CN106147952A - 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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- CN106147952A CN106147952A CN201510188843.3A CN201510188843A CN106147952A CN 106147952 A CN106147952 A CN 106147952A CN 201510188843 A CN201510188843 A CN 201510188843A CN 106147952 A CN106147952 A CN 106147952A
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Abstract
The present invention relates to grease field, specifically provide a kind of lubricant composition and preparation method thereof.Described lubricant composition contains silicone oil base oil and the rubber particles with cross-linked structure prepared by cross-linking radiation method being dispersed in described silicone oil base oil, described silicone oil base oil is continuous phase, described rubber particles is dispersion phase, and relative to the described silicone oil base oil of 100 weight portions, the content of described rubber particles is 10-180 weight portion.The lubricant composition that the present invention provides can regulate viscosity effectively along with the change of temperature, temperature limit width, compared with the lubricant composition containing the rubber particles obtained by peroxide crosslinking, its kinematic viscosity when 40 DEG C is relatively low, and kinematic viscosity is higher when 100 DEG C.Additionally, the lubricant composition that the present invention provides also has the antiwear and friction reduction property of excellence.
Description
Technical field
The present invention relates to a kind of lubricant composition, the preparation method of described lubricant composition and by this
The lubricant composition that method prepares.
Background technology
Grease is usually and is dispersed in one or more lube base oils by thickening agent, and through saponification
Reaction and obtain semisolid, kollag.Common grease thickener is divided into soap base, non-soap base
And hydrocarbyl type, soap base thickening agent mostly is soap, such as stearic acid calcium salt, 12-hydroxy stearic acid calcium
Salt, non-soap base thickening agent then includes organic polyureas, inorganic compound etc., and alkyl thickening agent is usually paraffin
Class.The grease using above-mentioned thickening agent to prepare typically can meet commonly used demand, but along with the modern times
Industrial boom, PERFORMANCE OF GREASES is required more and more higher by the high-grade, precision and advanced plant equipment continued to bring out, and needs
Meet broader use temperature range, more high shear rates, bigger load-up condition etc..Thus, novel
The exploitation of grease thickener or compound additive is in widespread attention.
Nano material refers to the solid material being made up of the ultrafine dust being smaller in size than 100 nanometers.Due to it
There is the features such as specific surface area is big, good dispersion, easy-sintering, hardness are big, and there is good antifriction
Compressive property and nanoparticle have certain repair to wear surface, and therefore, it can improve lube system
The service life of system.Additionally, just because of use the lubricating oil prepared of nano material additive, grease anti-
Mirror good tribological property, utilize nano material additive to prepare high-performance grease and have well
Prospect.
Prior art has had the report of a large amount of application about inorganic nano-particle in grease field
Road.Such as, CN104046407A discloses a kind of lubricating oil (fat) antiwear and antifriction compound additive, its
Consist of oxide nano rare earth Coated white mica, add base oil or lubrication with the ratio of 0.5-3%
In fat, i.e. can significantly reduce coefficient of friction, reduce wear scar diameter.CN104031717A discloses one
Planting aluminium nitride and copper mixing nanometer lubricating grease additive, this compound additive particle size range is
50-200nm.The grease using this additive to prepare has good antiwear and friction reduction property, and coefficient of friction can
Reduce 23.6-15.8%, 6-7 times can be extended friction durability.CN103525513A discloses a kind of high temperature
Lubricant composition and preparation method, wherein use boron nitride micropowder as thickening agent, with graphite microparticles and
MCA (melamine cyanurate) is as extreme pressure anti-wear additives, and the grease of preparation has the high temperatures of excellence
Energy, extreme pressure and antiwear behavior and oxidation stability.Although by adding the grease that inorganic nano material obtains
Compositions has high temperature resistant, pressure, the anti-wear performance of excellence, but life-time service easily sinters and remains in
Friction surface, affects lubricant effect.Additionally, most inorganic nano additives need to join with conventional thickening agent
Closing and use, the PERFORMANCE OF GREASES being prepared out can be improved, and therefore adds manufacture and uses
Cost.
Additionally, in addition to inorganic nano-particle, also have some to lead at grease about organic fine particles gel
The report of the application in territory.Such as, the patent of Rhein Chemie Rheinau GmbH's application
CN1856527A, CN1840622A and CN1861673A disclose a kind of non-crosslinkable organic
Micro gel in medium and the micro gel of crosslinking are for the temperature of modified non-crosslinked organic media
Degree relies on the purposes of performance.But, this several patents application is pointed out bar none, described micro gel
Be all use chemical crosslinking mode (such as, by with polyfunctional compound's crosslinking copolymerization or passed through
Oxide cross-links) micro gel for preparing rather than the micro gel with high-energy radiation crosslinking.On
State the micro gel that patent application thinks that high-energy radiation cross-links to be actually unable in preparing on an industrial scale, radiation
Property cobalt source the using with serious safety problem, and by the micro gel of crosslinking with radiation of high-energy radiation
Time in plastic matrix, can occur to tear effect between substrate and dispersion phase, thus compromise and contain
There are the mechanical performance of the plastics of this micro gel, swelling behavior, stress corrosion cracking performance etc..But,
Rhein Chemie Rheinau GmbH application patent CN1856527A, CN1840622A and
The viscosity temperature characteristic of the lubricant composition disclosed in CN1861673A is poor, gluing of this lubricant composition
Spend along with the reduction of temperature can be increased dramatically, and along with the rising of temperature can strongly reduce, but at low temperature
Lower viscosity is excessive or the at high temperature too small application the most not utilizing lubricant composition of viscosity, and this will be very
The application of this lubricant composition is limited in big degree.Therefore, need exploitation one badly and have the most viscous
The lubricant composition of warm nature energy.
