CN100400630C - Lubricating oil viscosity index improver - Google Patents
Lubricating oil viscosity index improver Download PDFInfo
- Publication number
- CN100400630C CN100400630C CNB2006100287204A CN200610028720A CN100400630C CN 100400630 C CN100400630 C CN 100400630C CN B2006100287204 A CNB2006100287204 A CN B2006100287204A CN 200610028720 A CN200610028720 A CN 200610028720A CN 100400630 C CN100400630 C CN 100400630C
- Authority
- CN
- China
- Prior art keywords
- viscosity index
- index improver
- lubricating oil
- ethylene
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Lubricants (AREA)
Abstract
The present invention relates to a viscosity index improver for lubricating oil, which mainly solves the problem that the viscosity index improver for lubricating oil in the prior art has high price or does not simultaneously give consideration to thickening capability, shear stability and oil product detergency. The present invention better solves the problem by the technical scheme that the improver comprises 1 to 25 wt% of ethylene-propylene copolymer, 0.0001 to 1.0 wt% carbon chain reinforcing agent and basic oil as the rest, and is used for the industrial production of the viscosity index improver for lubricating oil.
Description
Technical field
The present invention relates to a kind of lubricating oil viscosity index improver.
Background technology
According to the action principle to oil product, lubricating oil additive is divided into two big classes: functional additive and viscosity additive.Purification agent, dispersion agent, non-emulsifying agent, rust-preventive agent, anti-wear agent etc., the additive that can give the various performance characteristics of oil product is commonly referred to as functional agent.Viscosity additive then is another kind of, is the additive of " platform " of playing effectiveness for functional agent provides, and its effect is to give oil product due viscosity.Lubricating oil must be under suitable viscosity, and can be transported to needs lubricated position, effects such as lubricated, antirust, the cooling of bringing into play that it has.The proper lubrication oil viscosity should be less than 3 pools, and this viscosity is " critical pumpability viscosity " that guarantees smooth and easy fuel feeding, and greater than 3 centistokes, promptly greater than forming the MV minium viscosity that " liquid friction " needs.In the application scenario of lubricating requirement increasingly stringent, it is low excessively that general oil product often shows under the high temperature viscosity, can't form firm lubricant film, and thickness too during low temperature loses the flowability that pumping needs, and promptly shows sticking warm nature difference and the low characteristics of viscosity index.So in order to ensure that lubricating oil can perhaps in quite wide region, remain in the range of viscosities of lubricating requirement under quite wide temperature condition, need to add polymkeric substance-tackifier, make oil product reach viscosity criterion.The tackifier that add not only need to give oil product due viscosity, i.e. thickening ability, but also to improve the sticking warm nature of oil product, make oil product have excellent high-temperature lubrication and low-temperature fluidity.Therefore the tackifier of current use are viscosity index improver.
VI improver makes lubricating oil have excellent high-temperature lubrication and low-temperature fluidity, it is also important that with it: the viscosity loss of thickened oil under shearing action that has added VI improver can not be excessive, promptly requires VI improver to have certain shear stability.According to the thickened oil of different purposes requirement interpolation VI improvers, viscosity loss should be lower than prescribed value under the effect of mechanical shear stress.Manufacturer and user use thickening ability D and shear stability S as the fundamental property that defines the VI improver range of application, and D is a pair of relevant with the molecular weight size with polymer architecture with S, and the VI improver characteristic of mutual " contradiction ".The shear stability of polymkeric substance in oil product, refer to polymer molecular chain and under mechanical effect, disconnect the complexity of (being commonly referred to degraded), depend on polymer architecture and molecular weight size, the big more shear stability of VI improver of the same type, molecular weight is poor more.In the product specification of lubricating oil viscosity index improver, the quality of shear stability S is weighed with shear stability index (SSI).SSI numerical value is big more, represents that its shear stability is poor more; Numerical value is more little, and shear stability is good more.SSI measures with the diesel fuel nozzle method in CNPC's standard (Q/SYRH300-2002).And thickening ability D is opposite with shear stability S, and along with the change of viscosity modifier molecular weight is big, the quantity of interpolation increases (concentration raising), and oil viscosity is just high more, and promptly thickening ability is big more.
Viscosity index improver uses in lubricating oil nearly 70 years history, and itself is also always in company with using machinery development and applied environment to change and develop.Viscosity index improver commonly used mainly contains four big classes: polymethacrylate of bringing into use the 1950's (PMA) and polyisobutene (PIB), the ethylene-propylene copolymer (OPC) and the hydrogenated styrene diene copolymer (HSD) of the exploitation sixties.Because ethylene-propylene copolymer (abbreviation ethylene-propylene copolymer) VI improver has that thickening ability is strong, shear stability good, high-temperature behavior and the good characteristics of on-the-spot use properties, in I. C. engine oil, be used widely, in the consumption of viscosity index of internal combustion engine oil properties-correcting agent, account for more than 80%.
