CN106147935B - A kind of lubricant composition and preparation method thereof - Google Patents
A kind of lubricant composition and preparation method thereof Download PDFInfo
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- CN106147935B CN106147935B CN201510189139.XA CN201510189139A CN106147935B CN 106147935 B CN106147935 B CN 106147935B CN 201510189139 A CN201510189139 A CN 201510189139A CN 106147935 B CN106147935 B CN 106147935B
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Abstract
The present invention relates to lubricating grease field, a kind of lubricant composition and preparation method thereof is specifically provided.The butadiene-styrene rubber particle with cross-linked structure prepared by cross-linking radiation method that the lubricant composition contains base oil and is dispersed in the base oil, the base oil is continuous phase, the butadiene-styrene rubber particle is dispersed phase, and the base oil relative to 100 parts by weight, the content of the butadiene-styrene rubber particle are 10-180 parts by weight.Lubricant composition provided by the invention can effectively adjust viscosity with the variation of temperature, temperature limit is wide, compared with the lubricant composition containing the butadiene-styrene rubber particle obtained by peroxide crosslinking, at 40 DEG C, kinematic viscosity is lower, and kinematic viscosity is higher at 100 DEG C.In addition, lubricant composition provided by the invention also has excellent antiwear and friction reduction property.
Description
Technical field
It is prepared the present invention relates to a kind of lubricant composition, the preparation method of the lubricant composition and by this method
Obtained lubricant composition.
Background technique
Lubricating grease is usually that thickening agent is dispersed in one or more of lube base oils, and obtains by saponification
Semisolid, the solid lubricant arrived.Common grease thickener is divided into soap base, non-soap base and hydrocarbyl type, soap base thickening agent
Mostly fatty acid salt, such as stearic acid calcium salt, 12- hydroxy stearic acid calcium salt, non-soap base thickening agent then includes organic polyureas, inorganization
Object etc. is closed, alkyl thickening agent is usually paraffin class.It generally can satisfy using lubricating grease prepared by above-mentioned thickening agent commonly used
Demand, but as modern industry rapidly develops, the high-grade, precision and advanced mechanical equipment continued to bring out is higher and higher to PERFORMANCE OF GREASES requirement,
Need to meet broader use temperature range, more high shear rates, more big load condition etc..Novel lubricating grease thickening agent as a result,
Or the exploitation of compound additive is in widespread attention.
Nano material refers to the solid material that the ultrafine dust by size less than 100 nanometers forms.Since it has than table
The features such as area is big, good dispersion, easy-sintering, big hardness, and there is good antifriction compressive property and nanoparticle opposite grinding
There is certain repair on damage surface, and therefore, it can be improved the service life of lubricating system.In addition, just because of using nanometer material
Lubricating oil, the lubricating grease of feed additives preparation reflect good tribological property, prepare high property using nano material additive
Energy lubricating grease has good prospect.
There is the report of the largely application about inorganic nano-particle in lubricating grease field in the prior art.For example,
CN104046407A discloses a kind of lubricating oil (rouge) antiwear and antifriction compound additive, consisting of oxide nano rare earth coats
Ultra-fine muscovite is added in base oil or lubricating grease with the ratio of 0.5-3%, it can is significantly reduced coefficient of friction, is reduced mill
Spot diameter.CN104031717A discloses a kind of aluminium nitride and copper mixing nanometer lubricating grease additive, this compound additive grain
Degree range is 50-200nm.Lubricating grease using the preparation of this additive has good antiwear and friction reduction property, and coefficient of friction can reduce
23.6-15.8%, friction durability can extend 6-7 times.CN103525513A discloses a kind of high temperature lubricating oil/fat composition and preparation
Method, wherein using boron nitride micro mist as thickening agent, using graphite microparticles and MCA (melamine cyanurate) as extreme-pressure anti-wear
The lubricating grease of agent, preparation has excellent high-temperature behavior, extreme pressure and antiwear behavior and oxidation stability.Although by adding inorganic receive
The lubricant composition that rice material obtains has excellent high temperature resistant, pressure resistance, wear-resisting property, but it is residual that easy sintering is used for a long time
Friction surface is stayed in, lubricant effect is influenced.In addition, most inorganic nano additives need to be used cooperatively with conventional thickening agent, this
The PERFORMANCE OF GREASES that sample is prepared can be improved, therefore increase manufacturing cost and use cost.
In addition, there are also the answering in lubricating grease field about organic fine particles gel other than inorganic nano-particle
Report.For example, Rhein Chemie Rheinau GmbH application patent CN1856527A, CN1840622A and
CN1861673A discloses the micro gel of a kind of micro gel in non-crosslinkable organic media and crosslinking for changing
The purposes of the temperature-independent performance of the non-crosslinked organic media of property.However, this several patents application is pointed out bar none, institute
State micro gel and be by the way of chemical crosslinking (for example, by with polyfunctional compound's crosslinking copolymerization or pass through peroxide
Compound crosslinking) micro gel that is prepared, rather than the micro gel being crosslinked with high-energy radiation.Above-mentioned patent application thinks high
The micro gel of energy crosslinking with radiation is actually unable in be prepared on an industrial scale, and the use of the high-energy radiation of radioactivity cobalt source is with tight
The safety problem of weight, the and when micro gel of crosslinking with radiation is used in plastic matrix, can be between matrix and dispersed phase
Tearing effect occurs, to compromise the mechanical performance of the plastics containing the micro gel, swelling behavior, stress corrosion cracking
Energy is equal.However, in patent CN1856527A, CN1840622A and CN1861673A of Rhein Chemie Rheinau GmbH's application
The viscosity temperature characteristic of disclosed lubricant composition is poor, and the viscosity of the lubricant composition can sharply increase with the reduction of temperature
Greatly, it can strongly reduce as the temperature rises, but viscosity is excessive at low temperature or viscosity is too small unfavorable at high temperature
With the application of lubricant composition, this will greatly limit the application of the lubricant composition.Therefore, it needs to develop
A kind of lubricant composition with preferable viscosity temperature characteristic.
