CN104411811A - Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver - Google Patents
Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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Abstract
The present invention provides a poly(meth)acrylate viscosity index improver that has a polymer chain containing a structural unit represented by general formula (1), and that has a weight average molecular weight (Mw) of at least 100,000 and a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of at most 1.6. [In formula (1), R1 represents hydrogen or a methyl group, and R2 represents a C1-36 alkyl group.]
Description
Technical field
The present invention relates to poly-(methyl) acrylic ester viscosity index improver and contain lubricating oil additive and the lubricating oil composition of this viscosity index improver.
Background technology
In the past, in the field of lubricating oil, be studied from the improvement of viewpoint to lubricating oil of energy saving.Particularly in recent years, the trend of environment of preserving our planet is high, and the requirement energy saving of lubricating oil being improved to effect strengthens further.
Such as, the lubricating oil used in the oil engine of motor car engine etc. is (also referred to as " lubricating oil for IC engines " or " engine oil ".) when, as one of means improving province's burnup, known to adding to lubricant base the method that viscosity index improver improves oil body index.
In addition, the lubricating oil such as ATF, MTF, CVTF of such as using in the variable-speed motor of automobile are (also referred to as " variable-speed motor lubricating oil " or " drive system oil ".) when, as one of means improving province's burnup, can list variable-speed motor lubricating oil lowering viscousity to reduce the method for viscous resistance.But, during by variable-speed motor with lubricating oil lowering viscousity, likely produce the other problem such as leakage of oil, sintering.
Therefore, as improving other method economizing burnup, the method using viscosity index improver is had.The method improves variable-speed motor oil body index by using viscosity index improver, maintains the viscosity under high-temperature area and the viscosity increase under suppression low-temperature region.
About viscosity index improver, propose the use of various viscosity index improver up to now, particularly propose the use (such as with reference to patent documentation 1 ~ 7) of a lot of poly-(methyl) acrylic ester viscosity index improver.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 7-48421 publication
Patent documentation 2: Japanese Unexamined Patent Publication 7-62372 publication
Patent documentation 3: Japanese Unexamined Patent Publication 6-145258 publication
Patent documentation 4: Japanese Unexamined Patent Publication 3-100099 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2002-302687 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2004-124080 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2005-187736 publication
Summary of the invention
the problem that invention will solve
But, such as, in lubricating oil for IC engines, when using above-mentioned existing poly-(methyl) acrylic ester viscosity index improver, in order to reach practical upper province fully burnup, in shear viscosity, there is room for improvement.Particularly economize in the high 0W-20 of the requirement of burnup, need the shear viscosity at 150 DEG C to be maintained level high to a certain degree, reduce by 100 DEG C on the other hand at shear viscosity.On the other hand, when utilizing existing poly-(methyl) acrylic ester viscosity index improver, the shear viscosity at maintaining 150 DEG C and shear viscosity at reduction by 100 DEG C is difficult.
In addition, such as, in variable-speed motor lubricating oil, as one of reason economizing burnup variation, the frictional dissipation during transmission of the gear being positioned at drive unit can be listed.Therefore, if the lubricating oil that under can realizing shear conditions, viscous resistance is low, then can reduce frictional dissipation, province's burnup can be improved further.
But above-mentioned existing viscosity index improver realizes the improvement of the viscosity characteristics of high-temperature area and low-temperature region by high viscosity index (HVI), reduce in effect also insufficient in frictional dissipation.
Therefore, the object of the invention is to, the viscosity index improver that can reach province's burnup and the lubricating oil additive containing this viscosity index improver and lubricating oil composition are provided.
In addition, another object of the present invention is to, the viscosity index improver that can maintain the shear viscosity at 150 DEG C and the shear viscosity at fully reducing by 100 DEG C is provided, and contain lubricating oil additive and the lubricating oil composition of this viscosity index improver.
In addition, another object of the present invention is, provides the viscosity index improver can giving sufficient frictional dissipation reduction effect to lubricating oil, and contains lubricating oil additive and the lubricating oil composition of this viscosity index improver.
for the scheme of dealing with problems
The present inventor etc. have carried out in depth studying, found that, by having specific structure, weight-average molecular weight and weight-average molecular weight Mw meet poly-(methyl) acrylic ester viscosity index improver of specified conditions (hereinafter referred to as " first poly-(methyl) acrylic ester viscosity index improver " with the ratio Mw/Mn of number-average molecular weight Mn.), the shear viscosity at 150 DEG C can be maintained and the shear viscosity at fully reducing by 100 DEG C, thus complete the present invention.
Namely, the invention provides a kind of poly-(methyl) acrylic ester viscosity index improver, it has the polymeric chain containing the structural unit shown in following general formula (1), weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is more than 100000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.
[in formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.]
In addition, the present inventor etc. have carried out in depth studying, found that, by having specific structure, weight-average molecular weight and weight-average molecular weight Mw meet poly-(methyl) acrylic ester viscosity index improver of specified conditions (hereinafter referred to as " first poly-(methyl) acrylic ester viscosity index improver " with the ratio Mw/Mn of number-average molecular weight Mn.), frictional dissipation can be given and reduce effect, thus complete the present invention.
Namely, the invention provides a kind of poly-(methyl) acrylic ester viscosity index improver, it has the polymeric chain containing the structural unit shown in following general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is less than 100000, and weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.
[in formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.]
In addition, the invention provides a kind of lubricating oil additive, it contains at least one be selected from above-mentioned first poly-(methyl) acrylic ester viscosity index improver and second poly-(methyl) acrylic ester viscosity index improver.
In addition, the invention provides a kind of lubricating oil composition, it contains lubricant base and is selected from least one in above-mentioned first poly-(methyl) acrylic ester viscosity index improver and second poly-(methyl) acrylic ester viscosity index improver.
the effect of invention
According to the present invention, the viscosity index improver that can reach province's burnup and the lubricating oil additive containing this viscosity index improver and lubricating oil composition can be provided.
In addition, according to the present invention, the viscosity index improver that can maintain the shear viscosity at 150 DEG C and the shear viscosity at fully reducing by 100 DEG C can be provided, and contain lubricating oil additive and the lubricating oil composition of this viscosity index improver.
In addition, according to the present invention, the viscosity index improver that can reduce frictional dissipation can be provided, and contain lubricating oil additive and the lubricating oil composition of this viscosity index improver.
Embodiment
Below, the preferred embodiment of the present invention is described in detail, but the present invention is not by the following any restriction of embodiment.
