-temperature high shear viscosity.

Further, in the present invention, a compound having both an aromatic group and a conjugated diene bond in one molecule is not contained in the conjugated diene derived from the component of the structural unit (b), but is contained from the structural unit. An aromatic vinyl compound of the component (a). In the structural unit (a), the content of the structural unit derived from the compound having both the aromatic group and the conjugated diene bond in the one molecule is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 1% by mass or less.

<Structural unit derived from conjugated diene (b)>

The above copolymer contains a structural unit (b) derived from a conjugated diene. The copolymer contains, as the structural unit (b), a structural unit (b1) derived from bacteriocin, but may further contain a structural unit (b2) derived from a conjugated diene other than bacteriophthene.

The total amount of the structural unit (b) derived from the leucoene is from 1 to 100% by mass, preferably from 40 to 100% by mass, more preferably from 50 to 30% by weight of the structural unit (b) of the conjugated diene. 100% by mass, more preferably 55 to 100% by mass, still more preferably 60 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.

Further, in the total amount of the structural unit (b) derived from the conjugated diene, the content of the structural unit (b2) derived from the conjugated diene other than the bacteriophthene is from 0 to 99% by mass, preferably from 0 to 60. The mass %, more preferably 0 to 50% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass.

The mycophenolate is a raw material extracted from a plant such as sugar cane, and can be industrially produced by using a microorganism. Next, the viscosity index uppering agent of the present invention is obtained by using such bacteriocin as a raw material, so that it can be produced with a small environmental load.

(Structural unit derived from bacteriocin (b1))

The bacteriophthene derived from the component of the structural unit (b1) may be any of α-bacteria green olefin and β-bacteria green olefin represented by the following formula (I), and they may be used in combination.

The content of the structural unit derived from β-bacteria green in the structural unit (b1) is preferably 60% by mass or more from the viewpoints of ease of production of the modified copolymer, oil viscosity index, and high-temperature high shear viscosity. More preferably, it is 80% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.

(Structural unit (b2) derived from conjugated diene other than bacteriocin)

The copolymer may further contain a structural unit (b2) derived from a conjugated diene other than bacteriophthene. Examples of the conjugated diene other than the bacteriophthene derived from the component of the structural unit (b2) include butadiene, isoprene, 2,3-dimethyl-butadiene, and 2-phenyl. -butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene 1,3,7-octanetriene, laurelene and chloroprene. These may be used alone or in combination of two or more. Among them, at least one of butadiene, isoprene and laurelene is more preferable, and at least one of butadiene and isoprene is more preferable.

<Other structural units (c)>

The above copolymer may contain other structural units (c) in addition to the above structural units (a), (b1) and (b2).

Examples of the component derived from the structural unit (c) include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1- Terpene, 1-undecene, 1-dodecene, 1-tridecene, 14-tetraene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, Unsaturated hydrocarbon compound such as 1-nonene, 1-eicene; acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid, anti-butyl Aenedioic acid, crotonic acid, itaconic acid, 2-propenyl mercaptoethanesulfonic acid, 2-methylpropenylethanesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, 2-methyl A functional group-containing unsaturated compound such as acrylamide-2-methylpropanesulfonic acid, vinyl sulfonate, vinyl acetate or methyl vinyl ether. These may be used alone or in combination of two or more.

<copolymer>

The copolymer of the present invention comprises the above structural unit (a) derived from an aromatic vinyl compound and the above structural unit (b) derived from a conjugated diene. Further, the copolymer may further contain the above structural unit (c).

The total content of the structural unit (a) and the structural unit (b) in the copolymer is based on the viewpoint of improving the oil viscosity index and the high temperature and high shear viscosity. The amount is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 99% by mass or more.

Further, from the same viewpoint, the content of the structural unit (c) in the total amount of the structural units constituting the copolymer is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, more preferably 1% by mass or less.

The content of the structural unit (a) in the copolymer is preferably from 1 to 99% by mass, more preferably from 2 to 90% by mass, still more preferably from 3 to 99% by mass, from the viewpoint of the viscosity of the oil and the high shear viscosity. It is preferably 85 to 80% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 50% by mass, still more preferably 15 to 45% by mass.

The mass ratio of the total amount of the structural unit (a) to the total amount of the structural unit (b) [(a)/(b)] is preferably from the viewpoint of the oil viscosity index and the high-temperature high shear viscosity. /99 to 99/1, more preferably 2/98 to 90/10, more preferably 3/97 to 85/15, still more preferably 5/95 to 80/20, still more preferably 10/90 to 50 /50, and even better 15/85 to 45/55.

The copolymer of the present invention may be any of a block copolymer and a random copolymer. Hereinafter, the two kinds of copolymers will be described.