Summary of the invention
The defect that the purpose of the invention is to overcome existing lubricant composition viscosity temperature characteristic poor, and one kind is provided
It the preparation method of lubricant composition, a kind of lubricant composition with excellent viscosity temperature characteristic and is prepared by this method
Lubricant composition.
The present inventor has found that Rhein Chemie Rheinau GmbH applies several above-mentioned after further investigation
Dispersed phase in lubricant composition disclosed in patent CN1856527A, CN1840622A and CN1861673A is using multifunctional
The micro gel that compound or peroxide are obtained by chemical crosslinking mode, although the grease composition containing the microgel particle
Object can reduce the coefficient of friction of organic media to a certain extent, but the viscosity of these lubricant compositions is by the shadow of temperature
Sound is larger, and temperature too high (viscosity is too small) or too low (viscosity is too big) will limit the use of the lubricant composition, applicable for temperature
It is relatively narrow to spend range.And the rubber particles with cross-linked structure that are prepared by cross-linking radiation method and by using multifunctional chemical combination
The rubber particles with cross-linked structure that object or peroxide carry out chemical crosslinking preparation have entirely different microstructure.When
It is right when dispersed phase in lubricant composition is the butadiene-styrene rubber particle with cross-linked structure prepared by cross-linking radiation method
The lubricant composition answered has good viscosity temperature characteristic, very well can adjust viscosity with the variation of temperature, reduces
Low temperature viscosity simultaneously improves high temperature viscosity, therefore, can largely make up variation shadow caused by viscosity as temperature
It rings.In addition, high-energy radiation actually very cleaning, the safe and efficient energy, at present by many developed countries widely
It is that there are some using Chemical Crosslinking Methods (peroxide) instead for fields such as health care, food processing, industrial productions
Very important problem, such as the environmental pollution that production efficiency is not high, peroxide is remained and be may cause, these can all be limited
Make its application.Based on this, the present invention is completed.
Specifically, the present invention provides a kind of lubricant compositions, wherein the lubricant composition contain base oil and
The butadiene-styrene rubber particle with cross-linked structure prepared by cross-linking radiation method being dispersed in the base oil, the basis
Oil is continuous phase, and the butadiene-styrene rubber particle is dispersed phase, and the base oil relative to 100 parts by weight, the butylbenzene rubber
The content of micelle is 10-180 parts by weight.
The present invention also provides a kind of preparation method of lubricant composition, this method is by base oil and passes through cross-linking radiation
The butadiene-styrene rubber particle to be dispersed with cross-linked structure of method preparation is mixed and is dispersed, and relative to 100 parts by weight
The base oil, the dosage of the butadiene-styrene rubber particle to be dispersed are 10-180 parts by weight.
The present invention also provides lubricant compositions prepared by the above method.
Lubricant composition provided by the invention can effectively adjust viscosity with the variation of temperature, and viscosity temperature characteristic is excellent
Different, butadiene-styrene rubber particle therein makes base oil that stabilization be kept to not easily run off up to nano-dispersion, therefore, the lubrication
The temperature limit of oil/fat composition is wide, and viscosity higher can still be maintained under high temperature high shear, can satisfy 100 DEG C or more
Using the lubricating requirement of temperature occasion, be suitble to the field of all grease applications, especially temperature be higher, antiwear and antifriction require it is high
Field, as heavy load is mechanical, the lubrication occasion of running equipment steady in a long-term, and can also be compounded with other lubricating additives
It uses, prepares special lubricant composition.In addition, the antiwear and friction reduction property of lubricant composition provided by the invention is excellent,
The wearability of lubricant composition had not only can be improved in the butadiene-styrene rubber particle of nano-dispersion, but also can play similar micro- bearing and make
With to increase rolling friction and reduce interface friction force.
Since cross-linking radiation makes special construction possessed by rubber particles, lubricant composition provided by the invention it is resistance to old
Change is had excellent performance, not easy to change, therefore this lubricant composition can be used as the lubricating grease haveing excellent performance and use, and especially answer
For the field more demanding to the viscosity temperature characteristic, ageing properties and frictional behaviour that lubricate oil systems.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is a kind of infrared spectrum of butadiene-styrene rubber particle provided by the invention；
Fig. 2 is the microscopic appearance figure of the lubricant composition obtained by the method for embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Lubricant composition provided by the invention, which contains base oil and is dispersed in the base oil, passes through cross-linking radiation
The butadiene-styrene rubber particle with cross-linked structure of method preparation, the base oil are continuous phase, and the butadiene-styrene rubber particle is point
Dephasing.Wherein, the butadiene-styrene rubber particle is in stable dispersion state, and the base relative to 100 parts by weight in base oil
Plinth oil, the content of the butadiene-styrene rubber particle are 10-180 parts by weight.
The lubricant composition provided according to the present invention, as discussed previously with respect to the base oil of 100 parts by weight, institute
The content for stating butadiene-styrene rubber particle is 10-180 parts by weight, but in order to enable base oil and butadiene-styrene rubber particle play better association
Same mating reaction, and so that the lubricant composition arrived has better viscosity temperature characteristic, it is preferable that relative to 100 weight
The base oil of part, the content of the butadiene-styrene rubber particle are 10-160 parts by weight, more preferably 10-120 parts by weight.
The lubricant composition provided according to the present invention, it is preferable that the average grain diameter of the butadiene-styrene rubber particle is 20-
2000nm, more preferably 50-1000nm, particularly preferred 70-500nm.It is controlled when by the average grain diameter of the butadiene-styrene rubber particle
When within the above range, the viscosity of lubricant composition can be more effectively adjusted, broader use temperature range is suitable for.