[the first embodiment: first poly-(methyl) acrylic ester viscosity index improver]
Poly-(methyl) acrylic ester viscosity index improver of the first embodiment has the polymeric chain containing the structural unit shown in following general formula (1).The weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is (hereinafter sometimes referred to simply as " Mw ".) be more than 100000, weight-average molecular weight Mw and number-average molecular weight Mn (hereinafter sometimes referred to simply as " Mn ".) ratio Mw/Mn (hereinafter sometimes referred to simply as " Mw/Mn ".) be less than 1.6.
[in formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.]
R
1can be any one of hydrogen or methyl, be preferably methyl.
As R
2the carbonatoms of shown alkyl is 1 ~ 36 as mentioned above, from the viewpoint of operability and ease of manufacturing, is preferably 1 ~ 30, is more preferably 1 ~ 26, more preferably 1 ~ 22.In addition, R
2shown alkyl can be straight-chain or branched.
When the structural unit shown in above-mentioned general formula (1) contained by polymeric chain is more than 2, R
1and R
2can be identical or different between structural unit.Containing R
2when two or more structural unit different, consider from province's burnup characteristics and deliquescent viewpoint, with the total amount of the structural unit contained by polymeric chain for benchmark, R
2structural unit for methyl preferably contains 10 ~ 45 quality %, more preferably contains 15 ~ 45 quality %, further preferably containing 20 ~ 45 quality %.In addition, from the viewpoint of province's burnup characteristics, with the total amount of the structural unit contained by polymeric chain for benchmark, R
2the structural unit of to be carbonatoms the be alkyl of more than 18 preferably containing more than 10 quality %, more preferably containing more than 15 quality %, further preferably containing more than 20 quality %.
Polymeric chain only can contain the structural unit shown in above-mentioned general formula (1), or except the structural unit shown in above-mentioned general formula (1), can also containing the structural unit beyond the structural unit shown in above-mentioned general formula (1).In addition, the end of polymeric chain is not particularly limited.Being preferably in this polymeric chain, is only the polymeric chain of hydrogen atom containing the structural unit shown in above-mentioned general formula (1), end, i.e. polymeric chain shown in following general formula (2).
In formula (2), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36, n is the integer meeting above-mentioned condition to select with Mw and Mw/Mn.N is such as the integer of 400 ~ 2,000.
Weight-average molecular weight Mw is 100, more than 000, from the viewpoint of province's burnup, is preferably 125, more than 000, is more preferably 150, more than 000, more preferably 175, more than 000.The upper limit of Mw is not particularly limited, and Mw is such as 500, less than 000.
Number-average molecular weight Mn meets above-mentioned condition with Mw/Mn and suitably selects.HTHS viscosity at reduction by 100 DEG C, Mn is preferably 75, and more than 000, be more preferably 94, more than 000, more preferably 110, more than 000.The upper limit of Mn is not particularly limited, and Mn is such as 300, less than 000.
Mw/Mn is less than 1.6, from the viewpoint of province's burnup, is preferably less than 1.5, is more preferably less than 1.4, more preferably less than 1.2.In addition, from the viewpoint of the yield of poly-(methyl) acrylate, Mw/Mn is preferably more than 1.0, is more preferably more than 1.01, more preferably more than 1.02.
It should be noted that, " weight-average molecular weight Mw ", " number-average molecular weight Mn " alleged in the present invention and the ratio Mw/Mn of number-average molecular weight Mn " the weight-average molecular weight Mw with " refers to Mw, Mn and Mw/Mn (polystyrene (standard test specimen) scaled value) of being obtained by gpc analysis.Specifically, such as can measure as follows.
Use tetrahydrofuran (THF) as solvent, carry out diluting and preparing the solution that sample solution concentration is 2 quality %.This sample solution uses GPC device (Waters Alliance2695) to analyze.The flow velocity of solvent is 1ml/ minute, use can analyzing molecules amount be 10,000 to 256,000 chromatographic column, using specific refractory power as detector implement analyze.It should be noted that, use the clear and definite polystyrene standard of molecular weight to try to achieve the relation of chromatographic column retention time and molecular weight, production standard curve in addition, by obtained retention time determination molecular weight.
The manufacture method of poly-(methyl) acrylic ester viscosity index improver of present embodiment is not particularly limited, can list and such as add initiator to containing in the mixing solutions of (methyl) alkyl acrylate, polymerization agent and solvent, be polymerized the method for (methyl) alkyl acrylate at an established temperature.
As (methyl) alkyl acrylate, (methyl) alkyl acrylate shown in following general formula (3) can be used.
In formula (3), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.
R
1be preferably methyl.As R
2the carbonatoms of shown alkyl, is preferably 1 ~ 30, is more preferably 1 ~ 26, more preferably 1 ~ 22.
As (methyl) alkyl acrylate, can be used alone two or more (methyl) alkyl acrylate shown in above-mentioned general formula (3) a kind of or used in combination, preferred used in combination two or more.Used in combination two or more when, with (methyl) alkyl acrylate total amount for benchmark, R
2for the content of (methyl) methyl acrylate of methyl be preferably 5 ~ 50 quality %, be more preferably 10 ~ 50 quality %, more preferably 20 ~ 45 quality %.In addition, with (methyl) alkyl acrylate total amount for benchmark, R
2the content of to be carbonatoms be (methyl) alkyl acrylate of the alkyl of more than 18 is preferably more than 10 quality %, is more preferably more than 15 quality %, more preferably more than 20 quality %.
As polymerization agent, such as, dithiobenzoic acid cumyl ester etc. can be used to have the compound of thiocarbonyl.As preferred polymerization agent, dithiobenzoic acid cumyl ester can be exemplified.
As solvent, such as, can use highly purified mineral oil, phenylmethylether, toluene.As preferred solvent, highly purified mineral oil can be exemplified.
As initiator, such as, can use the two methyl valeronitrile of azobis isobutyronitrile, azo, the two methylbutyronitrile of azo.As preferred initiator, azobis isobutyronitrile can be exemplified.
As temperature of reaction during polymerization (methyl) alkyl acrylate, be preferably 70 ~ 120 DEG C, be more preferably 80 ~ 110 DEG C, more preferably 90 ~ 100 DEG C.By making temperature of reaction be in above-mentioned scope, the Mw/Mn of poly-(methyl) acrylic ester viscosity index improver obtained is easily less than 1.6.Such as, have when temperature of reaction is 90 ~ 100 DEG C Mw/Mn be 1.0 ~ 1.2 tendency, have when temperature of reaction is 100 ~ 110 DEG C Mw/Mn be 1.2 ~ 1.4 tendency, have when temperature of reaction is 110 ~ 120 DEG C Mw/Mn be 1.4 ~ 1.6 tendency.