Summary of the invention
The invention aims to the defect overcoming existing lubricant composition viscosity temperature characteristic poor, and
There is provided a kind of and there is the lubricant composition of excellent viscosity temperature characteristic, the preparation method of a kind of lubricant composition
And the lubricant composition prepared by the method.
The present inventor finds after further investigation, Rhein Chemie Rheinau GmbH's application
Grease group disclosed in above-mentioned several patents CN1856527A, CN1840622A and CN1861673A
Dispersion phase in compound is to use polyfunctional compound or peroxide to be obtained by chemical crosslinking mode
Micro gel, although the lubricant composition containing this microgel particle can reduce organic to a certain extent
The coefficient of friction of medium, but the viscosity of these lubricant compositions is influenced by temperature relatively big, and temperature is too
High (viscosity is the least) or the lowest (viscosity is the biggest) all can limit the use of this lubricant composition, is suitable for
Temperature range is narrower.And the rubber particles with cross-linked structure prepared by cross-linking radiation method with pass through
Polyfunctional compound or peroxide is used to carry out the rubber grain with cross-linked structure of chemical crosslinking preparation
Son has diverse microstructure.When the dispersion phase in lubricant composition is by cross-linking radiation side
When prepared by method has the rubber particles of cross-linked structure, corresponding lubricant composition has good gluing
Warm nature energy, it is possible to very well regulate viscosity along with the change of temperature, reduces low temperature viscosity and improves height
Temperature viscosity, therefore, it can make up the impact caused viscosity due to the change of temperature to a great extent.
Additionally, high-energy radiation the most very cleaning, safety and the efficient energy, the most by a lot of flourishing
Country is widely used for the fields such as health care, food processing, commercial production, is to use chemistry to hand on the contrary
There is some very important problems, as the highest in production efficiency, peroxide in linked method (peroxide)
Residual and the environmental pollution etc. that may cause, these all can limit its application.
Additionally, due to silicone oil base oil is basically identical with the chemical constitution of rubber particles, according to structure phase
Like compatibility principle, both are fully compatible, and rubber particles will significantly improve the limit of silicone oil base oil
Boundary's greasy property, and improve viscosity temperature characteristic and antiwear and friction reduction property further, this is for promoting silicone oil basis
The greasy property of oil, widen the equal important in inhibiting of range of application of silicone oil base oil.
Based on above-mentioned discovery, the present inventor completes the present invention.
Specifically, the invention provides a kind of lubricant composition, wherein, described lubricant composition contains
Have silicone oil base oil and be dispersed in described silicone oil base oil by prepared by cross-linking radiation method having
The rubber particles of cross-linked structure, described silicone oil base oil is continuous phase, and described rubber particles is dispersion
Phase, and relative to the described silicone oil base oil of 100 weight portions, the content of described rubber particles is 10-180
Weight portion.
Present invention also offers the preparation method of a kind of lubricant composition, the method by silicone oil base oil and
By cross-linking radiation method prepare there is cross-linked structure treat that dispersed silicon rubber particles carries out mixing and dividing
Dissipate, and relative to the described silicone oil base oil of 100 weight portions, described in treat the consumption of dispersed silicon rubber particles
For 10-180 weight portion.
Present invention also offers the lubricant composition prepared by said method.
The lubricant composition that the present invention provides can regulate viscosity effectively along with the change of temperature, viscous temperature
Excellent performance, rubber particles therein disperses up to nanoscale, and makes silicone oil base oil keep stable
Not easily run off, therefore, the temperature limit width of this lubricant composition, under high temperature high shear still
Viscosity higher can be kept, it is possible to meet the lubricating requirement of 100 DEG C of temperature occasions used above, be suitable for institute
There is the field that the field of grease applications, especially temperature are higher, antiwear and antifriction requirement is high, such as heavy load
Machinery, the lubrication occasion running equipment steady in a long-term, and can also compounding with other lubricating additives make
With, prepare special lubricant composition.Additionally, the wear-resistant of lubricant composition that the present invention provides subtracts
Rub excellent performance, and the scattered rubber particles of nanoscale both can improve the wearability of lubricant composition,
Similar micro-bearing effect can be played again, thus increase rolling friction and reduce interface friction force.