At present, 80%～90% I. C. engine oil is a multi-grade oil, and diesel engine oil very major part also is a multi-grade oil.Along with engine and mechanical means develop and the requirement of environmental protection and energy saving to high-speed, small volume, high-power direction, also more and more harsher to the requirement of employed viscosity index improver, improve requirement on the specification again and again to the viscosity index improver shear stability.The method of improving shear stability has two kinds, and the one, the molecular weight of reduction viscosity index improver, this is the way that improves shear stability S with loss thickening ability D.Nearly all viscosity index improver can both improve shear stability by reducing molecular weight.The shear stability of a certain class viscosity index improver is closely to link to each other with its molecular weight: just more little shear stability is good more for molecular weight, reduce but thickening ability is corresponding, this addition that just needs to strengthen viscosity index improver satisfies other requirement of oil viscosity level, and the amount of polymer increase of adding can bring a series of problems such as detergency variation of I. C. engine oil.The another kind of method that improves shear stability is by changing polymer architecture, improve the critical polymerization degree and improve stability, make polymkeric substance in the higher thickening ability of maintenance, having shear stability preferably.Thereby have only the polymkeric substance that those are rational in infrastructure, shear stability good, thickening capabilities is strong and don't make the detergency variation, could satisfy growing requirement for shear stability.Under the guidance of this theory, many new viscosity index improvers had appearred in recent years, to satisfy the requirement of harsh day by day SSI value.For example the hydrogenated styrene isoprene copolymer HSD of Shell additive company has two kinds of segmented copolymer and starlike multipolymers.The SSI of segmented copolymer product SV 150 is 10%, star-shape polymer SV 260, and SV250 and SV 200, SSI is respectively 25%, 15% and 5%.Simultaneously, with the ethylene-propylene copolymer product OCP ratio of identical shear stability, the thickening capabilities of HSD type viscosity index improver is much higher.Yet the intrinsic deficiency that some structures that also have HSD cause, price makes it to be difficult to be accepted by most of users far above problems such as OCP in addition.
Ethylene-propylene copolymer (OCP) type viscosity index improver because of its rich raw material sources, advantages such as production technique is simple, product price is cheap, good combination property, be most widely used viscosity index improver always.The early stage widely used OCP of China is the ECA9291 of Exxon company, and its diesel fuel nozzle method shear stability index SSI is about 50%, and the viscosity index improver product major part of producing both at home and abroad is that SSI is 35%～39% OCP product at present.Yet along with modern engine and oil specification development thereof, requiring to use diesel fuel nozzle method SSI is 25%, perhaps the better viscosity index improver of shear stability stability.And the SSI of OCP type viscosity index improver rests on 26% level basically at present.
Document " chemical engineer, No.3,2001:48～49 " discloses a kind of OCP type viscosity index improver (T612), and its SSI is 50%, and thickening capabilities is 6 centistokes.The SSI of the disclosed ethylene-propylene copolymer viscosity index improver T 613B of document " lubricating oil, 18 (6), 2003:48～52 " is 22%, and thickening capabilities is 4.8 centistokes.Document " oilman skill, 18 (4), 2000:16～18 " disclosed OCP type viscosity index improver (SHL-615) SSI is 25%, and thickening capabilities is 5.5 centistokes.So in order to adapt to the raising that the viscosity index improver shear stability is required, the OCP product can only take to reduce molecular weight and corresponding thickening capabilities solves.But add-on increases, and has caused the detergency variation of oil product, use cost to rise, and particularly SSI is 20% o'clock, and the add-on that needs can be more.
Summary of the invention
Technical problem to be solved by this invention is the selling at exorbitant prices of prior art medium viscosity index improving agent, and perhaps the problem that can not take into account simultaneously of thickening capabilities, shear stability and oil product detergency provides a kind of new lubricating oil viscosity index improver.This lubricating oil viscosity index improver has that thickening capabilities is strong, shear stability good, have the good characteristics of detergency simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of lubricating oil viscosity index improver comprises following component by weight percentage:
A) 1～25% ethylene-propylene copolymer;
B) 0.0001～1.0% carbochain toughener;
C) base oil of surplus;
Wherein ethylene-propylene copolymer is the copolymer of ethene and copolymerization of propylene, the weight-average molecular weight M of ethylene-propylene copolymer
w=1.0 * 10
5～2.5 * 10
5, weight-average molecular weight M
wWith number-average molecular weight M
nRatio M
w/ M
n=0.5～2.5; The carbochain toughener is selected from least a in halohydrocarbon, fragrant nitrile or the aromatic nitrile halide; The kinematic viscosity v of base oil under 100 ℃
100Be 2.5～10.0 centistokes.