Reaction times suitably can be selected according to Mw and Mw/Mn as the kind of (methyl) alkyl acrylate of raw material, polymerization agent, solvent and initiator and the reaction conditions such as consumption, temperature of reaction, poly-(methyl) acrylate of object.As the preferred reaction times, 10 ~ 14 hours can be exemplified.
The polymerization of (methyl) alkyl acrylate is preferably carried out in a nitrogen atmosphere.
[the second embodiment: lubricating oil additive]
The lubricating oil additive of the second embodiment of the present invention contains poly-(methyl) acrylic ester viscosity index improver, this poly-(methyl) acrylic ester viscosity index improver has the polymeric chain containing the structural unit shown in above-mentioned general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is 100, more than 000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.It should be noted that, poly-(methyl) acrylic ester viscosity index improver in present embodiment is identical with the viscosity index improver in above-mentioned first embodiment, and at this, the repetitive description thereof will be omitted.
Lubricating oil additive only can comprise above-mentioned poly-(methyl) acrylic ester viscosity index improver, or also can be the mixture (i.e. compositions of additives) of this viscosity index improver and other additive.When lubricating oil additive is the mixture of this viscosity index improver and other additive, their mixture ratio is not particularly limited, suitably can selects according to purposes.
As other additive, the additive etc. such as viscosity index improver, antioxidant, abrasion resisting agent (or extreme pressure agent), corrosion inhibitor, rust-preventive agent, viscosity index improver, pour point depressant, non-emulsifying agent, metal passivator, defoamer, Ashless friction conditioning agent beyond above-mentioned poly-(methyl) acrylic ester viscosity index improver can be listed.These additives can be used alone one or combinationally use two or more.
As the viscosity index improver beyond above-mentioned poly-(methyl) acrylic ester viscosity index improver, poly-(methyl) acrylic ester viscosity index improver, polyisobutene system viscosity index improver, ethylene-propylene copolymer system viscosity index improver, the hydrogenated styrene-butadiene copolymerization system viscosity index improver etc. beyond above-mentioned poly-(methyl) acrylic ester viscosity index improver can be listed.
As antioxidant, the ashless antioxidant such as phenol system, amine system can be listed, the metal system antioxidants such as zinc system, copper system, molybdenum system.
As phenol system antioxidant, such as 4 can be listed, 4 '-methylene-bis (2,6 di t butyl phenol), 4,4 '-bis-(2,6 di t butyl phenol), 4,4 '-bis-(2-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4 '-isopropylidene two (2,6 di t butyl phenol), 2,2 '-methylene-bis(4-methyl-6-nonyl phenol), 2,2 '-isobutylene two (4,6-xylenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-ethylphenol, 2,4 dimethyl 6 tert butyl phenol, 2,6-, bis--uncle-alpha, alpha-dimethyl amino-p-cresol, 2,6-di-t-butyl-4-(N, N-dimethylaminomethylphenol), 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), two (3-methyl-4-hydroxyl-5-t-butylbenzyl) thioether, two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, 2,2 '-sulfo--di ethylene bis [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], tridecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, tetramethylolmethane-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], octyl group-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, octadecyl 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, octyl group-3-(3-methyl-5-di-tert-butyl-hydroxy phenyl) propionic ester etc.They can be used in combination two or more.
As amine system antioxidant, such as aromatic amines compound, alkyl diphenylamine, alkyl naphthylamines, phenyl-a-naphthylamine, alkyl phenyl-alpha-naphthylamine etc. can be listed and use and normally used known amine system antioxidant as lubricating oil.
As corrosion inhibitor, such as benzotriazole system, azimido-toluene system, thiadiazoles system or imidazole compound etc. can be listed.
As rust-preventive agent, such as mahogany acid (ester) salt, alkyl benzene sulphonate (ABS) (ester) salt, dinonylnaphthalene sulfonic acid (ester) salt, alkenyl succinate acid esters or polyol ester etc. can be listed.
As metal passivator, such as tetrahydroglyoxaline, pyrimidine derivatives, alkyl thiadiazoles, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1 can be listed, 3,4-thiadiazoles polysulfide, 1,3,4-thiadiazolyl group-2,5-two dialkyl dithio amino formate, 2-(alkyl dithio) benzoglyoxaline or β-(adjacent carboxybenzyl sulfo-) propionitrile etc.
As defoamer, can list such as 25 DEG C time kinematic viscosity be 1,000 ~ 100,000mm
2the ester of the silicone oil of/s, alkenylsuccinic derivatives, polyhydroxy fatty race alcohol and longer chain fatty acid, methyl salicylate and adjacent hydroxy-benzyl alcohol etc.
As Ashless friction conditioning agent, the Ashless friction conditioning agent of lubricating oil can be used as and normally used any compound, the straight chained alkyl of alkyl or alkenyl, the especially carbonatoms 6 ~ 30 at least in such as molecule with 1 carbonatoms 6 ~ 30 or the Ashless friction such as amine compound, fatty acid ester, fatty amide, lipid acid, fatty alcohol, the fatty ether conditioning agent etc. of straight-chain alkenyl can be listed.In addition, can also use record in Japanese Unexamined Patent Publication 2009-286831 publication nitrogenous compound and sour modification derivant etc. thereof, illustrative various Ashless friction conditioning agent in International Publication No. 2005/037967 brochure.
In addition, the lubricating oil additive of present embodiment can also contain solvent.As solvent, highly purified mineral oil, phenylmethylether, toluene can be used.Among these, preferably use highly purified mineral oil.When lubricating oil additive contains solvent, from the viewpoint of the operability as additive, with the total amount of lubricating oil additive for benchmark, the content of solvent is preferably 5 ~ 75 quality %, is more preferably 30 ~ 60 quality %.
[the 3rd embodiment: lubricating oil composition]
The lubricating oil composition of the 3rd embodiment contains lubricant base and poly-(methyl) acrylic ester viscosity index improver, this poly-(methyl) acrylic ester viscosity index improver has the polymeric chain containing the structural unit shown in above-mentioned general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is 100, more than 000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.At this, the lubricating oil composition of present embodiment comprises the mode of the lubricating oil additive containing lubricant base and above-mentioned second embodiment.Poly-(methyl) acrylic ester viscosity index improver in present embodiment is identical with poly-(methyl) acrylic ester viscosity index improver in above-mentioned first embodiment and the second embodiment, other additive in other additive contained in lubricating oil composition in addition and solvent and the second embodiment and solvent phase with, at this, the repetitive description thereof will be omitted.