(block copolymer)

The copolymer in the present invention may be a block copolymer comprising the polymer block (A) mainly composed of the structural unit (a) derived from the aromatic vinyl compound, and the structural unit derived from the conjugated diene (b) is the main polymer block (B).

Here, the term "main body" means that the polymer block (A) is contained in an amount of 50% by mass or more based on the total mass of the polymer block (A). The structural unit (a) of the aromatic vinyl compound preferably contains 70% by mass or more of the structural unit (a) derived from the aromatic vinyl compound, and more preferably contains 90% by mass or more. In the same manner, the polymer block (B) contains 50% by mass or more of the structural unit (b) derived from the conjugated diene, and preferably contains 65, based on the total mass of the polymer block (B). The mass % or more of the structural unit (b) derived from the conjugated diene is more preferably 80% by mass or more.

Preferably, the polymer block (B) contains from 1 to 100 masses % is derived from the structural unit (b1) of bacteriocin, and contains 99 to 0% by mass of the structural unit (b2) derived from a conjugated diene other than bacteriophthene. Here, the preferred specific examples and content ratios of the structural units (b1) and (b2) are as described above.

Further, to the extent that the object of the present invention is not impaired, The polymer block (b) may also have a small amount of structural units derived from other copolymerizable monomers. Examples of such other copolymerizable monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 1,3-dimethylbenzene. Ethylene, stilbene, 1-vinylnaphthalene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenyl An anionically polymerizable copolymerizable monomer such as an aromatic vinyl compound such as butyl)styrene. These other copolymerizable monomers may be used alone or in combination of two or more. In the case of having the above structural unit derived from another copolymerizable monomer, the bonding form may be any of a random shape and a tapered shape.

In the case where the polymer block (b) contains the structural unit derived from another copolymerizable monomer, the content thereof is preferably 35% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.

The bonding form of the polymer block (A) and the polymer block (B) is not particularly limited, and may be linear, branched, radial, or a combination of two or more of them. Among them, from the viewpoint of the modified oil viscosity index and the high-temperature high shear viscosity, when the polymer block (A) is represented by A and the polymer block (B) is represented by B, (AB) _l and A-( BA) _m , B-(AB) _n (l, m, n are each independently an integer of 1 or more), each block is bonded in a linear form, and (AB) _p X, (BA) _q X (p and q each independently represent an integer of 3 or more; and X is a coupling agent residue) means that each block is bonded to a form of radiation.

In view of the bonding form, a diblock copolymer represented by A-B or a triblock represented by A-B-A is preferred from the viewpoint of improving the oil viscosity index and the high temperature and high shear viscosity.

Further, the block copolymer may have two or more polymer blocks (A) or two or more polymer blocks (B), and each polymer block may be a polymer embedded in the same structural unit. The segment may also be a polymer block comprising different structural units. For example, in the two polymer blocks (A) of the triblock copolymer represented by [A-B-A], the respective aromatic vinyl compounds may be of the same type or may be different.

The peak top molecular weight of the polymer block (A), from the lifting oil The effect of the viscosity index and the ease of production of the oil composition are preferably 10,000 or more and 60,000 or less, and more preferably 15,000 or more and 50,000 or less. When the peak top molecular weight of the polymer block (A) is less than 10,000, the effect of improving the oil viscosity index may be lowered. On the other hand, when it is more than 60,000, the solubility of the obtained block copolymer in oil is lowered, so that the oil viscosity index improving effect may not be obtained. In addition, block copolymer There are two or more cases of the polymer block (A), and the peak top molecular weight of at least one of the polymer blocks is preferably in the above range.

Further, the block copolymer contains at least one polymer block selected from polymer blocks (A) and (A') mainly composed of a structural unit (a) derived from an aromatic vinyl compound. And the polymer block (B) mainly composed of the structural unit (b) derived from the conjugated diene, the bonding form is AB or AB-A', and the peak of the polymer block (A') A block copolymer having a molecular weight of 1,000 or more and less than 10,000 is more preferable. In terms of the peak top molecular weight of the polymer block (A'), it is particularly preferably 1,000 or more and 8,000 or less. When the peak molecular weight of the polymer block (A') is less than 10,000, since the hydrogenated block copolymer can be prevented from forming a gel-like network in the oil composition, the obtained oil composition can be suppressed at 40 ° C and 100 ° C. The dynamic viscosity increases and it is easier to use as a lubricant.

The peak top molecular weights of the polymer blocks (A) and (A') were determined by measuring a part of the reaction liquid in the synthesis of the block copolymer and measuring the method described in the examples below.