Owing to cross-linking radiation makes the special construction that rubber particles had, the grease composition that the present invention provides
The ageing-resistant performance of thing is excellent, and the most easy to change, the most this lubricant composition can be as excellent performance
Grease use, be especially applicable to the viscosity temperature characteristic to lubricating oil system, ageing properties and frictional property
Higher field can be required.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The lubricant composition that the present invention provides contains silicone oil base oil and is dispersed in described silicone oil base oil
In the rubber particles with cross-linked structure prepared by cross-linking radiation method, described silicone oil base oil
For continuous phase, described rubber particles is dispersion phase, and relative to the described silicone oil basis of 100 weight portions
Oil, the content of described rubber particles is 10-180 weight portion.Wherein, described rubber particles is at silicon
In stable dispersion state in oil base oil.
The lubricant composition provided according to the present invention, as discussed previously with respect to described in 100 weight portions
Silicone oil base oil, the content of described rubber particles is 10-180 weight portion, but so that Silicon-oil-based
Plinth oil and rubber particles play more preferable coordinated effect, and and then make the lubricant composition obtained
There is more preferable viscosity temperature characteristic, it is preferable that relative to the described silicone oil base oil of 100 weight portions, described
The content of rubber particles is 10-160 weight portion, more preferably 10-120 weight portion.
The lubricant composition provided according to the present invention, it is preferable that the mean diameter of described rubber particles
For 20-2000nm, more preferably 50-1000nm, particularly preferred 70-500nm.When by described silicone rubber
When the mean diameter of particle controls within the above range, it is possible to more effectively regulation lubricant composition is viscous
Degree, is suitable for broader use temperature range.
The lubricant composition provided according to the present invention, it is preferable that the gel content of described rubber particles
It is more than 60 weight %, more than more preferably 75 weight %, more than particularly preferably 80 weight %.When
When the gel content of described rubber particles is controlled within the above range, it is possible to along with temperature change more
Effectively regulate the viscosity of lubricant composition, be suitable for broader use temperature range.In the present invention,
Described gel content be this area for characterizing a kind of Common Parameters of rubber cross degree, its according to
Method disclosed in CN1402752A records.
The kind of described rubber particles is not particularly limited by the present invention, for example, it is possible to selected from methyl
Rubber particles, ethyl rubber particles, hydroxyl rubber particles, hydrogeneous methyl silicone rubber particle, first
Base vinylsiloxane rubber particle, methyl vinyl phenyl rubber particles, methyl ethylene trifluoro propyl silicon
Rubber particles, phenylene silicone rubber particle, phenylene ether base rubber particles, nitrile silicone rubber particle, silicon boron
At least one in rubber particles and fluorosioloxane rubber particle.
Additionally, the rubber particles that the present invention provides is preferably equal phase structure.In the present invention, described " equal
Phase structure " refer to observe under existing microtechnique, do not find layering, split-phase etc. in rubber particles
The most homogeneous phenomenon.
The lubricant composition provided according to the present invention, the high-energy ray source used by described cross-linking radiation is concrete
At least one in cobalt source, ultraviolet, high-energy electron accelerator can be selected from, it is preferable that described high energy is penetrated
The wavelength of line source is less than 0.1 μm, for example, cobalt source.Additionally, generally, the dosage of irradiation should make
The gel content obtaining the rubber particles after rubber latex cross-linking radiation reaches more than 60 weight %, preferably
Reach more than 75 weight %, more than more preferably up to 80 weight %.Specifically, the dosage of irradiation is permissible
For 0.1-30Mrad, preferably 0.5-20Mrad.
The kind of described silicone oil base oil is not particularly limited by the present invention, can be unmodified silicone oil,
Can also be unmodified silicone oil, it is also possible to for the mixture of modified silicon oil Yu unmodified silicone oil.
Specifically, the example of described unmodified silicone oil includes but not limited to: methyl-silicone oil, ethyl silicon oil,
Phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, methyl ethoxy silicon
Oil, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil,
Hydroxyl hydrogen silicone oil and containing at least one in nitrile silicone, preferably methyl-silicone oil.
Described unmodified silicone oil refer to use some modified group to substitute the part methyl group in silicone oil and
The modified silicon oil obtained, modified silicon oil is not only a kind of extraordinary silicon with common dimethicone speciality
Oil, and according to import different modified groups, silicone oil is endowed multiple new characteristic, as water solublity,
The compatibility or with the reactivity of various other materials, coating etc..The example of described modified silicon oil include but
Be not limited to: amino-modified silicone oil, epoxy-modified silicone oil, polyether modified silicon oil, Carboxyl Modified Polydimethylsiloxane,
Alcoholic extract hydroxyl group modified silicon oil, phenolic group modified silicone oil, sulfhydryl modified silicone oil, polysiloxane-polyethers are embedding
Section modification by copolymerization silicone oil, alkyl and polyether modified silicon oil, alkyl ether polyether silicone oil, epoxy radicals are polyether-modified
Silicone oil, amino-polyether block silicone oil, glycerol ether silicone oil, phosphoric acid cruel base silicone oil, glycosyl polyethers silicone oil and
At least one in Radix Betae base silicone oil.