Be not particularly limited as lubricant base, the lubricant base used in common lubricating oil can be used.Specifically, mineral oil system lubricant base, synthetic oil system lubricant base can be used or be selected from the mixture etc. of two or more lubricant base among these with arbitrary ratio mixing.
As mineral oil system lubricant base, can list and such as crude oil atmospheric distillation be obtained atmospheric resids, underpressure distillation is carried out to this atmospheric resids and obtains lubricating oil distillate, obtained lubricating oil distillate carried out to more than a kind in the process such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrofining and refine the base oil obtained; Or by by wax isomerization mineral oil, GTL wax (Gas toliquid wax) isomerized method and manufacture the basic wet goods obtained.
As synthetic oil system lubricating oil, such as polybutene or its hydride can be exemplified; Poly-alpha-olefin or its hydride such as 1-octene oligomers, 1-decene oligopolymer; The diester such as pentanedioic acid double tridecyl ester, hexanodioic acid two (2-ethylhexyl) ester, diisodecyl adipate, hexanodioic acid double tridecyl ester, sebacic acid two (2-ethylhexyl) ester; The polyol esters such as trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate, tetramethylolmethane pelargonate; The fragrant family synthetic oil such as alkylnaphthalene, alkylbenzene or their mixture etc.
Kinematic viscosity during 100 DEG C of lubricant base is preferably 2.5 ~ 10.0mm
2/ s, be more preferably 3.0 ~ 8.0mm
2/ s, more preferably 3.5 ~ 6.0mm
2/ s.In addition, the viscosity index of lubricant base is preferably 90 ~ 165, is more preferably 100 ~ 155, more preferably 120 ~ 150.
In order to easily play the effect of the additives such as poly-(methyl) acrylic ester viscosity index improver of the first embodiment, the saturated composition adopting stratographic analysis to obtain to lubricant base is preferably more than 80%, be more preferably more than 85%, more preferably more than 90%, most preferably be more than 95%.
With lubricating oil composition total amount for benchmark, the content of poly-(methyl) acrylic ester viscosity index improver of the first embodiment is preferably 0.1 ~ 20.0 quality %, is more preferably 0.5 ~ 15.0 quality %, more preferably 1.0 ~ 10.0 quality %.When this content is more than above-mentioned lower value, easily obtain sufficient additive effect, on the other hand, when this content is below above-mentioned higher limit, shear stability raises, and burnup persistence improves.
Kinematic viscosity during 100 DEG C of lubricating oil composition is preferably 3.0 ~ 16.3mm
2/ s, be more preferably 3.5 ~ 12.5mm
2/ s, more preferably 4.0 ~ 9.3mm
2/ s.When kinematic viscosity when 100 DEG C is more than above-mentioned lower value, easily guarantee oilness, on the other hand, when kinematic viscosity when 100 DEG C is below above-mentioned higher limit, economizes burnup and improve further.It should be noted that, kinematic viscosity during in the present invention 100 DEG C refers to kinematic viscosity when 100 DEG C that specify in JIS K-2283-1993.
The viscosity index of lubricating oil composition is preferably 150 ~ 250, is more preferably 160 ~ 240, more preferably 170 ~ 230.When viscosity index is more than above-mentioned lower value, province's burnup can be improved further while maintenance HTHS viscosity, easily reduce low temperature viscosity in addition.On the other hand, when viscosity index is below above-mentioned higher limit, the solvability of low-temperature fluidity, additive and the suitability with sealing material can be guaranteed.It should be noted that, the viscosity index in the present invention refers to the viscosity index specified in JIS K-2283-1993.
HTHS viscosity during 150 DEG C of lubricating oil composition is preferably more than 1.7mPas, is more preferably more than 2.0mPas, more preferably more than 2.3mPas, most preferably be more than 2.6mPas.When HTHS viscosity when 150 DEG C is more than above-mentioned lower value, the evaporation of lubricating oil composition can be suppressed, can oilness be guaranteed.In addition, HTHS viscosity during 100 DEG C of lubricating oil composition is preferably below 5.2mPas, is more preferably below 5.1mPas, more preferably below 5.0mPas.When HTHS viscosity when 100 DEG C is below above-mentioned higher limit, higher province's burnup can be obtained.It should be noted that, 150 DEG C in the present invention or 100 DEG C time the high-temperature high shear viscosity of HTHS viscosity when referring to 150 DEG C or 100 DEG C specifying in ASTM D-4683.
The lubricating oil composition of the viscosity index improver of the first embodiment described above, the lubricating oil additive of the second embodiment and the 3rd embodiment can use in lubricating oil for IC engines, drive system lubrication wet goods widely field, is especially useful in the field of lubricating oil for IC engines.For the fuel of the oil engine in this situation, any one in gasoline or diesel oil fuel can be used.
[the 4th embodiment: second poly-(methyl) acrylic ester viscosity index improver]
Poly-(methyl) acrylic ester viscosity index improver of the 4th embodiment has the polymeric chain containing the structural unit shown in following general formula (1).The weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is (hereinafter sometimes referred to simply as " Mw ".) less than 100,000, weight-average molecular weight Mw and number-average molecular weight Mn is (hereinafter sometimes referred to simply as " Mn ".) ratio Mw/Mn (hereinafter sometimes referred to simply as " Mw/Mn ".) be less than 1.6.
[in formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.]
R
1can be any one of hydrogen or methyl, be preferably methyl.
As R
2the carbonatoms of shown alkyl is 1 ~ 36 as mentioned above, from the viewpoint of operability and ease of manufacturing, is preferably 1 ~ 30, is more preferably 1 ~ 26, more preferably 1 ~ 22.In addition, R
2shown alkyl can be straight-chain or branched.