(random copolymer)

Further, the copolymer of the present invention randomly polymerizes the structural unit (a) derived from the aromatic vinyl compound, the structural unit (b1) derived from the bacteriophthene, and the structure of the conjugated diene other than the bacteriochlorene. a random copolymer of unit (b2).

<Hydrogenated copolymer>

The hydrogenated copolymer constituting the viscosity index upward agent of the present invention is obtained by hydrogenating the above copolymer, and the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene is hydrogenated by 50 mol% or more. That is, the hydrogenation rate is 50 mol% or more.

Here, the hydrogenation rate is such that the number of moles of the double bond derived from the conjugated diene per 1 mole of the copolymer is M1, and the double bond of the hydrogenated copolymer per mole of the conjugated diene is contained. When the number of moles is set to M2, the value shown by the following formula is used.

Hydrogenation rate = (1-M2/M1) × 100 (% by mole)

The hydrogenation rate is preferably 60 mol% or more, more preferably 70 mol% or more, from the viewpoint of improving the heat resistance or shear stability of the oil, or the viscosity index and the high temperature and high shear viscosity. Further, the hydrogenation ratio can be determined by the method described in the examples below.

The peak top molecular weight (Mp) of the hydrogenated copolymer, composed of oil The ease of manufacture and the oil viscosity index are preferably from 4,000 to 1,500,000, more preferably from 9,000 to 1,200,000, still more preferably from 20,000 to 1,100,000, most preferably from 100,000 to 800,000.

Further, the peak top molecular weight (Mp) in the present specification means the value measured by the method described in the examples below.

The molecular weight distribution (Mw/Mn) of the hydrogenated copolymer is preferably from 1 to 4, more preferably from 1 to 3, still more preferably from 1 to 2. When the molecular weight distribution is within this range, the viscosity of the hydrogenated block copolymer is small.

[Manufacturing method of hydrogenated copolymer]

The hydrogenated copolymer can be suitably produced by a polymerization process of obtaining a copolymer comprising a structural unit (a) derived from an aromatic vinyl compound and a structural unit (b) derived from a conjugated diene by anionic polymerization. And a step of hydrogenating 50 mol% or more of the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene. The hydrogenation step can be carried out in the same manner as the hydrogenation step of the hydrogenated block copolymer described later.

Hereinafter, the method for producing the hydrogenated block copolymer will be described in more detail.

[Method for Producing Hydrogenated Block Copolymer]

The hydrogenated block copolymer can be suitably produced by an anionic polymerization to obtain a polymer block (A) mainly composed of the structural unit (a) derived from the aromatic vinyl compound, and The structural unit (b) derived from the conjugated diene is a polymerization step of a block copolymer of the main polymer block (B); and 50 mol% or more of the structural unit derived from the conjugated diene (b) The carbon-carbon double bond hydrogenation step.

<polymerization step>

The block copolymer can be produced by a solution polymerization method, a method described in JP-A-2012-502135, and JP-A-2012-502136. Among them, a solution polymerization method is preferred, and a known method such as anionic polymerization or cationic polymerization, or a radical polymerization method can be preferably applied. Among them, an anionic polymerization method is preferred. In the anionic polymerization method, a conjugated diene other than an aromatic vinyl compound, bacteriophage, and/or bacteriocin is sequentially added in the presence of a solvent, an anionic polymerization initiator, and a Lewis base as needed, to obtain an embedded layer. The segment copolymer is preferred.

Examples of the anionic polymerization initiator include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as barium, magnesium, calcium, strontium, and barium; and barium-based rare earth metals such as barium and strontium; and the alkali metal and alkaline earth. A metal-like or lanthanide-based rare earth metal compound. Among them, preferred are compounds containing an alkali metal and an alkali metal, and an organic alkali metal compound.

Examples of such an organic alkali metal compound include Such as methyl lithium, ethyl lithium, n-butyl lithium, secondary lithium, three-stage lithium, lithium, benzene lithium, lithium stilbene, dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1 , an organic lithium compound such as 4-dilithium-2-ethylcyclohexane or 1,3,5-trilithium benzene; sodium naphthalene or potassium naphthalene. Among them, an organolithium compound is preferred, and n-butyllithium, a secondary lithium hydride, and a secondary lithium hydride are particularly preferred. Further, the organic alkali metal compound may be reacted with a secondary amine such as diisopropylamine, dibutylamine, dihexylamine or dibenzylamine, and may be used as the organic alkali metal guanamine.

The amount of the organic alkali metal compound used for the polymerization differs depending on the molecular weight of the block copolymer, but generally, the total amount of the conjugated diene other than the aromatic vinyl compound and the bacteriochlorene and/or bacteriophthene The amount is in the range of 0.01 to 3% by mass.