Additionally, the lubricant composition that the present invention provides can also be containing conventional additive.Described interpolation
The kind of agent includes but not limited to: age resistor, antiwear additive, antilubricant, antioxidant, anti-foaming agent, antirust
Agent, detersive, dispersant, pigment, extreme pressure composition, friction protection compositions, detersive, coupling
At least one in agent etc..The consumption of described additive can be the conventional selection of this area, to this ability
Field technique personnel all can know, therefore not to repeat here.
The preparation method of the lubricant composition that the present invention provides includes silicone oil base oil and passes through irradiation
Cross-linked structure that prepared by cross-linking method have treat that dispersed silicon rubber particles mixes and disperses, and relatively
In the described silicone oil base oil of 100 weight portions, described in treat that the consumption of dispersed silicon rubber particles is 10-180
Weight portion.
According to the preparation method of the lubricant composition that the present invention provides, as discussed previously with respect to 100 weights
The described silicone oil base oil of amount part, described in treat that the consumption of dispersed silicon rubber particles is 10-180 weight portion,
But so that silicone oil base oil and treat that dispersed silicon rubber particles plays more preferable coordinated effect, go forward side by side
And make the lubricant composition obtained have more preferable viscosity temperature characteristic, it is preferable that relative to 100 weight portions
Described silicone oil base oil, described in treat that the consumption of dispersed silicon rubber particles is 10-160 weight portion, especially
It is preferably 10-120 weight portion.
The preparation method of lubricant composition provided according to the present invention, it is preferable that described in treat dispersed silicon rubber
Micelle is for being 20-2000nm, more preferably 50-1000nm by mean diameter, be particularly preferably
The rubber particles group that the rubber particles of 70-500nm is reunited and formed.When treating dispersed silicon rubber by described
After particle is dispersed in silicone oil base oil, the rubber particles of reunion can be disperseed well, from
And with 20-2000nm, preferably with 50-1000nm, more preferably with the average particle size distribution of 70-500nm
In silicone oil base oil.Treat described in additionally, that the mean diameter of dispersed silicon rubber particles is preferably
20-2000nm, more preferably 50-1000nm, particularly preferably 70-500nm.
The preparation method of lubricant composition provided according to the present invention, it is preferable that described in treat dispersed silicon rubber
The gel content of micelle is more than 60 weight %, more than more preferably 75 weight %, particularly preferably
More than 80 weight %.When the described gel content treating dispersed silicon rubber particles is controlled within the above range
Time, it is possible to along with the change of temperature more effectively regulates the viscosity of lubricant composition, it is suitable for broader
Use temperature range.
Described treat that dispersed silicon rubber particles preferably has equal phase structure.In the present invention, described " homogeneously tie
Structure " refer to observe under existing microtechnique, do not find layering, split-phase in treating dispersed silicon rubber particles
Deng the most homogeneous phenomenon.
Described treat that dispersed silicon rubber particles can be selected from methyl silicone rubber particle, ethyl rubber particles, hydroxyl
Base rubber particles, hydrogeneous methyl silicone rubber particle, methyl vinyl silicone rubber particle, methyl ethylene
Phenyl siloxane rubber particle, methyl ethylene trifluoro propyl rubber particles, phenylene silicone rubber particle, Asia
In phenylate base rubber particles, nitrile silicone rubber particle, silicon boron rubber particles and fluorosioloxane rubber particle at least
A kind of.
High-energy ray source tool in the described preparation process treating dispersed silicon rubber particles, used by cross-linking radiation
Body can be selected from least one in cobalt source, ultraviolet, high-energy electron accelerator, it is preferable that described high energy
Radiogenic wavelength is less than 0.1 μm, for example, cobalt source.Additionally, generally, the dosage of irradiation should
The gel content making the rubber particles after rubber latex cross-linking radiation reaches more than 60 weight %, excellent
Choosing reaches more than 75 weight %, more than more preferably up to 80 weight %.Specifically, the dosage of irradiation can
Think 0.1-30Mrad, preferably 0.5-20Mrad.
Described treat that dispersed silicon rubber particles can be commercially available, it is also possible to known in art technology
Various methods prepare.Such as, treat described in that dispersed silicon rubber particles can be the Shen according to the present invention
Ask someone the international patent application WO01/40356 (priority date 1999 submitted for 18th in JIUYUE in 2000
On December 3) and the international monopoly Shen submitted June 15 calendar year 2001 of applicant of the present invention
Please the powder for preparing of the method that provides of WO01/98395 (priority date on June 15th, 2000)
Rubber particles.Treat that dispersed silicon rubber particles is dried without with interleaving agent by prepared by said method
The most free flowable rubber micropowder, each of which rubber particle is all homogeneous, and the most single microgranule exists
It is all homogenizing on composition, under the observation of existing microtechnique, in microgranule, does not find layering, split-phase etc.