When the structural unit shown in above-mentioned general formula (1) contained by polymeric chain is more than 2, R
1and R
2can be identical or different between structural unit.Containing R
2when two or more structural unit different, from the viewpoint of viscosity temperature characteristic, with the total amount of the structural unit contained by polymeric chain for benchmark, R
2structural unit for methyl preferably contains 10 ~ 45 quality %, more preferably contains 15 ~ 45 quality %, further preferably containing 20 ~ 45 quality %.In addition, from the viewpoint of province's burnup characteristics, with the total amount of the structural unit contained by polymeric chain for benchmark, R
2the structural unit of to be carbonatoms the be alkyl of more than 18 preferably containing more than 10 quality %, more preferably containing more than 15 quality %, further preferably containing more than 20 quality %.
Polymeric chain only can contain the structural unit shown in above-mentioned general formula (1), or except the structural unit shown in above-mentioned general formula (1), can also containing the structural unit beyond the structural unit shown in above-mentioned general formula (1).In addition, the end of polymeric chain is not particularly limited.Being preferably in this polymeric chain, is only the polymeric chain of hydrogen atom containing the structural unit shown in above-mentioned general formula (1), end, i.e. polymeric chain shown in following general formula (2).
In formula (2), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36, n is the integer meeting above-mentioned condition to select with Mw and Mw/Mn.N is such as the integer of 40 ~ 450.
Weight-average molecular weight Mw, less than 100,000, from the viewpoint of province's burnup characteristics, is preferably 80, less than 000, is more preferably 70, less than 000, more preferably 60, less than 000.The lower limit of Mw is not particularly limited, and Mw is such as 10, more than 000.
Number-average molecular weight Mn meets above-mentioned condition with Mw/Mn and suitably selects.From the viewpoint of province's burnup characteristics, Mn is preferably 6, and more than 000, be more preferably 10, more than 000, more preferably 12, more than 500.The upper limit of Mn is not particularly limited, and Mn is such as 60, less than 000.
Mw/Mn is less than 1.6, from the viewpoint of province's burnup, is preferably less than 1.5, is more preferably less than 1.4, more preferably less than 1.3.In addition, from the viewpoint of province's burnup, Mw/Mn is preferably more than 1.0, is more preferably more than 1.01, more preferably more than 1.02.
It should be noted that, " weight-average molecular weight Mw ", " number-average molecular weight Mn " alleged in the present invention and the ratio Mw/Mn of number-average molecular weight Mn " the weight-average molecular weight Mw with " refers to Mw, Mn and Mw/Mn (polystyrene (standard test specimen) scaled value) of being obtained by gpc analysis.Specifically, such as can measure as follows.
Use tetrahydrofuran (THF) as solvent, carry out diluting and preparing the solution that sample solution concentration is 2 quality %.This sample solution uses GPC device (Waters Alliance2695) to analyze.The flow velocity of solvent is 1ml/ minute, use can analyzing molecules amount be 10,000 to 256,000 chromatographic column, using specific refractory power as detector implement analyze.It should be noted that, use the clear and definite polystyrene standard of molecular weight to try to achieve the relation of chromatographic column retention time and molecular weight, production standard curve in addition, by obtained retention time determination molecular weight.
The manufacture method of poly-(methyl) acrylic ester viscosity index improver of present embodiment is not particularly limited, can list and such as add initiator to containing in the mixing solutions of (methyl) alkyl acrylate, polymerization agent and solvent, be polymerized the method for (methyl) alkyl acrylate at an established temperature.
As (methyl) alkyl acrylate, (methyl) alkyl acrylate shown in following general formula (3) can be used.
In formula (3), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.
R
1be preferably methyl.As R
2the carbonatoms of shown alkyl, is preferably 1 ~ 36, is more preferably 1 ~ 30, more preferably 1 ~ 22.
As (methyl) alkyl acrylate, can be used alone two or more (methyl) alkyl acrylate shown in above-mentioned general formula (3) a kind of or used in combination, preferred used in combination two or more.Used in combination two or more when, with (methyl) alkyl acrylate total amount for benchmark, R
2for the content of (methyl) methyl acrylate of methyl be preferably 5 ~ 50 quality %, be more preferably 10 ~ 50 quality %, more preferably 20 ~ 45 quality %.In addition, with (methyl) alkyl acrylate total amount for benchmark, R
2the content of to be carbonatoms be (methyl) alkyl acrylate of the alkyl of more than 18 is preferably more than 10 quality %, is more preferably more than 15 quality %, more preferably more than 20 quality %.
As polymerization agent, such as, can use dithiobenzoic acid cumyl ester, material containing thiocarbonyl.As preferred polymerization agent, dithiobenzoic acid cumyl ester can be exemplified.
As solvent, such as, can use highly purified mineral oil, phenylmethylether, toluene.As preferred solvent, highly purified mineral oil can be exemplified.
As initiator, such as, can use the two methyl pentane nitrile of azobis isobutyronitrile, azo, the two methylbutyronitrile of azo.As preferred initiator, azobis isobutyronitrile can be exemplified.
As temperature of reaction during polymerization (methyl) alkyl acrylate, be preferably 70 ~ 120 DEG C, be more preferably 80 ~ 110 DEG C, more preferably 80 ~ 120 DEG C.By making temperature of reaction be in above-mentioned scope, the Mw/Mn of poly-(methyl) acrylic ester viscosity index improver obtained is easily less than 1.6.Such as, have when temperature of reaction is 90 ~ 100 DEG C Mw/Mn be 1.0 ~ 1.2 tendency, have when temperature of reaction is 100 ~ 110 DEG C Mw/Mn be 1.2 ~ 1.4 tendency, have when temperature of reaction is 110 ~ 120 DEG C Mw/Mn be 1.4 ~ 1.6 tendency.
Reaction times suitably can be selected according to Mw and Mw/Mn as the kind of (methyl) alkyl acrylate of raw material, polymerization agent, solvent and initiator and the reaction conditions such as consumption, temperature of reaction, poly-(methyl) acrylate of object.As the preferred reaction times, 10 ~ 14 hours can be exemplified.
The polymerization of (methyl) alkyl acrylate is preferably carried out in a nitrogen atmosphere.
[the 5th embodiment: lubricating oil additive]
The lubricating oil additive of the 5th embodiment of the present invention contains poly-(methyl) acrylic ester viscosity index improver, this poly-(methyl) acrylic ester viscosity index improver has the polymeric chain containing the structural unit shown in above-mentioned general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is less than 100,000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.It should be noted that, poly-(methyl) acrylic ester viscosity index improver in present embodiment is identical with the viscosity index improver in above-mentioned 4th embodiment, and at this, the repetitive description thereof will be omitted.