In the technique scheme, the consumption preferable range of ethylene-propylene copolymer is 3～20%, and more preferably scope is 5～15%; The consumption preferable range of carbochain toughener is 0.0005～0.5%, and more preferably scope is 0.001～0.05%.The preferred version of ethylene-propylene copolymer is its weight-average molecular weight M
wWith number-average molecular weight M
nRatio M
w/ M
n=1.5～1.8.The halohydrocarbon preferred version is for being selected from halogenated aryl hydrocarbon, and more preferably scheme is to be selected from least a in bromobenzene or the chlorinated benzene; Fragrance nitrile preferred version is to be selected from least a in cyanobenzene, phthalonitrile, Isophthalodinitrile or the para-Phthalonitrile; The aromatic nitrile halide preferred version is for being selected from o-Cyanochlorobenzene, p-Cyanochlorobenzene, 2, at least a in 6-dichlorobenzonitrile, 2,4 dichloro benzene formonitrile HCN or the 4-6-chlorophenyl nitrile; The kinematic viscosity preferred version of base oil under 100 ℃ is v
100Be 4.5～8.0 centistokes, more preferably scheme v
100Be 4.5～6.0 centistokes; The kinematic viscosity preferred version of base oil under 40 ℃ is v
40Be 15～40 centistokes, more preferably scheme is v
40Be 20～32 centistokes; The base oil preferred version is to be selected from least a in HVI100, MVI100, HVI150, MVI150 neutral oil, No. 40 transformer oil, No. 20 turbine oils or No. 20 machinery oil, and more preferably scheme is for being selected from HVI150 neutral oil.
In the technique scheme, preferred version is also to comprise in the lubricating oil viscosity index improver being selected from d by weight percentage) 0.0001～0.5% degradation of promoter, e) 0.001～1% oxidation inhibitor or f) at least a in the solubility promoter; Wherein said degradation of promoter consumption preferable range is 0.001～0.1%, and more preferably scope is 0.005～0.05%; The degradation of promoter preferred version is the superoxide that is selected from aromatic hydrocarbons, and more preferably scheme is to be selected from least a in peroxidation benzene, peroxidation toluene, dicumyl peroxide or the dicumyl peroxide.Described oxidation inhibitor consumption preferable range is 0.01～0.2%, and more preferably scope is 0.03～0.15%; The oxidation inhibitor preferred version is for being selected from phenol type or amine type oxidation inhibitor, and the phenol type antioxidant preferred version is for being selected from 2,6 ditertiary butyl p cresol or 2, at least a in the 6-di-tert-butylphenol; Amine type oxidation inhibitor preferred version is to be selected from least a in N-phenyl-αNai An, alkyl benzene amine or the naphthylamines.Described solubility promoter preferred version is for being selected from the C10 aromartic cut, and more preferably scheme is for being selected from naphtha reforming C10 aromartic cut; The weight ratio of base oil and solubility promoter is 0.2～5: 1, and preferable range is 0.5～2: 1.
Component of the present invention is ethylene-propylene copolymer a), is the binary glue of ethene and copolymerization of propylene.The ethylene-propylene copolymer molecular weight is big more, and molecular chain is long more, tends to fracture more, and shear stability is poor more; When molecular weight was identical, molecular weight distribution was narrow more, and shear stability is good more, because the molecular amounts that can be sheared reduces relatively.The weight-average molecular weight M of ethylene-propylene copolymer among the present invention
wBe 1.0 * 10
5～2.5 * 10
5, weight-average molecular weight M
wWith number-average molecular weight M
nThe ratio preferred version be M
w/ M
nBe 0.5～2.5, more preferably scheme is M
w/ M
nBe 1.5～1.8.Its consumption is 1～25% by weight percentage, and preferable range is 3～20%, and more preferably scope is 5～15%.