In the case of a solvent, if it does not The adverse effect is not particularly limited, and examples thereof include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, and methylcyclopentane. A saturated alicyclic hydrocarbon such as an alkane; an aromatic hydrocarbon such as benzene, toluene or xylene; and the like. These may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited.

The action of the Lewis base controls the microstructure in the structural unit (b1) derived from the myostatin and the structural unit (b2) derived from the conjugated diene other than the myostene. Examples of the Lewis base include dibutyl ether, diethyl ether, tetrahydrofuran, and An ether compound such as alkane or ethylene glycol diethyl ether; pyridine; a tertiary amine such as N,N,N',N'-tetramethylethylenediamine or trimethylamine; an alkali metal alkoxide such as a tertiary potassium pentoxide; Phosphine compounds and the like. In the case where a Lewis base is used, the amount thereof is usually in the range of 1 mol of the anionic polymerization initiator, preferably 0.01 to 1000 mol.

The temperature of the polymerization reaction, usually between -80 and 150 ° C, It is preferably from 0 to 100 ° C, more preferably from 10 to 90 ° C. The form of the polymerization reaction may be either batchwise or continuous. The monomer is continuously or intermittently supplied to the polymerization reaction liquid so that the amount of the aromatic conjugated compound other than the aromatic vinyl compound, the bacteriophthene, and/or the bacteriophthene in the polymerization reaction system is in a specific range; The block copolymer can be produced by sequentially polymerizing so that each monomer in the polymerization reaction liquid has a specific ratio.

In the polymerization reaction, an alcohol such as methanol or isopropyl alcohol is added as a polymerization stopper, and the reaction can be stopped. The obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate a block copolymer, or the polymerization reaction liquid is washed with water, separated, and then dried to separate the block copolymer.

{modified copolymer}

In the present polymerization step, as described above, an unmodified block copolymer can also be obtained, but the modified block copolymer can also be obtained as follows.

The block copolymer may also be modified before the hydrogenation step described later. Examples of the functional group which can be introduced include an amine group, an alkoxyalkyl group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl group, a thiol group, an isocyanate group, an acid anhydride, and the like.

In the block copolymer modification method, for example, tin tetrachloride, tetrachlorodecane, dimethyldichlorodecane, dimethyldiethoxylate which can react with the polymerization active terminal before the addition of the polymerization stopper is added. Base decane, tetramethoxy decane, tetraethoxy decane, 3-aminopropyl triethoxy decane, tetraethoxypropyl-1,3-diamine methylcyclohexane, 2,4-methyl extension Phenyl diisocyanate a coupling agent such as a coupling agent, or a polymerization terminal modifier such as 4,4'-bis(diethylamino)benzophenone or N-vinylpyrrolidone, or an additional modifier described in JP-A-2011-132298 The method. Further, the copolymer may be grafted using maleic anhydride or the like after the separation.

The position at which the functional group is introduced may be at the polymerization end of the block copolymer or in the side chain. Further, the above functional groups may be used alone or in combination of two or more. The above-mentioned modifier, for the anionic polymerization initiator, is usually preferably in the range of 0.01 to 10 mol.

<Hydrogenation step>

The hydrogenated block copolymer can be obtained by subjecting the block copolymer obtained by this method to hydrogenation. A well-known method can be used for the method of hydrogenation. For example, in a solution in which a block copolymer is dissolved in a solvent which does not affect the hydrogenation reaction, a Ziegler-based catalyst is present; nickel or platinum supported on carbon, cerium oxide, diatomaceous earth, or the like is present. A palladium, rhodium, ruthenium metal catalyst; an organic metal complex having cobalt, nickel, palladium, rhodium or ruthenium metal, etc., which is subjected to a hydrogenation reaction as a hydrogenation catalyst. In the hydrogenation step, a hydrogenation catalyst may be added to the polymerization reaction liquid containing the block copolymer obtained by the method for producing the block copolymer to carry out a hydrogenation reaction. In the present invention, palladium carbon in which palladium is supported on carbon is preferred.

In the hydrogenation reaction, the hydrogen pressure is preferably from 0.1 to 20 MPa, more preferably from 100 to 200 ° C, more preferably from 1 to 20 hours.

The hydrogenation rate of the carbon-carbon double bond in the polymer block (B) in the block copolymer, which is determined by the heat resistance or shear stability of the lifted oil, or the viscosity The viewpoint of the number and the high-temperature high shear viscosity is preferably 50% by mole or more, more preferably 60% by mole or more, and still more preferably 70% by mole or more. Further, the hydrogenation rate can be calculated by the method described in the examples below.