Lubricating oil additive only can comprise above-mentioned poly-(methyl) acrylic ester viscosity index improver, or also can be the mixture (i.e. compositions of additives) of this viscosity index improver and other additive.When lubricating oil additive is the mixture of this viscosity index improver and other additive, their mixture ratio is not particularly limited, suitably can selects according to purposes.As other additive, identical with other additive in above-mentioned second embodiment, at this, the repetitive description thereof will be omitted.
In addition, the lubricating oil additive of present embodiment can also contain solvent.As solvent, highly purified mineral oil, solvent treatment mineral oil, synthetic oil can be used.Among these, preferably use highly purified mineral oil.When lubricating oil additive contains solvent, with the total amount of lubricating oil additive for benchmark, the content of solvent is preferably 5 ~ 75 quality %, is more preferably 30 ~ 60 quality %.
[the 6th embodiment: lubricating oil composition]
The lubricating oil composition of the 6th embodiment contains lubricant base and poly-(methyl) acrylic ester viscosity index improver, this poly-(methyl) acrylic ester viscosity index improver has the polymeric chain containing the structural unit shown in above-mentioned general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is less than 100,000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn.At this, the lubricating oil composition of present embodiment comprises the mode of the lubricating oil additive containing lubricant base and above-mentioned 5th embodiment.Poly-(methyl) acrylic ester viscosity index improver in present embodiment is identical with poly-(methyl) acrylic ester viscosity index improver in above-mentioned 4th embodiment and the 5th embodiment, other additive in other additive that can contain in lubricating oil composition in addition and solvent and the 5th embodiment and solvent phase with, at this, the repetitive description thereof will be omitted.
Lubricant base is identical with the lubricant base in above-mentioned 3rd embodiment, and at this, the repetitive description thereof will be omitted.
With lubricating oil composition total amount for benchmark, the content of poly-(methyl) acrylic ester viscosity index improver of the 4th embodiment is preferably 0.1 ~ 20.0 quality %, is more preferably 0.5 ~ 15.0 quality %, more preferably 1.0 ~ 10.0 quality %.When this content is more than above-mentioned lower value, easily obtain sufficient additive effect, on the other hand, when this content is below above-mentioned higher limit, shear stability raises, and burnup persistence improves.
Kinematic viscosity during 100 DEG C of lubricating oil composition is preferably 2.0 ~ 16.3mm
2/ s, be more preferably 2.5 ~ 12.5mm
2/ s, more preferably 3.0 ~ 10.0mm
2/ s.When kinematic viscosity when 100 DEG C is more than above-mentioned lower value, easily guarantee oilness, on the other hand, when kinematic viscosity when 100 DEG C is below above-mentioned higher limit, economizes burnup and improve further.It should be noted that, kinematic viscosity during in the present invention 100 DEG C refers to kinematic viscosity when 100 DEG C that specify in JIS K-2283-1993.
The viscosity index of lubricating oil composition is preferably 130 ~ 250, is more preferably 140 ~ 240, more preferably 160 ~ 230.When viscosity index is more than above-mentioned lower value, province's burnup can be improved further while maintenance HTHS viscosity, easily reduce low temperature viscosity in addition.On the other hand, when viscosity index is below above-mentioned higher limit, the solvability of low-temperature fluidity, additive and the suitability with sealing material can be guaranteed.It should be noted that, the viscosity index in the present invention refers to the viscosity index specified in JIS K-2283-1993.
The lubricating oil composition of the viscosity index improver of the 4th embodiment described above, the lubricating oil additive of the 5th embodiment and the 6th embodiment can use in lubricating oil for IC engines, drive system lubrication wet goods widely field, is especially useful in the field of drive system lubricating oil.For the drive unit in this situation, can be any one in automatic speed variator (AT), stepless automatic transmission machine (CVT) and hand gear machine (TM).
Embodiment
Below, list embodiment and more specific description is carried out to the present invention, but the present invention is not by any restriction of following embodiment.
[embodiment 1-1]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 1-1 ").
Methyl methacrylate (the R in formula (3) is dropped in the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth
1and R
2it is all the compound of methyl.Below be recited as " C1-MA ".) 12g, the stearyl methacrylate (R in formula (3)
1for methyl, R
2for the compound of stearyl (carbonatoms is the straight chained alkyl of 18).Below be recited as " C18-MA ".) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.030g and the highly purified mineral oil 30g as solvent, form homogeneous solution under stirring.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.052g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 110 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, measure weight-average molecular weight Mw and number-average molecular weight Mn by gpc analysis.Its result, weight-average molecular weight Mw is 230,000, number-average molecular weight Mn is 152,000, Mw/Mn is 1.51.The step of gpc analysis as described below.
Use tetrahydrofuran (THF) as solvent, carry out diluting and preparing the solution that sample solution concentration is 2 quality %.This sample solution uses GPC device (Waters Alliance2695) to analyze.The flow velocity of solvent is 1ml/ minute, use can analyzing molecules amount be 10,000 to 256,000 chromatographic column, using specific refractory power as detector implement analyze.It should be noted that, use the clear and definite polystyrene standard of molecular weight to try to achieve the relation of chromatographic column retention time and molecular weight, production standard curve in addition, by obtained retention time determination molecular weight.
[embodiment 1-2]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 1-2 ").
In the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth, drop into methyl methacrylate (C1-MA) 12g, stearyl methacrylate (C18-MA) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.031g and the highly purified mineral oil 30g as solvent, under stirring, form homogeneous solution.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.051g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 100 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 1-1, weight-average molecular weight Mw is 220,000, number-average molecular weight Mn is 167,000, Mw/Mn is 1.32.
[embodiment 1-3]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 1-3 ").
In the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth, drop into methyl methacrylate (C1-MA) 12g, stearyl methacrylate (C18-MA) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.033g and the highly purified mineral oil 30g as solvent, under stirring, form homogeneous solution.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.055g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 90 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 1-1, weight-average molecular weight Mw is 210,000, number-average molecular weight Mn is 186,000, Mw/Mn is 1.13.
[comparative example 1-1]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 1-4 ").
In the 300ml tetra-neck reaction flask being provided with agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction dropping funnel, drop into the highly purified mineral oil 30g as solvent, implement nitrogen purging limit at the oil bath inner edges of 85 DEG C and stir 1 hour.Drop in Sample introduction dropping funnel as methyl methacrylate (C1-MA) 12g of starting monomer and stearyl methacrylate (C18-MA) 18g, the raw material that mixes as azobis isobutyronitrile (AIBN) 0.12g of radical initiator, with 70 minutes, this raw material is added drop-wise in reaction flask.Then, keep stirring and implementing polymerization in 8 hours under stream of nitrogen gas at 85 DEG C, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.Then, 130 DEG C, implement vacuum distilling in 3 hours under 1mmHg, thus by above-mentioned solution removal unreacted monomer.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 1-1, weight-average molecular weight Mw is 260,000, number-average molecular weight Mn is 158,000, Mw/Mn is 1.65.