The lubricant composition provided according to the present invention, it is preferable that the gel content of the butadiene-styrene rubber particle is 60 weights
Measure % or more, more preferably 75 weight % or more, particularly preferably 80 weight % or more.When coagulating the butadiene-styrene rubber particle
When glue content is controlled within the above range, the viscosity of lubricant composition can be more effectively adjusted with the variation of temperature, it can
Adapt to broader use temperature range.In the present invention, the gel content is this field for characterizing rubber cross degree
A kind of Common Parameters, measure according to method disclosed in CN1402752A.
In the present invention, the butadiene-styrene rubber particle can be the unmodified rubber obtained by styrene and butadiene copolymer
Particle, or the modified rubber particle that styrene and butadiene and other olefin-copolymerizations obtain.Wherein, other described alkene
The type of hydrocarbon can be selected according to the composition of target butadiene-styrene rubber particle, can be known to this those skilled in the art,
This is not repeated.It is preferably containing carboxyl and/or ester group when the butadiene-styrene rubber particle is modified styrene butadiene rubber particle
Modified styrene butadiene rubber particle is (that is, the butadiene-styrene rubber particle is by styrene, butadiene and alkene containing carboxyl and/or ester group
Hydrocarbon is copolymerized to obtain), for example, carboxylic styrene-butadiene rubber particle.In the butadiene-styrene rubber particle, the content of styrol structural unit can
Think 5-90 weight %, preferably 10-70 weight %.
In addition, butadiene-styrene rubber particle provided by the invention is preferably equal phase structure.In the present invention, described " equal phase structure "
Refer to and observe under existing microtechnic do not have to find the not homogeneous phenomenons such as layering, split-phase in butadiene-styrene rubber particle.
The lubricant composition provided according to the present invention, high-energy ray source used in the cross-linking radiation can be selected from cobalt
At least one of source, ultraviolet, high-energy electron accelerator, it is preferable that the wavelength in the high-energy ray source less than 0.1 μm, such as
For cobalt source.In addition, under normal circumstances, the dosage of irradiation should make the gel of the butadiene-styrene rubber particle after rubber latex cross-linking radiation
Content reaches 60 weight % or more, preferably reaches 75 weight % or more, more preferably up to 80 weight % or more.Specifically, it irradiates
Dosage can be 0.1-30Mrad, preferably 0.5-20Mrad.
The present invention is not particularly limited the type of the base oil, can be mineral base oil, or synthesis
Base oil can also be the mixture of both the above base oil.
It includes: that low viscosity refers to that the mineral base oil, which divide according to China base oil classification standard QSHR 001-95,
Number mineral base oil (viscosity index (VI) VI≤40), medium viscosity index mineral base oil (40 < viscosity index (VI) VI≤90), high viscosity
Index mineral base oil (90 < viscosity index (VI) VI≤120), very high viscosity index (HVI) mineral base oil (120 < viscosity index (VI) VI≤
And superhigh viscosity index mineral base oil (viscosity index (VI) VI > 140) five class base oils 140).And according to GB/T1995-1998 state
Family's standard " oil product viscosity index (VI) calculating method " is defined, and viscosity index (VI) (VI) indicates that oil viscosity varies with temperature this spy
The about quantitative values of one of sign.For oil product similar in kinematic viscosity, viscosity index (VI) is higher, indicates that oil viscosity varies with temperature more
It is small.Specifically, the mineral base oil mainly includes alkane, cycloalkane, aromatic hydrocarbons, cycloalkanes aromatic hydrocarbons and oxygen-containing, nitrogenous, sulfur-bearing is organic
The non-hydrocarbon compounds such as compound and colloid, asphalitine, wherein almost without alkene.The mineral base oil can be by crude oil
The mixture of middle higher boiling, the hydro carbons of high relative molecular mass and non-hydrocarbons by air-distillation/vacuum distillation, solvent refining,
The techniques such as dewaxing, depitching are made.From the point of view of mineral base oil distillate, hydro carbons carbon number distribution is generally C20-C40, boiling point model
About 300-550 DEG C is enclosed, relative molecular mass is 250-1000 or higher.
The synthetic base oil is prepared using methodology of organic synthesis, has and stablize chemical structure and particularity
The lubricating oil of energy.The synthetic base oil is selected from synthesis hydrocarbon, alkylaromatic hydrocarbon, synthetic ester, polyethers, halogenated hydrocarbons, polysiloxanes and contains
At least one of fluorocarbon oil.The synthetic base oil of above-mentioned each type can be single pure material or the mixing being made of homologue
Object.Wherein, the synthesis hydrocarbon is selected from ethylene low polymer, propylene oligomer, polybutene, polyisobutene, poly alpha olefin (PAO), gathers
At least one of the halogenated product of internal olefin and above-mentioned synthesis hydrocarbon.Wherein, the poly alpha olefin do not include ethylene low polymer,
Propylene oligomer and poly 1-butene.The alkylaromatic hydrocarbon is selected from alkylbenzene, alkylnaphthalene and contains hetero atom (oxygen, sulphur, halogen
Deng) at least one of alkylaromatic hydrocarbon.The synthetic ester is selected from monoesters, dibasic acid esters, polyol ester, polymer esters, carbonic ester, phosphorus
At least one of acid esters, citrate, esters of silicon acis and olefin-acrylic lipin polymer.The polyethers is selected from aliphatic
At least one of polyethers, polyphenylene oxide, poly- polythiaether and perfluoroalkyl polyethers.The polysiloxanes is selected from two polysiloxanes, three
At least one of polysiloxanes, four polysiloxanes, eight polysiloxanes and the poly- tetrasiloxane of ring.
In addition, lubricant composition provided by the invention can also contain common additive.The type of the additive
Including but not limited to: anti-aging agent, antiwear additive, antilubricant, antioxidant, anti-foaming agent, antirust agent, detersive, dispersing agent, pigment, pole
Press at least one of composition, friction protection composition, detersive, coupling agent etc..The dosage of the additive can be this
The conventional selection in field can know that therefore not to repeat here to this those skilled in the art.