The most homogeneous phenomenon.This powdered rubber be by by corresponding rubber latex cross-linking radiation by rubber particles
Particle diameter fixed.
Additionally, in the described cross-linking radiation preparation process treating dispersed silicon rubber particles, friendship can not be used
Connection auxiliary agent, it is possible to use crosslinking coagent.Described crosslinking coagent can be selected from simple function group crosslinking coagent,
More than two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent and five functional groups
Any one in crosslinking coagent.The example of described simple function group crosslinking coagent includes but not limited to: (first
Base) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, in (methyl) glycidyl acrylate extremely
Few one；The example of described two functional group's crosslinking coagents includes but not limited to: 1,4-butanediol two (methyl)
Acrylate, 1,6-HD two (methyl) acrylate, diethylene glycol two (methyl) acrylate,
Triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, divinylbenzene
In at least one；The example of described trifunctional crosslinking coagent includes but not limited to: trimethylolpropane
Three (methyl) acrylate and/or tetramethylolmethane three (methyl) acrylate；Described four-functional group cross-links
The example of auxiliary agent includes but not limited to: tetramethylolmethane four (methyl) acrylate and/or ethoxyquin Ji Wusi
Alcohol four (methyl) acrylate；The example of the described five above crosslinking coagents of functional group includes but not limited to:
Dipentaerythritol five (methyl) acrylate.In this article, described (methyl) acrylate refers to third
Olefin(e) acid ester or methacrylate.These crosslinking coagents can be applied in combination in any way, as long as they
Contribute to cross-linking under irradiation.Additionally, the addition of described crosslinking coagent is generally dry glue in latex
0.1-10 weight % of weight, preferably 0.5-9 weight %, more preferably 0.7-7 weight %.
Additionally, the preparation method of the lubricant composition of present invention offer can also include additive and silicon
Oil base oil and treat that dispersed silicon rubber particles together mixes and disperses.
The kind of described silicone oil base oil and additive has been described above being described, and does not goes to live in the household of one's in-laws on getting married at this
State.
The mode of described mixing and redispersion is not particularly limited by the present invention, as long as enabling to described
Treat that dispersed silicon rubber particles is effectively dispersed in silicone oil base oil thus obtains using silicone oil base oil as even
The continuous lubricant composition mutually and with rubber particles as dispersion phase.One according to the present invention is excellent
Embodiment, described mixing scattered mode is selected to include:
(1) treat that dispersed silicon rubber particles adds in described silicone oil base oil and passes through mechanical agitation by described
Mixing so that described in treat dispersed silicon rubber particles dispersion or be suspended in described silicone oil base oil, at the beginning of obtaining
Walk scattered compositions；
(2) described preliminary scattered compositions is carried out redispersion, until the rubber particles after Fen San
Mean diameter reach in the range of 20-2000nm, preferably reach in the range of 50-1000nm, more excellent
Choosing reaches in the range of 70-500nm.Silicon is enabled to by this preferred mixing scattered mode
Rubber particles is dispersed in silicone oil base oil with initial size, the viscosity temperature characteristic of the lubricant composition obtained
More preferably.
According to the another kind of preferred implementation of the present invention, the preparation method of described lubricant composition is also wrapped
Including step (3), product step (2) obtained is being not less than at a temperature of 80 DEG C, preferably the lowest
At a temperature of 100 DEG C, more preferably place at 100-200 DEG C at least 1 hour, preferably place at least 2
Hour, more preferably place at least 4 hours, after most preferably placing 4-10 hour, the product obtained is entered
Row secondary redispersion, the rubber particles and the silicone oil base oil that so enable to crosslinking fully infiltrate and molten
Swollen, and rubber particles with less particle size dispersion in silicone oil base oil, thus obtain viscosity temperature characteristic
Preferably lubricant composition.Additionally, in step (3), the product of step (2) is being not less than 80
Place at least 1 hour period at a temperature of DEG C, can coordinate and accomplished continuously or intermittently stir, so that stirring material
It is heated evenly.
Mechanical agitation mixing described in step (1) can be entered in existing various mechanical mixing equipments
OK, for example, it is possible to carry out in the mechanical mixing equipment such as homogenizer, kneader.The present invention is to institute
The condition stating mechanical agitation mixing is also not particularly limited, as long as being prepared by cross-linking radiation method making
The performance treating dispersed silicon rubber particles and silicone oil base oil with cross-linked structure there is no any change
Under premise, make by cross-linking radiation method prepare there is cross-linked structure treat that dispersed silicon rubber particles disperses
Or be suspended in silicone oil base oil, these those skilled in the art all can be known, therefore not to repeat here.