[embodiment 1-4 ~ 1-15, comparative example 1-2 ~ 1-4]
The compounding amount of raw material changes as shown in table 1,3,5,7, in addition synthesizes poly-(methyl) acrylic ester viscosity index improver in the same manner as any one in above-mentioned synthesis condition 1-1 ~ 1-4.It should be noted that, in table, the R in C12-MA expression (3)
1for methyl, R
2for the compound of dodecyl (carbonatoms is the straight chained alkyl of 12), in addition, the R in C22-MA expression (3)
1for methyl, R
2for the compound of docosyl (carbonatoms is the straight chained alkyl of 22).Mw, Mn and Mw/Mn of poly-(methyl) acrylic ester viscosity index improver obtained are shown in table 2,4,6,8.
The preparation > of < lubricating oil composition
By poly-(methyl) acrylic ester viscosity index improver obtained respectively in embodiment 1-1 ~ 1-15 and comparative example 1-1 ~ 1-4, performance additive containing metal system (calcium sulphonate system) scavenging agent, ashless dispersant (succinimide), friction modifier (XU 61518.10) and abrasion resisting agent (zinc dithiophosphate), and highly purified mineral oil (GroupIII base oil, 100 DEG C time kinematic viscosity: 4.2mm
2/ s, VI:125) compounding with the ratio shown in table 2,4,6,8, prepare lubricating oil composition.
The evaluation > of < lubricating oil composition
For each lubricating oil composition of embodiment 1-1 ~ 1-15 and comparative example 1-1 ~ 1-4, respectively by according to following standard method to kinematic viscosity when 100 DEG C, viscosity index and 100 DEG C and 150 DEG C time HTHS viscosity measure.Result is shown in table 2,4,6,8.
Kinematic viscosity: JIS K-2283-1993
Viscosity index: JIS K 2283-1993
HTHS viscosity: ASTM D-4683
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[embodiment 2-1]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 2-1 ").
Methyl methacrylate (the R in formula (3) is dropped in the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth
1and R
2it is all the compound of methyl.Below be recited as " C1-MA ".) 12g, the stearyl methacrylate (R in formula (3)
1for methyl, R
2for the compound of stearyl (carbonatoms is the straight chained alkyl of 18).Below be recited as " C18-MA ".) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.081g and the highly purified mineral oil 30g as solvent, form homogeneous solution under stirring.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.014g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 110 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, measure weight-average molecular weight Mw and number-average molecular weight Mn by gpc analysis.Its result, weight-average molecular weight Mw is 83,000, number-average molecular weight Mn is 55,000, Mw/Mn is 1.51.The step of gpc analysis as described below.
Use tetrahydrofuran (THF) as solvent, carry out diluting and preparing the solution that sample solution concentration is 2 quality %.This sample solution uses GPC device (Waters Alliance2695) to analyze.The flow velocity of solvent is 1ml/ minute, use can analyzing molecules amount be 10,000 to 256,000 chromatographic column, using specific refractory power as detector implement analyze.It should be noted that, use the clear and definite polystyrene standard of molecular weight to try to achieve the relation of chromatographic column retention time and molecular weight, production standard curve in addition, by obtained retention time determination molecular weight.Pass through obtained molecular weight (Mw and Mn) can calculate arm molecular weight (Mw and Mn) divided by the functional group number of initiator.
[embodiment 2-2]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 2-2 ").
In the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth, drop into methyl methacrylate (C1-MA) 12g, stearyl methacrylate (C18-MA) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.085g and the highly purified mineral oil 30g as solvent, under stirring, form homogeneous solution.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.013g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 100 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 2-1, weight-average molecular weight Mw is 78,000, number-average molecular weight Mn is 59,000, Mw/Mn is 1.32.
[embodiment 2-3]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 2-3 ").
In the removable flask of 300ml five neck being provided with anchor shaped metal agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction mouth, drop into methyl methacrylate (C1-MA) 12g, stearyl methacrylate (C18-MA) 18g, dithiobenzoic acid cumyl ester (CDTBA) 0.084g and the highly purified mineral oil 30g as solvent, under stirring, form homogeneous solution.This solution is cooled to 0 DEG C in ice bath, uses surge pump to implement the vacuum outgas/nitrogen purging of 5 secondary response systems.Further, azobis isobutyronitrile (AIBN) 0.014g as radical initiator is dropped into by Sample introduction mouth under stream of nitrogen gas, then at solution temperature 90 DEG C, implement polymerization in 12 hours in a nitrogen atmosphere, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 2-1, weight-average molecular weight Mw is 85,000, number-average molecular weight Mn is 75,000, Mw/Mn is 1.13.
[comparative example 2-1]
Poly-(methyl) acrylic ester viscosity index improver of synthesis under following condition (" synthesis condition 2-4 ").
In the 300ml tetra-neck reaction flask being provided with agitating vane (with vacuum-sealing), serpentine condenser, nitrogen importing stop,threeway and Sample introduction dropping funnel, drop into the highly purified mineral oil 30g as solvent, implement nitrogen purging limit at the oil bath inner edges of 85 DEG C and stir 1 hour.Drop in Sample introduction dropping funnel as methyl methacrylate (C1-MA) 12g of starting monomer and stearyl methacrylate (C18-MA) 18g, the raw material that mixes as azobis isobutyronitrile (AIBN) 0.068g of radical initiator, with 70 minutes, this raw material is added drop-wise in reaction flask.Then, keep stirring and implementing polymerization in 8 hours under stream of nitrogen gas at 85 DEG C, obtain the solution containing poly-(methyl) acrylic ester viscosity index improver.Then, 130 DEG C, implement vacuum distilling in 3 hours under 1mmHg, thus by above-mentioned solution removal unreacted monomer.
For obtained poly-(methyl) acrylic ester viscosity index improver, carry out the result of gpc analysis in the same manner as embodiment 2-1, weight-average molecular weight Mw is 18,000, number-average molecular weight Mn is 11,000, Mw/Mn is 1.65.