The preparation method of lubricant composition provided by the invention includes preparing by base oil and by cross-linking radiation method
The butadiene-styrene rubber particle to be dispersed with cross-linked structure mixed and dispersed, and the basis relative to 100 parts by weight
Oil, the dosage of the butadiene-styrene rubber particle to be dispersed are 10-180 parts by weight.
The preparation method of the lubricant composition provided according to the present invention, as discussed previously with respect to described in 100 parts by weight
Base oil, the dosage of the butadiene-styrene rubber particle to be dispersed are 10-180 parts by weight, but in order to enable base oil and fourth to be dispersed
Benzene rubber particles play the role of better coordinated, and so that the lubricant composition arrived has preferably viscous warm nature
It can, it is preferable that relative to the base oil of 100 parts by weight, the dosage of the butadiene-styrene rubber particle to be dispersed is 10-160 weight
Measure part, particularly preferably 10-120 parts by weight.
The preparation method of the lubricant composition provided according to the present invention, it is preferable that the butadiene-styrene rubber particle to be dispersed
For the butadiene-styrene rubber particle cluster for by average grain diameter being 20-2000nm, more preferably 50-1000nm, particularly preferably 70-500nm
Poly- and formation rubber particles group.After the butadiene-styrene rubber particle to be dispersed is dispersed in base oil, the butylbenzene of reunion
Rubber particles can be dispersed well, thus with 20-2000nm, preferably with 50-1000nm, more preferably with 70-500nm's
Average particle size distribution is in base oil.In addition, the average grain diameter of the butadiene-styrene rubber particle to be dispersed is preferably 20-2000nm,
More preferably 50-1000nm, particularly preferably 70-500nm.
The preparation method of the lubricant composition provided according to the present invention, it is preferable that the butadiene-styrene rubber particle to be dispersed
Gel content be 60 weight % or more, more preferably 75 weight % or more, particularly preferably 80 weight % or more.When will be described
When gel content wait disperse butadiene-styrene rubber particle controls within the above range, can more effectively it be adjusted with the variation of temperature
The viscosity of lubricant composition is suitable for broader use temperature range.
The butadiene-styrene rubber particle to be dispersed is preferably equal phase structure.In the present invention, described " equal phase structure " refers to
It is observed under existing microtechnic, does not have to find the not homogeneous phenomenons such as layering, split-phase in butadiene-styrene rubber particle to be dispersed.
The butadiene-styrene rubber particle to be dispersed can be to pass through cross-linking radiation system by styrene and butadiene copolymer emulsions
It is standby and obtain after being dried by spray drying process wait disperse unmodified butadiene-styrene rubber particle, or styrene and butadiene
And other alkene copolymer latex liquid are crossed cross-linking radiation and are prepared and by being obtained after spray drying process drying to disperse modified
Butadiene-styrene rubber particle.Wherein, the type of other alkene can be carried out according to the composition of target butadiene-styrene rubber particle to be dispersed
Selection, can know this those skilled in the art, therefore not to repeat here.When the butadiene-styrene rubber particle to be dispersed is wait disperse
When modified styrene butadiene rubber particle, preferably containing carboxyl and/or ester group to disperse modified butadiene-styrene rubber particle (that is, described
Butadiene-styrene rubber particle to be dispersed passes through spoke by styrene, butadiene and olefin copolymer lotion containing carboxyl and/or ester group
Prepare according to crosslinking and obtained by spray drying), for example, carboxylic styrene-butadiene rubber particle to be dispersed.
In the preparation process of the butadiene-styrene rubber particle to be dispersed, high-energy ray source used in cross-linking radiation specifically can be with
Selected from least one of cobalt source, ultraviolet, high-energy electron accelerator, it is preferable that the wavelength in the high-energy ray source is less than 0.1 μ
M, for example, cobalt source.In addition, under normal circumstances, the dosage of irradiation should make the butadiene-styrene rubber particle after rubber latex cross-linking radiation
Gel content reach 60 weight % or more, preferably reach 75 weight % or more, more preferably up to 80 weight % or more.Specifically
Ground, the dosage of irradiation can be 0.1-30Mrad, preferably 0.5-20Mrad.
The butadiene-styrene rubber particle to be dispersed can be commercially available, can also be according to various well known to art technology
Method is prepared.For example, the butadiene-styrene rubber particle to be dispersed can be applicant according to the invention in September 18 in 2000
The international patent application WO01/40356 (priority date on December 3rd, 1999) and applicant of the present invention that day submits are in 2001
The method that the international patent application WO01/98395 (priority date on June 15th, 2000) that on June 15, in submits is provided is prepared into
The butylbenzene powdered rubber particle arrived.By above method preparation without adding interleaving agent after dispersing butadiene-styrene rubber particle and being drying
I.e. free flowable rubber micro mist, wherein each rubber particle is homogeneous, i.e., single particle is all equal in composition
Matter, do not have to find the not homogeneous phenomenons such as layering, split-phase in particle under the observation of existing microtechnic.The powdered rubber is
The partial size of rubber particles is able to fixation and by corresponding rubber latex cross-linking radiation.