According to the preparation method of the lubricant composition that the present invention provides, dividing again described in step (2)
Dissipate and the secondary redispersion described in step (3) can grind at homogenizer, bead independently of one another
Machine, three-roll grinder, single screw extrusion machine, multi-screw extruder, kneader, dissolvers and ultrasound wave
At least one mixing apparatus in disperser is carried out, preferably at homogenizer, three-roll grinder and ultrasound wave
Carrying out in disperser, the preferred mixing apparatus of these three has processing output height, good mixing effect, follow-up
Clean fairly simple advantage.Most preferably, the redispersion in step (2) and two in step (3)
Secondary being redispersed in homogenizer is carried out.In dispersive process, according to different dust dispersion quality requirements, need
Cycles samples is cooled down, then iterates through mixing apparatus and repeatedly disperse, until being dispersed in silicone oil basis
In the range of the mean diameter of the rubber particles in oil reaches 20-2000nm, preferably reach 50-1000nm
In the range of, in the range of more preferably up to 70-500nm.Additionally, the present invention is to described redispersion and secondary
The condition of redispersion is not particularly limited, as long as making silicone oil base oil and rubber particles disperse
In journey, performance is not destroyed, and makes the particle diameter of rubber particles reach 20-2000nm, preferably reach
These those skilled in the art all can be known by 50-1000nm, more preferably up to 70-500nm,
This does not repeats.
Additionally, the placement described in step (3) is preferably carried out in existing various airtight firing equipments,
Specifically can carry out in high temperature oven, vacuum high-temperature baking oven, heating kettle or similar airtight adding in heat container,
So can improve heat treatment efficiency, save the energy, silicone oil base oil and silicone rubber can also be reduced simultaneously
Particle contacts with air (oxygen), reduces thermal oxide degree, makes properties of product keep stable.
Present invention also offers the lubricant composition prepared by said method.
Hereinafter will be described the present invention by embodiment.
(1) raw material used in embodiment and comparative example is as follows:
Methyl-silicone oil A, Japan XINYUE produces, and the trade mark is 201-50, and viscosity (25 DEG C) is 50cp
(1cp=1mPa s).
Methyl-silicone oil B, Japan XINYUE produces, and the trade mark is 201-350, and viscosity (25 DEG C) is 350cp.
Treating dispersed silicon rubber particles, Sinopec produces, and the trade mark is VP601, mean diameter 100nm,
Gel content 88 weight %, examines under a microscope, and this does not find to divide in treating dispersed silicon rubber particles
Layer, noted phase separation phenomena, it is carried out cross-linking radiation method by methyl vinyl silicone rubber emulsion employing cobalt source and prepares
And be dried to obtain by spray drying method.
Peroxide crosslinking rubber particles is prepared according to method disclosed in patent CN1840622A
And using spray drying process to obtain, rubber latex is that methyl vinyl silicone rubber emulsion is (with preparation respectively
Treat that the composition of the rubber latex that dispersed silicon rubber particles VP601 used is identical), the cross-linking agent of employing is
Cumyl peroxide (DCP), the mean diameter of the final peroxide crosslinking rubber particles obtained is
100nm, gel content is 88 weight %.
(2) following instrument and equipment and the assay method of the experimental data in embodiment and comparative example measures:
(1) dynamic viscosity: use NDJ-5S type numeral rotating cylinder viscometer to test 40 DEG C and 100 respectively
The dynamic viscosity of the lubricant composition at DEG C, wherein, uses the heating of oil bath temperature control.
(2) oil mass is divided: according to SH/T 0324-92 " grease Stencil oil-dividing algoscopy (static method) "
Standard method is tested, and specifically, is positioned over by sample on 100 mesh copper mesh, stands in 100 DEG C of baking ovens
Within 24 hours, further take out measurement point oil mass.
(3) coefficient of friction: the interface friction of measuring lubricating grease compositions on electronic tension tester
Can, load is 0.2kg, compares aluminum-steel (unlubricated) and the confficient of static friction μ of aluminum-steel (having lubrication)s
With coefficient of kinetic friction μk, wherein, uncoated any grease group in unlubricated expression aluminum-steel material surface
Compound, has lubrication to represent on aluminum-steel surface and has been coated with corresponding lubricant composition.
Embodiment 1
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil A and 10 weight portions are treated, and dispersed silicon rubber particles VP601 mixes also
Mechanical agitation is uniform, and then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 280 turns
/ minute, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.By said mixture material 150
Keeping 4 hours in DEG C high temperature oven, circulate five times again by three-roll grinder homogenizing, during homogenizing, roller turns
Speed is 280 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition, and it moves
Power viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Comparative example 1
This comparative example is for lubricant composition that reference is described and preparation method thereof.