[oil composition]

The oil composition of the present invention comprises a base oil and the aforementioned viscosity index upward agent.

The oil composition can be suitably used as engine oil, automatic transmission fluid, gear lubricating oil, and hydraulic oil.

The content of the viscosity index upward agent in the oil composition is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 7% by mass, still more preferably from 0.2 to 5% by mass, still more preferably from 0.5 to 5% by mass.

<base oil>

Examples of the base oil include fuel oils such as middle distillate fuels, synthetic and natural lubricating oils, unrefined oils, and industrial oils. The base oil may be at least one of a paraffinic system, a naphthene system, and an aromatic group. Further, the base oil may be at least one of a natural oil or a synthetically prepared oil.

<Other additives>

The oil composition of the present invention may also contain rust preventives, antioxidants, surfactants, pour point depressants, detergent dispersants, metal inerting agents, antifoaming agents, and friction modifiers. , an extreme pressure agent, one or more additional viscosity index upwards and other additives.

<Method for producing oil composition>

The oil composition of the present invention can be produced by a known production method in the art.

For example, the oil composition of the present invention can be produced by mixing the above base oil with the above viscosity index upward agent. Mixing can be carried out using a well-known mixing device.

The mixing is preferably carried out while heating on one side. The heating temperature is preferably 80 to 180 °C.

In the case where the oil composition of the present invention is used for engine oil, automatic transmission fluid, gear lubricating oil, hydraulic oil, etc., the dynamic viscosity at 40 ° C is preferably in the range of 40 to 120 mm ² /sec, more preferably 50 to 70 mm ² /sec range. Further, from the same viewpoint, it is preferred that the dynamic viscosity at 100 ° C is in the range of 6 to 25 mm ² /sec, more preferably in the range of 8 to 15 mm ² /sec. If it is within this range, the fuel cost of the vehicle can be reduced when used in the above applications.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited to the examples. Further, β-bacteria green (purity: 97.6 mass%, manufactured by Amyris Biotechnology Co., Ltd.) is obtained by purifying with a molecular sieve of 3 Å and distilling under a nitrogen atmosphere to remove zingiberene, bisabolene, and bacteria. Greenene epoxide, farnesol isomer, E, E-greenolinol, squalene, ergosterol, and several dimers of bacteriocin Hydrocarbon-based impurities are used in the polymerization below.

(1) Determination of molecular weight distribution (Mw/Mn) and peak top molecular weight (Mp)

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer obtained in each of the examples and the comparative examples were determined by GPC (gel permeation chromatography) in terms of conversion of standard polystyrene molecular weight. Got it. Further, the peak position of the peak of the molecular weight distribution (Mw/Mn) is defined as the peak top molecular weight (Mp). The measuring device and conditions are as follows.

‧Installation: GPC device "GPC8 020" made by Tosoh Corporation

‧Separation column: "TSKgel G4000 HXL" manufactured by Tosoh Corporation

‧Detector: "RI-8020" made by Tosoh Corporation

‧Eluant: tetrahydrofuran

‧ Eluent flow rate: 1.0ml / min

‧ Sample concentration: 5mg/10ml

‧ Column temperature: 40 ° C

(2) Method for measuring hydrogenation rate

In each of the examples and the comparative examples, the block copolymer and the hydrogenated block copolymer after hydrogenation were each dissolved in a deuterated chloroform solvent, and ¹ H was measured at 50 ° C using "Lambda-500" manufactured by JEOL Ltd. - NMR. The hydrogenation rate of the polymer block (B) in the hydrogenated block copolymer is calculated from the following formula from the proton peak having a carbon-carbon double bond appearing in the range of 4.5 to 6.0 ppm of the obtained spectrum.

Hydrogenation rate = {1 - (the number of moles of carbon-carbon double bonds per 1 mole of hydrogenated block copolymer) / (the number of moles of carbon-carbon double bonds per 1 mole of block copolymer) }×100 (mole%)

(3) Dynamic viscosity

The dynamic viscosity at 40 ° C and 100 ° C was measured in accordance with JIS K2283.

(4) Viscosity index

The viscosity index was measured in accordance with JIS K2283.

(5) high temperature and high shear viscosity

The high temperature high shear viscosity at 150 ° C was measured in accordance with ASTM D4683.