In addition, cross-linking aid can not be used in the cross-linking radiation preparation process of the butadiene-styrene rubber particle to be dispersed,
Also cross-linking aid can be used.The cross-linking aid can be selected from simple function group cross-linking aid, two functional group's cross-linking aids, three officials
Cross-linking aid, any one in the above cross-linking aid of four-functional group cross-linking aid and five functional groups can be rolled into a ball.The simple function group
The example of cross-linking aid includes but is not limited to: (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, the contracting of (methyl) acrylic acid
At least one of water glyceride；The example of two functional group cross-linking aid includes but is not limited to: two (first of 1,4- butanediol
Base) acrylate, 1,6-hexylene glycols two (methyl) acrylate, diethylene glycol two (methyl) acrylate, two (first of triethylene glycol
Base) acrylate, neopentyl glycol two (methyl) acrylate, at least one of divinylbenzene；The trifunctional crosslinking
The example of auxiliary agent includes but is not limited to: trimethylolpropane tris (methyl) acrylate and/or pentaerythrite three (methyl) propylene
Acid esters；The example of the four-functional group cross-linking aid includes but is not limited to: pentaerythrite four (methyl) acrylate and/or ethoxy
Change pentaerythrite four (methyl) acrylate；The example of the above cross-linking aid of five functional groups includes but is not limited to: two seasons penta
Tetrol five (methyl) acrylate.Herein, described (methyl) acrylate refers to acrylate or methacrylate.This
A little cross-linking aids can be applied in combination in any way, as long as they facilitate crosslinking under irradiation.In addition, the crosslinking
The additional amount of auxiliary agent is generally the 0.1-10 weight % of dry glue weight in latex, preferably 0.5-9 weight %, more preferably 0.7-
7 weight %.
In addition, the preparation method of lubricant composition provided by the invention can also include by additive and base oil and to
Dispersion butadiene-styrene rubber particle is mixed and is dispersed together.
The type of the base oil and additive has been described herein above, and therefore not to repeat here.
The present invention is not particularly limited the mode of the mixing and redisperse, as long as enabling to the fourth to be dispersed
Benzene rubber particles are effectively dispersed in base oil, to obtain using base oil as continuous phase and be point with butadiene-styrene rubber particle
The lubricant composition of dephasing.A preferred embodiment of the invention, the mixing and the mode dispersed include:
(1) the butadiene-styrene rubber particle to be dispersed is added in the base oil and is mixed by mechanical stirring, so that institute
It states butadiene-styrene rubber particle dispersion to be dispersed or is suspended in the base oil, the composition tentatively dispersed；
(2) composition tentatively dispersed is subjected to redisperse, until the average grain of the butadiene-styrene rubber particle after dispersion
Diameter reach 20-2000nm in the range of, preferably reach 50-1000nm in the range of, in the range of more preferably up to 70-500nm.
Pass through this preferred mixing and enable to butadiene-styrene rubber particle to be dispersed in base oil with initial size by way of dispersing, obtains
The viscosity temperature characteristic of the lubricant composition arrived is more preferably.
According to another preferred method of implementation of the present invention, the preparation method of the lubricant composition further includes step
(3), product step (2) obtained not less than 80 DEG C at a temperature of, preferably not less than 100 DEG C at a temperature of, most preferably
100-200 DEG C at a temperature of place at least 1 hour, preferably place at least 2 hours, more preferably place at least 4 hours, most preferably
Obtained product is subjected to secondary redisperse after placing 4-10 hours, enables to the butadiene-styrene rubber particle and base of crosslinking in this way
Plinth oil sufficiently infiltrates and is swollen, and butadiene-styrene rubber particle with smaller particle size dispersion in base oil, thus obtain glue warm nature
It can better lubricant composition.In addition, in step (3), by the product of step (2) not less than 80 DEG C at a temperature of place to
During 1 hour few, it can cooperate and accomplished continuously or intermittently stir, so that stirring material is heated more evenly.
The mixing of mechanical stirring described in step (1) can carry out in existing various mechanical mixing equipments, for example, can
To be carried out in the mechanical mixing equipments such as high-speed mixer, kneader.The present invention does not have the condition that the mechanical stirring mixes yet
Have and particularly limit, if make the butadiene-styrene rubber particle to be dispersed with cross-linked structure prepared by cross-linking radiation method with
Under the premise of the performance of base oil does not have any variation, make to prepare by cross-linking radiation method with cross-linked structure wait disperse
Butadiene-styrene rubber particle disperses or is suspended in base oil, can know to this those skilled in the art, therefore not to repeat here.
The preparation method of the lubricant composition provided according to the present invention, redisperse and step described in step (2)
(3) the secondary redisperse described in can be squeezed out in homogenizer, bead mill, three-roll grinder, single screw rod each independently
It carries out at least one of machine, multi-screw extruder, kneader, dissolvers and ultrasonic disperser mixing apparatus, preferably exists
It is carried out in homogenizer, three-roll grinder and ultrasonic disperser, these three preferred mixing apparatus have processing output height, mixing
The advantage that effect is good, subsequent cleaning is fairly simple.Most preferably, the secondary redisperse in the redisperse of step (2) and step (3)
It is carried out in homogenizer.In dispersion process, according to different dispersion quality requirements, need by cycles samples cooling, then repeatedly
Repeatedly dispersed by mixing apparatus, until the average grain diameter for the butadiene-styrene rubber particle being dispersed in base oil reaches 20-
It within the scope of 2000nm, preferably reaches within the scope of 50-1000nm, within the scope of more preferably up to 70-500nm.In addition, the present invention is to institute
The condition for stating redisperse and secondary redisperse is not particularly limited, as long as dispersing base oil and butadiene-styrene rubber particle
Performance is not destroyed in journey, and is made the partial size of butadiene-styrene rubber particle reach 20-2000nm, preferably reached 50-1000nm, more
70-500nm is preferably reached, this those skilled in the art can be known, therefore not to repeat here.
It, specifically can be in addition, placement described in step (3) preferably carries out in existing various airtight heating equipment
It is carried out in high temperature oven, vacuum high-temperature baking oven, heating kettle or similar airtight heating container, heat treatment efficiency can be improved in this way,
It is energy saving, while the contact of base oil and butadiene-styrene rubber particle with air (oxygen) can also be reduced, thermal oxide degree is reduced,
Properties of product are made to keep stablizing.
The present invention also provides lubricant compositions prepared by the above method.