Prepare lubricant composition according to the method for embodiment 1, except for the difference that, dispersed silicon rubber grain will be treated
The peroxide crosslinking rubber particles of sub-VP601 identical weight part substitutes, and obtains reference grease group
Compound, its dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 2
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil A and 30 weight portions are treated, and dispersed silicon rubber particles VP601 mixes also
Mechanical agitation is uniform, and then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 280 turns
/ minute, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.By said mixture material 150
Keeping 4 hours in DEG C high temperature oven, circulate five times again by three-roll grinder homogenizing, during homogenizing, roller turns
Speed is 280 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition, and it moves
Power viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 3
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil A and 50 weight portions are treated, and dispersed silicon rubber particles VP601 mixes also
Mechanical agitation is uniform, and then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 100 turns
/ minute, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.By said mixture material 150
Keeping 4 hours in DEG C high temperature oven, circulate five times again by three-roll grinder homogenizing, during homogenizing, roller turns
Speed is 100 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition, and it moves
Power viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 4
Lubricant oil composite that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil A and 100 weight portions are treated that dispersed silicon rubber particles VP601 mixes
And mechanical agitation is uniform, then in high pressure homogenizer, homogenizing circulates five times, and homogenization pressure is 100MPa,
The temperature of material all is controlled, less than 70 DEG C, to obtain mixture by every circulation primary by water-bath cooling
Material.Said mixture material is kept 4 hours in 150 DEG C of high temperature ovens, then by high pressure homogenizer the
Secondary homogenizing circulates five times, and homogenization pressures is 100MPa, obtains lubricant oil composite, its dynamic viscosity,
Point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 5
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil B and 10 weight portions are treated, and dispersed silicon rubber particles VP601 mixes also
Mechanical agitation is uniform, and then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 280 turns
/ minute, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.By said mixture material 150
Keeping 4 hours in DEG C high temperature oven, circulate five times again by three-roll grinder homogenizing, during homogenizing, roller turns
Speed is 280 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition, and it moves
Power viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 6
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil B and 50 weight portions are treated, and dispersed silicon rubber particles VP601 mixes also
Mechanical agitation is uniform, and then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 100 turns
/ minute, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.By said mixture material 150
Keeping 4 hours in DEG C high temperature oven, circulate five times again by three-roll grinder homogenizing, during homogenizing, roller turns
Speed is 100 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition, and it moves
Power viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
Embodiment 7
Lubricant composition that this embodiment provides for the present invention is described and preparation method thereof.
100 weight portion methyl-silicone oil B and 100 weight portions are treated that dispersed silicon rubber particles VP601 mixes
And mechanical agitation is uniform, then in three-roll grinder, homogenizing circulates five times, and during homogenizing, roller rotating speed is 100
Rev/min, during dispersion, clearance between roll is minimal to 10 μm, obtains mixed material.Said mixture material is existed
150 DEG C of high temperature ovens keep 4 hours, circulates five times again by three-roll grinder homogenizing, during homogenizing
Roller rotating speed is 100 revs/min, and during dispersion, clearance between roll is minimal to 5 μm, obtains lubricant composition,
Its dynamic viscosity, point oil mass and greasy property are shown in Tables 1 and 2 respectively.
The dynamic viscosity of table 1 lubricant composition and point oil mass
The greasy property of table 2 lubricant composition
From the results shown in Table 1, with containing the rubber particles obtained by peroxide crosslinking
Lubricant composition is compared, containing the silicone rubber grain with cross-linked structure obtained by cross-linking radiation method
Son lubricant composition (40 DEG C) viscosity when low temperature lower, and when high temperature (100 DEG C) viscosity
Higher, therefore, the lubricant composition that the present invention provides has more preferable viscosity temperature characteristic, applies temperature model
Enclose width.
Additionally, from the results shown in Table 2, the antiwear and antifriction of the lubricant composition that the present invention provides
Performance is the most excellent.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a lubricant composition, it is characterized in that, described lubricant composition contains base oil and the rubber particles with cross-linked structure prepared by cross-linking radiation method being dispersed in described base oil, described silicone oil base oil is continuous phase, described rubber particles is dispersion phase, and relative to the described silicone oil base oil of 100 weight portions, the content of described rubber particles is 10-180 weight portion.
Lubricant composition the most according to claim 1, wherein, relative to the described silicone oil base oil of 100 weight portions, the content of described rubber particles is 10-160 weight portion, preferably 10-120 weight portion.
Lubricant composition the most according to claim 1 and 2, wherein, the mean diameter of described rubber particles is 20-2000nm, preferably 50-1000nm, more preferably 70-500nm.
Lubricant composition the most according to claim 1 and 2, wherein, the gel content of described rubber particles is more than 60 weight %, more than preferably 75 weight %, more than more preferably 80 weight %.
Lubricant composition the most according to claim 1 and 2, wherein, described rubber particles has equal phase structure.
Lubricant composition the most according to claim 1 and 2, wherein, at least one in methyl silicone rubber particle, ethyl rubber particles, hydroxyl rubber particles, hydrogeneous methyl silicone rubber particle, methyl vinyl silicone rubber particle, methyl vinyl phenyl rubber particles, methyl ethylene trifluoro propyl rubber particles, phenylene silicone rubber particle, phenylene ether base rubber particles, nitrile silicone rubber particle, silicon boron rubber particles and fluorosioloxane rubber particle of described rubber particles.