[Example 1]

In a nitrogen-substituted and dried pressure-resistant container, 62.4 kg of cyclohexane as a solvent and 51.0 g of a secondary lithium hydride (10.5 mass% of a cyclohexane solution) as an anionic polymerization initiator were charged, and the temperature was raised to 50 ° C, and then added. 2.34 kg of styrene (1), further polymerized for 1 hour, followed by addition of 10.9 kg of β-bacterial green olefin, polymerization for 2 hours, further addition of 2.34 kg of styrene (2), polymerization for 1 hour, to obtain inclusion polymerization A reaction solution of a styrene-poly(β-bacteria green)-polystyrene triblock copolymer. In the reaction liquid, palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst was added in an amount of 5 mass% based on the block copolymer, and the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 °C. After cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated, and further dried by vacuum to obtain a hydride of a polystyrene-poly(β-bacteria green)-polystyrene triblock copolymer (hereinafter It is called "hydrogenated block copolymer (A1)"). Table 1 shows the results of measurement of various physical properties of various raw materials and the obtained hydrogenated block copolymer (A1).

By using the obtained hydrogenated block copolymer (A1) as a viscosity index upward agent, a paraffinic oil "Diana Fresia S-32" manufactured by Idemitsu Kosan Co., Ltd. was used as a base oil, and the base oils were as follows. The hydrogenated block copolymer (A1) was prepared as shown in Fig. 2, and mixed in a nitrogen-substituted pressure-resistant container at a heating temperature of 120 ° C for 6 hours at a rotation speed of 350 rpm to obtain an oil composition. The above evaluation was carried out for the oil composition. The results are shown in Table 2.

[Embodiment 2]

In a pressure-resistant container which was dried by nitrogen and dried, 62.4 kg of cyclohexane as a solvent and 40.6 g of dibutyllithium (10.5 mass% of a cyclohexane solution) as an anionic polymerization initiator were charged, and the temperature was raised to 50 ° C. Adding 13.0 kg of β-bacterial green olefin, performing polymerization for 2 hours, and then performing polymerization for 1 hour by adding 2.59 kg of styrene to obtain a poly(β-bacteria green)-polystyrene diblock copolymer. The reaction solution. To the reaction liquid, palladium carbon (palladium loading: 5 mass%) of a hydrogenation catalyst of 5% by mass based on the block copolymer was added, and the reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 °C. After releasing the pressure and releasing the pressure, the palladium carbon is removed by filtration, and the filtrate is concentrated and further dried under vacuum to obtain a hydride of a poly(β-bacteria green)-polystyrene diblock copolymer (hereinafter referred to as " Hydrogenated block copolymer (A2)"). The measurement results of various physical properties and various physical properties of the obtained hydrogenated block copolymer (A2) are shown in Table 1.

Next, the same procedure as in Example 1 was carried out except that the obtained hydrogenated block copolymer (A2) and the base oil were blended as shown in Table 2, and an oil composition was obtained, and the above evaluation was carried out. The results are shown in Table 2.

[Example 3]

The hydrogenated block copolymer (A3) and the oil composition were produced in the same manner as in Example 2 except that the preparation described in Table 1 was carried out, and the above evaluation was carried out. The results are shown in Tables 1 and 2.

[Example 4]

The hydrogenated block copolymer (A4) and the oil composition were produced in the same manner as in Example 1 except that the preparation described in Table 1 was carried out, and the above evaluation was carried out. The results are shown in Tables 1 and 2.

[Example 5]

In a pressure-resistant container which was dried by nitrogen and dried, 62.4 kg of cyclohexane as a solvent and 118.4 g of a secondary lithium hydride (10.5 mass% of a cyclohexane solution) as an anionic polymerization initiator were charged, and the temperature was raised to 50 ° C. Adding a mixture of 5.43 kg of β-bacterial green olefin and 4.32 kg of butadiene for 2 hours, followed by polymerization by adding 5.85 kg of styrene for 1 hour to obtain poly(β-bacteria green butylene/butyl A reaction solution of a diene)-polystyrene diblock copolymer. To the reaction liquid, palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst was added in an amount of 5 mass% based on the block copolymer, and the reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 °C. After cooling and depressurization, the palladium carbon is removed by filtration, and the filtrate is concentrated and further dried under vacuum to obtain a hydride of a poly(β-bacteria green/butadiene)-polystyrene diblock copolymer ( Hereinafter, it is referred to as "hydrogenated block copolymer (A5)"). Table 1 shows the results of measurement of various physical properties of the various raw materials and the obtained hydrogenated block copolymer (A5).

Next, the oil composition was obtained in the same manner as in Example 1 except that the obtained hydrogenated block copolymer (A5) and the base oil were prepared in the same manner as in Table 2, and the above evaluation was carried out. The results are shown in Table 2.

[Embodiment 6]

Except that the hydrogenated block copolymer (A5) and the base oil were blended as shown in Table 2, the same operation as in Example 5 was carried out to obtain an oil composition, and the above evaluation was carried out. The results are shown in Table 2.