The present invention will be described in detail by way of examples below.
(1) raw material used in embodiment and comparative example is as follows:
Mineral base oil, Sinopec production, trade mark Ib150, viscosity at 40 DEG C is 32.6mm2/ s, viscosity index (VI)
It is 90.
Synthetic base oil, Sinopec production, trade mark PAO40, poly alpha olefin, viscosity at 40 DEG C are 40.2mm2/ s,
Viscosity index (VI) is 120.
Butadiene-styrene rubber particle to be dispersed, Sinopec production, trade mark VP101, average grain diameter 100nm, gel content
It for 90 weight %, observes, should be layered in butadiene-styrene rubber particle to be dispersed without discovery, noted phase separation phenomena, by fourth under the microscope
Benzene rubber latex carries out cross-linking radiation method preparation using cobalt source and is obtained by spray drying process.It should butadiene-styrene rubber be dispersed
The infrared spectrum of particle is shown in Fig. 1.It will be seen from figure 1 that 1450cm-1、1700cm-1Etc. be styrol structural unit feature
Absorption peak, 920cm-1、970cm-1Etc. be butadiene structural units characteristic absorption peak.
Peroxide crosslinking butadiene-styrene rubber particle prepare and using spray according to method disclosed in patent CN1840622A
Mist drying means obtains, rubber latex be SBR emulsion (with prepare rubber used by butadiene-styrene rubber particle VP101 to be dispersed
The composition of latex solution is identical), the crosslinking agent used is cumyl peroxide (DCP), the peroxide crosslinking fourth finally obtained
The average grain diameter of benzene rubber particles is 100nm, and gel content is 90 weight %.
(2) the following instrument and equipment of the experimental data in embodiment and comparative example and measuring method measurement:
(1) dynamic viscosity: the lubricating grease group at 40 DEG C and 100 DEG C is tested respectively using NDJ-5S type number rotational viscometer
Close the dynamic viscosity of object, wherein heat using oil bath temperature control.
(2) divide oil mass: being tested according to SH/T 0324-92 " lubricating grease Stencil oil-dividing measuring method (static method) " standard method,
Specifically, sample is placed on 100 mesh copper mesh, stands 24 hours in 100 DEG C of baking ovens and further takes out measurement point oil mass.
(3) coefficient of friction: the interface friction performance of measuring lubricating grease composition, load are on electronic tension tester
0.2kg compares the confficient of static friction μ of aluminium-steel (unlubricated) and aluminium-steel (having lubrication)sWith dynamic friction coefficient μk, wherein it is unlubricated
It indicates uncoated any lubricant composition in aluminium-steel material surface, there is lubrication to indicate to have been coated in aluminium-steel surface accordingly
Lubricant composition.
(4) morphology observation: using rubber particles in Hitachi S4800 scanning electron microscope observation lubricant composition
Pattern.
Embodiment 1
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight mineral base oil Ib150 and 10 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machinery
Stir evenly, then homogenizing circulation five times in three-roll grinder, roller revolving speed is 280 revs/min when homogenizing, when dispersion between roller between
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by three
Roller mill homogenizing circulation five times, roller revolving speed is 280 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is moistened
Grease composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.In addition, the lubricant composition
Microscopic appearance is as shown in Figure 2.Figure it is seen that butadiene-styrene rubber particle can be uniformly dispersed in base oil.
Comparative example 1
The comparative example is for illustrating lubricant composition of reference and preparation method thereof.
Lubricant composition is prepared according to the method for embodiment 1, unlike, it will butadiene-styrene rubber particle VP101 be dispersed
It is substituted with the peroxide crosslinking butadiene-styrene rubber particle of identical weight part, obtains reference lubricant composition, dynamic viscosity is divided
Oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 2
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight mineral base oil Ib150 and 30 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machinery
Stir evenly, then homogenizing circulation five times in three-roll grinder, roller revolving speed is 280 revs/min when homogenizing, when dispersion between roller between
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by three
Roller mill homogenizing circulation five times, roller revolving speed is 280 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is moistened
Grease composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Comparative example 2
The comparative example is for illustrating lubricant composition of reference and preparation method thereof.
Lubricant composition is prepared according to the method for embodiment 2, unlike, it will butadiene-styrene rubber particle VP101 be dispersed
It is substituted with the peroxide crosslinking butadiene-styrene rubber particle of identical weight part, obtains reference lubricant composition, dynamic viscosity is divided
Oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 3
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight mineral base oil Ib150 and 50 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machinery
Stir evenly, then homogenizing circulation five times in three-roll grinder, roller revolving speed is 100 revs/min when homogenizing, when dispersion between roller between
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by three
Roller mill homogenizing circulation five times, roller revolving speed is 100 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is moistened
Grease composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 4
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight mineral base oil Ib150 and 100 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machine
Tool stirs evenly, and then homogenizing circulation five times in three-roll grinder, roller revolving speed is 100 revs/min when homogenizing, when dispersion between roller
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by
Three-roll grinder homogenizing circulation five times, roller revolving speed is 100 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is obtained
Lubricant composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 5
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight synthetic base oil PAO40 and 10 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machinery
Stir evenly, then homogenizing circulation five times in three-roll grinder, roller revolving speed is 280 revs/min when homogenizing, when dispersion between roller between
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by three
Roller mill homogenizing circulation five times, roller revolving speed is 280 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is moistened
Grease composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 6
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight synthetic base oil PAO40 and 50 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machinery
Stir evenly, then homogenizing circulation five times in three-roll grinder, roller revolving speed is 100 revs/min when homogenizing, when dispersion between roller between
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by three
Roller mill homogenizing circulation five times, roller revolving speed is 100 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is moistened
Grease composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 7
The embodiment is for illustrating lubricant composition provided by the invention and preparation method thereof.