[embodiment 2-4 ~ 2-14, comparative example 2-2 ~ 2-5]
The compounding amount of raw material changes as shown in table 9,11,13,15, in addition synthesizes poly-(methyl) acrylic ester viscosity index improver in the same manner as any one in above-mentioned synthesis condition 2-1 ~ 2-4.It should be noted that, in table, the R in C12-MA expression (3)
1for methyl, R
2for the compound of dodecyl (carbonatoms is the straight chained alkyl of 12), in addition, the R in C22-MA expression (3)
1for methyl, R
2for the compound of docosyl (carbonatoms is the straight chained alkyl of 22).Mw, Mn and Mw/Mn of poly-(methyl) acrylic ester viscosity index improver obtained are shown in table 2,4,6,8.
The preparation > of < lubricating oil composition
By poly-(methyl) acrylic ester viscosity index improver obtained respectively in embodiment 2-1 ~ 2-14 and comparative example 2-1 ~ 2-5, containing metal system (the calcium sulphonate system of TBN300mgKOH/g) scavenging agent, performance additive without residual dose of ash content (succinimide), friction modifier (oleylamide), abrasion resisting agent (phosphoric acid), antioxidant (pentanoic), metal passivator (thiadiazoles) and sulphur system additive (sulfuration ester), and highly purified mineral oil (GroupIII base oil, 100 DEG C time kinematic viscosity: 3.3mm
2/ s, VI:110) compounding with the ratio shown in table 10,12,14,16, prepare lubricating oil composition.
The evaluation > of < lubricating oil composition
For each lubricating oil composition of embodiment 2-1 ~ 2-14 and comparative example 2-1 ~ 2-5, respectively by the method according to following standard, kinematic viscosity when 100 DEG C and viscosity index are measured.Result is shown in table 10,12,14,16.
Kinematic viscosity: JIS K-2283-1993
Viscosity index: JIS K 2283-1993
In addition, for the rubbing characteristics of each lubricating oil composition of embodiment 2-1 ~ 2-14 and comparative example 2-1 ~ 2-5, use two cylinder rotational slide frictional testing machines, evaluated by the frictional coefficient under certain loading condition.Specifically, under the condition of test temperature 80 DEG C, load 142N, surface pressure 0.48GPa, circumferential speed 1.0m/s, slip ratio 5.1%, the frictional coefficient risen on-test in 10 minutes is average.Result is shown in table 10,12,14,16.
[table 9]
[table 10]
[table 11]
[table 12]
[table 13]
[table 14]
[table 15]
[table 16]
Claims (4)
1. poly-(methyl) acrylic ester viscosity index improver, it has the polymeric chain containing the structural unit shown in following general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is more than 100000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn
In formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.
2. poly-(methyl) acrylic ester viscosity index improver, it has the polymeric chain containing the structural unit shown in following general formula (1), the weight-average molecular weight Mw of this poly-(methyl) acrylic ester viscosity index improver is less than 100000, weight-average molecular weight Mw is less than 1.6 with the ratio Mw/Mn of number-average molecular weight Mn
In formula (1), R
1represent hydrogen or methyl, R
2represent that carbonatoms is the alkyl of 1 ~ 36.
3. a lubricating oil additive, it contains poly-(methyl) acrylic ester viscosity index improver described in claim 1 or 2.
4. a lubricating oil composition, it contains poly-(methyl) acrylic ester viscosity index improver described in lubricant base and claim 1 or 2.
Applications Claiming Priority (21)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-163619 | 2012-07-24 | ||
| JP2012-163622 | 2012-07-24 | ||
| JP2012163619 | 2012-07-24 | ||
| JP2012-163624 | 2012-07-24 | ||
| JP2012163624 | 2012-07-24 | ||
| JP2012163622 | 2012-07-24 | ||
| JP2013079830 | 2013-04-05 | ||
| JP2013-079830 | 2013-04-05 | ||
| JP2013-079832 | 2013-04-05 | ||
| JP2013-079816 | 2013-04-05 | ||
| JP2013079816 | 2013-04-05 | ||
| JP2013-079828 | 2013-04-05 | ||
| JP2013079832 | 2013-04-05 | ||
| JP2013079829 | 2013-04-05 | ||
| JP2013-079829 | 2013-04-05 | ||
| JP2013079828 | 2013-04-05 | ||
| JP2013142014A JP6018981B2 (en) | 2013-07-05 | 2013-07-05 | Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver |
| JP2013-142036 | 2013-07-05 | ||
| JP2013142036A JP6018982B2 (en) | 2013-07-05 | 2013-07-05 | Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver |
| JP2013-142014 | 2013-07-05 | ||
| PCT/JP2013/070100 WO2014017558A1 (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104411811A true CN104411811A (en) | 2015-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380034045.4A Pending CN104411811A (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20150203782A1 (en) |
| EP (1) | EP2878657B1 (en) |
| CN (1) | CN104411811A (en) |
| WO (1) | WO2014017558A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057606A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Viscosity index improver and preparation method and application thereof |
| CN113150857A (en) * | 2020-11-30 | 2021-07-23 | 大连同康新材料科技有限公司 | Application of polymethacrylate as viscosity index improver of energy-saving hydraulic oil and energy-saving hydraulic oil |
| CN114369196A (en) * | 2022-01-17 | 2022-04-19 | 新乡市瑞丰新材料股份有限公司 | Polymethacrylate viscosity index improver and preparation method thereof |
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| JP6420964B2 (en) * | 2014-03-31 | 2018-11-07 | 出光興産株式会社 | Lubricating oil composition for internal combustion engines |
| WO2016043195A1 (en) | 2014-09-17 | 2016-03-24 | 株式会社日本触媒 | Viscosity index improver, process for producing same, and lubricating oil composition |
| TW201736410A (en) | 2016-01-12 | 2017-10-16 | 可樂麗股份有限公司 | (meth)acrylate polymer |
| US10982167B2 (en) | 2016-09-21 | 2021-04-20 | Nippon Shokubai Co., Ltd. | Viscosity index improver and lubricating oil composition |
| US20200123295A1 (en) * | 2017-06-30 | 2020-04-23 | Kuraray Co., Ltd. | Methacrylic copolymer and solution containing same |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014017558A1 (en) | 2014-01-30 |
| EP2878657A4 (en) | 2015-07-08 |
| US20150203782A1 (en) | 2015-07-23 |
| EP2878657B1 (en) | 2018-06-13 |
| EP2878657A1 (en) | 2015-06-03 |
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