[Embodiment 7]

In a pressure-resistant container which was replaced by nitrogen and dried, 62.4 kg of cyclohexane as a solvent was charged as an anionic polymerization initiator. 104.9 g of secondary lithium hydride (10.5 mass% cyclohexane solution), and after heating to 50 ° C, a mixture of 4.88 kg of β-bacterial green olefin and 4.88 kg of isoprene was added, and polymerization was carried out for 2 hours, followed by addition. 5.85 kg of styrene was polymerized for 1 hour to obtain a reaction liquid containing a poly(β-bacteria green/isoprene)-polystyrene diblock copolymer. In the reaction liquid, palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst was added in an amount of 5 mass% based on the block copolymer, and the mixture was subjected to hydrogen pressure at 2 MPa and 150 ° C for 10 hours. reaction. After cooling and depressurization, the palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum drying is performed to obtain a hydride of poly(β-bacteria green/isoprene)-polystyrene diblock copolymer. (hereinafter referred to as "hydrogenated block copolymer (A6)"). Table 1 shows the results of measurement of various physical properties of various raw materials and the obtained hydrogenated block copolymer (A6).

Next, the same procedure as in Example 1 was carried out except that the obtained hydrogenated block copolymer (A6) and the base oil were blended as shown in Table 2, and an oil composition was obtained, and the above evaluation was carried out. The results are shown in Table 2.

[Embodiment 8]

Except that the hydrogenated block copolymer (A6) and the base oil were blended as shown in Table 2, the same operation as in Example 7 was carried out to obtain an oil composition, and the above evaluation was carried out. The results are shown in Table 2.

[Comparative Example 1]

In a pressure-resistant container which was dried by nitrogen and dried, 62.4 kg of cyclohexane as a solvent and 98.6 g of dibasic lithium hydride (10.5 mass% of a cyclohexane solution) as an anionic polymerization initiator were charged, and the temperature was raised to 50 ° C. 8.36 kg of isoprene was added, polymerization was carried out for 2 hours, and then polymerization was carried out for 1 hour by adding 5.34 kg of styrene to obtain polyisoprene. A reaction liquid of an ene-polystyrene diblock copolymer. In the reaction liquid, palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst was added in an amount of 5 mass% based on the block copolymer, and the mixture was subjected to hydrogen pressure at 2 MPa and 150 ° C for 10 hours. reaction. After releasing the pressure and releasing the pressure, the palladium carbon is removed by filtration, and the filtrate is concentrated and further dried under vacuum to obtain a hydrogenated product of a polyisoprene-polystyrene diblock copolymer (hereinafter referred to as "hydrogenated block". Copolymer (B1)"). The measurement results of various physical properties of the various raw materials and the obtained hydrogenated block copolymer (B1) are shown in Table 1.

Next, the same procedure as in Example 1 was carried out except that the obtained hydrogenated block copolymer (B1) was used as a viscosity index upward agent, and an oil composition was obtained, and the above evaluation was carried out. The results are shown in Table 2.

[Comparative Example 2]

The oil composition was obtained in the same manner as in Comparative Example 1, except that the hydrogenated block copolymer (B1) and the base oil were blended as shown in Table 2, and the above evaluation was carried out. The results are shown in Table 2.

[Comparative Example 3]

The hydrogenated block copolymer (B2) and the oil composition were produced in the same manner as in Comparative Example 1, except that the preparation described in Table 1 was carried out, and the above evaluation was carried out. The results are shown in Tables 1 and 2.

[Comparative Example 4]

In a pressure-resistant container which was dried by nitrogen and dried, 62.4 kg of cyclohexane as a solvent, 79.4 g of a secondary butyllithium (10.5 mass% of a cyclohexane solution) as an anionic polymerization initiator, and 375 g of a Lewis base were charged as a solvent. Tetrahydrofuran, after heating to 50 ° C, 0.47 kg of styrene (1) was added, and polymerization was carried out for 1 hour, followed by addition of 6.86 kg of isoprene. A mixture of 6.86 kg of butadiene was polymerized for 2 hours, and 1.40 kg of styrene (2) was further added for polymerization for 1 hour to obtain polystyrene-poly(isoprene/butadiene)-polystyrene. A reaction solution of a triblock copolymer. To the reaction liquid, palladium carbon (palladium loading: 5 mass%) as a hydrogenation catalyst was added in an amount of 5 mass% based on the block copolymer, and the reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 °C. After cooling and depressurization, the palladium carbon is removed by filtration, and the filtrate is concentrated and further dried under vacuum to obtain a polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer. Hydride (hereinafter referred to as "hydrogenated block copolymer (B3)"). Table 1 shows the results of measurement of various physical properties of the various raw materials and the obtained hydrogenated block copolymer (B3).