By 100 parts by weight synthetic base oil PAO40 and 100 parts by weight butadiene-styrene rubber particle VP101 to be dispersed is mixed and machine
Tool stirs evenly, and then homogenizing circulation five times in three-roll grinder, roller revolving speed is 100 revs/min when homogenizing, when dispersion between roller
Gap is minimal to 10 μm, obtains mixed material.Said mixture material is kept for 4 hours in 150 DEG C of high temperature ovens, again by
Three-roll grinder homogenizing circulation five times, roller revolving speed is 100 revs/min when homogenizing, and clearance between roll is minimal to 5 μm when dispersion, is obtained
Lubricant composition, dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
The dynamic viscosity of 1 lubricant composition of table and divide oil mass
The greasy property of 2 lubricant composition of table
From the results shown in Table 1, with contain the lubricating grease of butadiene-styrene rubber particle obtained by peroxide crosslinking
Composition is compared, the lubricant composition containing the butadiene-styrene rubber particle with cross-linked structure obtained by cross-linking radiation method
In low temperature (40 DEG C) viscosity is lower, and (100 DEG C) viscosity is higher at high temperature, therefore, grease composition provided by the invention
Object has better viscosity temperature characteristic, and temperature limit is wide.
In addition, from the results shown in Table 2, the antiwear and friction reduction property of lubricant composition provided by the invention is very excellent
It is different.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (43)
1. a kind of lubricant composition, which is characterized in that the lubricant composition contains base oil and is dispersed in the basis
The butadiene-styrene rubber particle with cross-linked structure prepared by cross-linking radiation method in oil, the base oil are continuous phase, institute
Stating butadiene-styrene rubber particle is dispersed phase, and the base oil relative to 100 parts by weight, the content of the butadiene-styrene rubber particle are
10-180 parts by weight, wherein the average grain diameter of the butadiene-styrene rubber particle is 20-2000nm, and the butadiene-styrene rubber particle coagulates
Glue content is 60 weight % or more.
2. lubricant composition according to claim 1, wherein relative to the base oil of 100 parts by weight, the fourth
The content of benzene rubber particles is 10-160 parts by weight.
3. lubricant composition according to claim 2, wherein relative to the base oil of 100 parts by weight, the fourth
The content of benzene rubber particles is 10-120 parts by weight.
4. lubricant composition according to claim 1, wherein the average grain diameter of the butadiene-styrene rubber particle is 50-
1000nm。
5. lubricant composition according to claim 4, wherein the average grain diameter of the butadiene-styrene rubber particle is 70-
500nm。
6. lubricant composition according to claim 1, wherein the gel content of the butadiene-styrene rubber particle is 75 weights
Measure % or more.
7. lubricant composition according to claim 6, wherein the gel content of the butadiene-styrene rubber particle is 80 weights
Measure % or more.
8. lubricant composition described in any one of -3 according to claim 1, wherein the butadiene-styrene rubber particle has equal
Phase structure.
9. lubricant composition described in any one of -3 according to claim 1, wherein the base oil is mineral base oil
And/or synthetic base oil.
10. lubricant composition according to claim 9, wherein the mineral base oil is selected from viscosity index (VI) VI≤40
Low-viscosity index mineral base oil, the medium viscosity index mineral base oil of 40 < viscosity index (VI) VI≤90,90 < viscosity index (VI)s
The high viscosity index (HVI) mineral base oil of VI≤120,120 < viscosity index (VI) VI≤140 very high viscosity index (HVI) mineral base oil, viscous
Spend at least one of the superhigh viscosity index mineral base oil of index VI > 140.
11. lubricant composition according to claim 9, wherein the synthetic base oil is selected from synthesis hydrocarbon, alkyl virtue
At least one of hydrocarbon, synthetic ester, polyethers, halogenated hydrocarbons, polysiloxanes and fluorine-containing oil.
12. lubricant composition according to claim 11, wherein it is low that the synthesis hydrocarbon is selected from ethylene low polymer, propylene
At least one of polymers, polybutene, polyisobutene, poly alpha olefin, poly-internal-olefins and halogenated product of above-mentioned synthesis hydrocarbon.
13. lubricant composition according to claim 11, wherein the alkylaromatic hydrocarbon be selected from alkylbenzene, alkylnaphthalene with
And contain at least one of heteroatomic alkylaromatic hydrocarbon.
14. lubricant composition according to claim 11, wherein the synthetic ester is selected from monoesters, dibasic acid esters, polyalcohol
At least one in ester, polymer esters, carbonic ester, phosphate, citrate, esters of silicon acis and olefin-acrylic lipin polymer
Kind.
15. lubricant composition according to claim 11, wherein the polyethers is selected from aliphatic polyether, polyphenylene oxide, gathers
At least one of polythiaether and perfluoroalkyl polyethers.
16. lubricant composition according to claim 11, wherein the polysiloxanes is selected from two polysiloxanes, trimerization
At least one of siloxanes, four polysiloxanes, eight polysiloxanes and the poly- tetrasiloxane of ring.
17. a kind of preparation method of lubricant composition, this method includes preparing by base oil and by cross-linking radiation method
Butadiene-styrene rubber particle to be dispersed with cross-linked structure is mixed and is dispersed, and the base oil relative to 100 parts by weight,
The dosage of the butadiene-styrene rubber particle to be dispersed is 10-180 parts by weight, wherein the butadiene-styrene rubber particle to be dispersed is by putting down
Equal partial size is the butadiene-styrene rubber particle aggregation of 20-2000nm and the rubber particles group formed, the butadiene-styrene rubber particle to be dispersed
Gel content be 60 weight % or more.
18. according to the method for claim 17, wherein the mixing and mode dispersed includes:
(1) the butadiene-styrene rubber particle to be dispersed is added in the base oil and by mechanical stirring mixing so that it is described to
The dispersion of dispersion butadiene-styrene rubber particle is suspended in the base oil, the composition tentatively dispersed；
(2) composition tentatively dispersed is subjected to redisperse, until the average grain diameter of the butadiene-styrene rubber particle after dispersion reaches
To in the range of 20-2000nm.