Lubricant composition the most according to claim 1 and 2, wherein, described silicone oil base oil is unmodified silicone oil and/or modified silicon oil；
Preferably, described unmodified silicone oil is selected from methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil and at least one contained in nitrile silicone；
Preferably, described modified silicon oil is selected from amino-modified silicone oil, epoxy-modified silicone oil, polyether modified silicon oil, Carboxyl Modified Polydimethylsiloxane, alcoholic extract hydroxyl group modified silicon oil, phenolic group modified silicone oil, sulfhydryl modified silicone oil, polysiloxane-polyether block modification by copolymerization silicone oil, alkyl and at least one in polyether modified silicon oil, alkyl ether polyether silicone oil, epoxy radicals polyether modified silicon oil, amino-polyether block silicone oil, glycerol ether silicone oil, phosphoric acid cruel base silicone oil, glycosyl polyethers silicone oil and Radix Betae base silicone oil.
8. the preparation method of a lubricant composition, the method include by silicone oil base oil and by cross-linking radiation method prepare there is cross-linked structure treat that dispersed silicon rubber particles mixes and disperses, and relative to the described silicone oil base oil of 100 weight portions, described in treat that the consumption of dispersed silicon rubber particles is 10-180 weight portion.
Method the most according to claim 8, wherein, described mixing scattered mode include:
(1) treat that dispersed silicon rubber particles adds in described silicone oil base oil and mixes by mechanical agitation by described so that described in treat that dispersed silicon rubber particles disperses or is suspended in described silicone oil base oil, obtain preliminary scattered compositions；
(2) described preliminary scattered compositions is carried out redispersion, until the mean diameter of the rubber particles after Fen San reaches in the range of 20-2000nm, preferably reaches in the range of 50-1000nm, in the range of more preferably up to 70-500nm.
Method the most according to claim 9, wherein, the method also includes step (3), product step (2) obtained is being not less than at a temperature of 80 DEG C, preferably being not less than at a temperature of 100 DEG C place at least 1 hour, preferably place at least 2 hours, more preferably place at least 4 hours, afterwards the product obtained is carried out secondary redispersion.
11. methods according to claim 10, wherein, redispersion described in step (2) and the secondary redispersion described in step (3) at least one mixing apparatus in homogenizer, bead mill, three-roll grinder, single screw extrusion machine, multi-screw extruder, kneader, dissolvers and ultrasonic disperser independently of one another is carried out, preferably at least one mixing apparatus in homogenizer, three-roll grinder and ultrasonic disperser is carried out, more preferably carry out in homogenizer；Preferably, being placed in airtight firing equipment described in step (3) is carried out.
12. methods according to claim 8, wherein, relative to the described silicone oil base oil of 100 weight portions, described in treat that the consumption of dispersed silicon rubber particles is 10-160 weight portion, preferably 10-120 weight portion.
13. methods described in any one in-12 according to Claim 8, wherein, described in treat dispersed silicon rubber particles be by mean diameter be 20-2000nm, be preferably 50-1000nm, the rubber particles of more preferably 70-500nm reunites the rubber particles group formed.
14. methods described in any one in-12 according to Claim 8, wherein, described in treat that the gel content of dispersed silicon rubber particles is more than 60 weight %, more than preferably 75 weight %, more than more preferably 80 weight %.
15. methods described in any one in-12 according to Claim 8, wherein, described in treat that dispersed silicon rubber particles has equal phase structure.
16. methods described in any one in-12 according to Claim 8, wherein, at least one in methyl silicone rubber particle, ethyl rubber particles, hydroxyl rubber particles, hydrogeneous methyl silicone rubber particle, methyl vinyl silicone rubber particle, methyl vinyl phenyl rubber particles, methyl ethylene trifluoro propyl rubber particles, phenylene silicone rubber particle, phenylene ether base rubber particles, nitrile silicone rubber particle, silicon boron rubber particles and fluorosioloxane rubber particle of dispersed silicon rubber particles is treated described in.
17. methods described in any one in-12 according to Claim 8, wherein, described silicone oil base oil is unmodified silicone oil and/or modified silicon oil；
Preferably, described unmodified silicone oil is selected from methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil and at least one contained in nitrile silicone；
Preferably, described modified silicon oil is selected from amino-modified silicone oil, epoxy-modified silicone oil, polyether modified silicon oil, Carboxyl Modified Polydimethylsiloxane, alcoholic extract hydroxyl group modified silicon oil, phenolic group modified silicone oil, sulfhydryl modified silicone oil, polysiloxane-polyether block modification by copolymerization silicone oil, alkyl and at least one in polyether modified silicon oil, alkyl ether polyether silicone oil, epoxy radicals polyether modified silicon oil, amino-polyether block silicone oil, glycerol ether silicone oil, phosphoric acid cruel base silicone oil, glycosyl polyethers silicone oil and Radix Betae base silicone oil.
18. lubricant compositions prepared by the method described in any one in claim 8-17.
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| CN107723077A (en) * | 2017-11-20 | 2018-02-23 | 苏州永创达电子有限公司 | A kind of durable environment-protective lubricant oil of high temperature lubricating |
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