Next, the same procedure as in Example 1 was carried out except that the obtained hydrogenated block copolymer (B3) and the base oil were blended as shown in Table 2, and an oil composition was obtained, and the above evaluation was carried out. The results are shown in Table 2.

[Comparative Example 5]

The above evaluation was carried out by using the base oil (Diana Fresia S-32, manufactured by Idemitsu Kosan Co., Ltd.) as Comparative Example 5. The results are shown in Table 2.

(*1) (b1)/(b) is the content of the structural unit (b1) derived from bacteriocin in the total amount of the structural unit (b) derived from the conjugated diene.

(*2) (a)/(b) is the mass ratio of the total amount of the structural unit (a) to the total amount of the structural unit (b).

(*3) St-F-St is polystyrene-poly(β-bacteria green)-polystyrene triblock copolymer, and F-St is poly(β-bacteria green)-polystyrene Segment copolymer, F/Bd-St is poly(β-bacteria green/butadiene)-polystyrene diblock copolymer, F/IP-St is poly(β-bacteria green/isoprene )-Polystyrene diblock copolymer, IP-St is polyisoprene-polystyrene diblock copolymer St-IP/Bd-St is polystyrene-polyisoprene/polybutylene An ene-polystyrene triblock copolymer.

(*4) The hydrogenation rate is the hydrogenation rate of the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene.

As is apparent from Tables 1 and 2, the hydrogenated block copolymers of Examples 1 to 8 are oil-viscosity indexes and high-temperature high shears, although they are made of a plant-derived raw material (β-bacteria). Excellent viscosity reduction effect. Moreover, it is understood that the oil viscosity index improving effect is excellent as compared with the case of using the hydrogenated block copolymers of Comparative Examples 1 to 4. Further, in the hydrogenated block copolymers of Examples 2 to 8, since the dynamic viscosity at 40 ° C and 100 ° C was sufficiently low, the fuel economy effect of the automobile was also excellent.

Claims (12)

A viscosity index upward agent comprising a viscosity index upward agent comprising a hydride of a copolymer derived from a structural unit (a) of an aromatic vinyl compound and a structural unit (b) derived from a conjugated diene, the conjugated second In the total amount of the structural unit (b) of the alkene, the content of the structural unit (b1) derived from farnesene is 1 to 100% by mass, and the structural unit derived from the conjugated diene other than the bacteriocin (b2) The content is 0 to 99% by mass, and the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene is hydrogenated at 50 mol% or more. A viscosity index upward agent according to claim 1, wherein the mass ratio of the total amount of the structural unit (a) derived from the aromatic vinyl compound to the total amount of the structural unit (b) derived from the conjugated diene [(a)/ (b)] is 1/99~99/1. A viscosity index upward agent according to claim 1 or 2, wherein the bacteriophthene is β-bacteria. The viscosity index topping agent according to any one of claims 1 to 3, wherein the peak top molecular weight (Mp) is 4,000 to 1,500,000. The viscosity index upward agent according to any one of claims 1 to 4, wherein the molecular weight distribution (Mw/Mn) is from 1 to 4. The viscosity index upward agent according to any one of claims 1 to 5, wherein the aromatic vinyl compound is styrene. The viscosity index upward agent according to any one of claims 1 to 6, wherein the conjugated diene other than the bacteriocin is at least 1 selected from the group consisting of isoprene, butadiene, and laurelene. Kind. The viscosity index upward agent according to any one of claims 1 to 7, which comprises a polymer block (A) mainly comprising the structural unit (a) derived from the aromatic vinyl compound, and the conjugated product The structural unit (b) of the diene is a hydride of the block copolymer of the polymer block (B) of the main body. A viscosity index upward agent as claimed in claim 8, wherein the carbon-carbon double bond in the polymer block (B) is hydrogenated at 50 mol% or more. An oil composition comprising a base oil and a viscosity index upward agent according to any one of claims 1 to 9. A method for producing a viscosity index upward agent according to any one of claims 1 to 9, which comprises obtaining a structural unit (a) derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene by anionic polymerization. a polymerization step of the copolymer of (b); and a step of hydrogenating 50 mol% or more of the carbon-carbon double bond in the structural unit (b) derived from the conjugated diene. A method for producing a viscosity index upward agent according to claim 11, which comprises obtaining a polymer block (A) mainly composed of a structural unit (a) derived from an aromatic diene compound by anionic polymerization, and a polymerization step of the block copolymer of the polymer block (B) from which the structural unit (b) of the conjugated diene is the main component; and 50 mol% or more of the structural unit derived from the conjugated diene (b) The step of hydrogenating the carbon-carbon double bond.