19. according to the method for claim 18, wherein the composition tentatively dispersed is subjected to redisperse, until point
The average grain diameter of butadiene-styrene rubber particle after dissipating reaches in the range of 50-1000nm.
20. according to the method for claim 19, wherein the composition tentatively dispersed is subjected to redisperse, until point
The average grain diameter of butadiene-styrene rubber particle after dissipating reaches in the range of 70-500nm.
21. according to the method for claim 18, wherein this method further includes step (3), the product that step (2) is obtained
Not less than 80 DEG C at a temperature of place at least 1 hour, obtained product is subjected to secondary redisperse later.
22. according to the method for claim 21, wherein this method further includes step (3), the product that step (2) is obtained
Not less than 100 DEG C at a temperature of place at least 2 hours, obtained product is subjected to secondary redisperse later.
23. according to the method for claim 22, wherein this method further includes step (3), the product that step (2) is obtained
Not less than 100 DEG C at a temperature of place at least 4 hours, obtained product is subjected to secondary redisperse later.
24. according to the method for claim 21, wherein two described in redisperse described in step (2) and step (3)
Secondary redisperse each independently in homogenizer, bead mill, three-roll grinder, single screw extrusion machine, multi-screw extruder, pinch
It is carried out at least one of conjunction machine, dissolvers and ultrasonic disperser mixing apparatus.
25. according to the method for claim 24, wherein two described in redisperse described in step (2) and step (3)
Secondary redisperse each independently at least one of homogenizer, three-roll grinder and ultrasonic disperser mixing apparatus into
Row.
26. according to the method for claim 24, wherein two described in redisperse described in step (2) and step (3)
Secondary redisperse carries out in homogenizer each independently.
27. according to the method for claim 21, wherein be placed in airtight heating equipment and carry out described in step (3).
28. according to the method for claim 17, wherein relative to the base oil of 100 parts by weight, the fourth to be dispersed
The dosage of benzene rubber particles is 10-160 parts by weight.
29. according to the method for claim 28, wherein relative to the base oil of 100 parts by weight, the fourth to be dispersed
The dosage of benzene rubber particles is 10-120 parts by weight.
30. according to the method for claim 17, wherein it is 50- that the butadiene-styrene rubber particle to be dispersed, which is by average grain diameter,
The butadiene-styrene rubber particle aggregation of 1000nm and the rubber particles group formed.
31. according to the method for claim 30, wherein it is 70- that the butadiene-styrene rubber particle to be dispersed, which is by average grain diameter,
The butadiene-styrene rubber particle aggregation of 500nm and the rubber particles group formed.
32. according to the method for claim 17, wherein the gel content of the butadiene-styrene rubber particle to be dispersed is 75 weights
Measure % or more.
33. according to the method for claim 32, wherein the gel content of the butadiene-styrene rubber particle to be dispersed is 80 weights
Measure % or more.
34. method described in any one of 7-29 according to claim 1, wherein the butadiene-styrene rubber particle to be dispersed has
Equal phase structure.
35. method described in any one of 7-29 according to claim 1, wherein the base oil be mineral base oil and/or
Synthetic base oil.
36. according to the method for claim 35, wherein the mineral base oil is selected from the low viscosity of viscosity index (VI) VI≤40
Index mineral base oil, the medium viscosity index mineral base oil of 40 < viscosity index (VI) VI≤90,90 < viscosity index (VI) VI≤120
High viscosity index (HVI) mineral base oil, 120 < viscosity index (VI) VI≤140 very high viscosity index (HVI) mineral base oil, viscosity index (VI) VI
At least one of superhigh viscosity index mineral base oil of > 140.
37. according to the method for claim 35, wherein the synthetic base oil is selected from synthesis hydrocarbon, alkylaromatic hydrocarbon, synthesis
At least one of ester, polyethers, halogenated hydrocarbons, polysiloxanes and fluorine-containing oil.
38. according to the method for claim 37, wherein the synthesis hydrocarbon is selected from ethylene low polymer, propylene oligomer, poly- fourth
Alkene, polyisobutene, poly alpha olefin, poly-internal-olefins and more than synthesize at least one of halogenated product of hydrocarbon.
39. according to the method for claim 37, wherein the alkylaromatic hydrocarbon is selected from alkylbenzene, alkylnaphthalene and containing miscellaneous
At least one of alkylaromatic hydrocarbon of atom.
40. according to the method for claim 37, wherein the synthetic ester is selected from monoesters, dibasic acid esters, polyol ester, polymer
At least one of ester, carbonic ester, phosphate, citrate, esters of silicon acis and olefin-acrylic lipin polymer.
41. according to the method for claim 37, wherein the polyethers be selected from aliphatic polyether, polyphenylene oxide, poly- polythiaether and
At least one of perfluoroalkyl polyethers.
42. according to the method for claim 37, wherein the polysiloxanes is selected from two polysiloxanes, cyclotrisiloxane, four
At least one of polysiloxanes, eight polysiloxanes and the poly- tetrasiloxane of ring.
43. the lubricant composition that the method as described in any one of claim 17-42 is prepared.
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| JP2013227438A (en) * | 2012-04-26 | 2013-11-07 | Mitsui Chemicals Inc | Lubricant composition |
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| CN100528939C (en) * | 2003-09-27 | 2009-08-19 | 莱茵化学莱茵瑙有限公司 | Microgels in non-crosslinkable organic media |
| CN1861673A (en) * | 2005-03-24 | 2006-11-15 | 莱茵化学莱茵瑙有限公司 | Microgels and thickening agents-containing compositions |
| JP2013227438A (en) * | 2012-04-26 | 2013-11-07 | Mitsui Chemicals Inc | Lubricant composition |
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