Component b of the present invention) carbochain toughener is selected from least a in halohydrocarbon, fragrant nitrile or the aromatic nitrile halide; Wherein the halohydrocarbon preferred version is for being selected from halogenated aryl hydrocarbon, and more preferably scheme is to be selected from least a in bromobenzene or the chlorinated benzene; Fragrance nitrile preferred version is to be selected from least a in cyanobenzene, phthalonitrile, Isophthalodinitrile or the para-Phthalonitrile; The aromatic nitrile halide preferred version is for being selected from o-Cyanochlorobenzene, p-Cyanochlorobenzene, 2, at least a in 6-dichlorobenzonitrile, 2,4 dichloro benzene formonitrile HCN or the 4-6-chlorophenyl nitrile.Under the situation of being heated, " weak bond " can appear on the ethylene-propylene copolymer polyolefin chain, become the initiation point of chain-breaking reaction.The effect of carbochain toughener is by introduce functional groups on polymer molecular chain, the position of " most fragile " in the reinforcing copolymer molecular chain, promptly strengthen the C-C bonding strength at the easiest generation chain rupture position in application process, make the viscosity modifier product in application process, keep shear stability preferably.Strengthening principle is: by de-hydrogen halide, perhaps cyanation makes the α hydrogen that links to each other with methyl on the ethylene-propylene copolymer macromolecule chain section deviate from, and connects phenyl group simultaneously, thereby has improved the stability of C-C chain link.The consumption of carbochain toughener is 0.0001～1.0% by weight percentage, and preferable range is 0.0005～0.5%, and more preferably scope is 0.001～0.05%.
Component c of the present invention) base oil plays the effect of additive carrier and the basic physicochemical property of assurance compositions of additives.The basis oil viscosity is all influential to the thickening ability and the shear stability index of viscosity index improver.The kinematic viscosity v of base oil of the present invention under 100 ℃
100Be 2.5～10 centistokes, preferred version v
100Be 4.5～8.0 centistokes, more preferably scheme v
100Be 4.5～6.0 centistokes; The kinematic viscosity preferred version v of base oil under 40 ℃
40Be 15～40 centistokes, more preferably scheme v
40Be 20～32 centistokes; The base oil preferred version is to be selected from least a in HVI100, MVI100, HVI150, MVI150 neutral oil, No. 40 transformer oil, No. 20 turbine oils or No. 20 machinery oil, and more preferably scheme is for being selected from HVI150 neutral oil.
Component d of the present invention) be degradation of promoter, its effect is to make ethylene-propylene copolymer that thermal oxidative reaction take place rapidly under lower temperature of reaction, is degraded to suitable molecular weight rapidly, makes simultaneously that molecular weight distribution narrows down, the colourity of product reduces.In degradation process, the degradation rate of polymkeric substance raises with temperature and is the logarithmic relationship increase, therefore in the production process of viscosity index improver, time expand, raising temperature all help improving degradation rate, and molecular weight is linear decline with rising, the prolongation of time of temperature.Yet lubricating oil itself is the rapid deterioration by oxidation of meeting under hot conditions for a long time: viscosity and acid number rise, the oxidation stability variation.For shortening time and reduction temperature, generally all adopt the technology of thermal-oxidative degradation.An important feature of oxidation of polyolefins is as long as very a little bit smaller chemical transformation just may cause the variation of very big physicals.For example the polymkeric substance of 100 monomer chain lengths just can make polymericular weight descend 2 to 3 times as long as absorb a Sauerstoffatom.Though temperature has reduced some, under the thermooxidizing condition, the oxidation of oil product aggravation itself can cause rotten equally.Degradation of promoter of the present invention has solved this problem just.
Degradation of promoter of the present invention is an organo-peroxide, mainly is the superoxide of aromatic hydrocarbons, comprises peroxidation benzene, peroxidation toluene, dicumyl peroxide or dicumyl peroxide.The adding of degradation of promoter makes ethylene-propylene copolymer be degraded to suitable molecular weight rapidly, and molecular weight distribution is narrowed down.With dicumyl peroxide (DCP) is example, and organo-peroxide promotes that the mechanism of polymer degradation at first is that the DCP thermolysis is a free radical:
Then, these free radicals seize the hydrogen atom of tertiary carbon atom on the polymer molecular chain, form free radical chain:
Then have the polymer molecular chain generation chain rupture of free radical:
Be the complex reaction of various free radicals at last, in reaction process with the consumption of DCP quantity, polymer molecule is chain rupture constantly, free radical compound mutually, reach a certain balance at last, this moment, free radical exhausted, and no longer included the source of free radical, this shows as the viscosity degradation of polymkeric substance, the mobile improvement just the molecular-weight adjusting to of polymkeric substance needs and lower numerical value.By weight percentage, the amount ranges of degradation of promoter is 0.0001～0.5%, and preferable range is 0.001～0.1%, and more preferably scope is 0.005～0.05%.
Component e of the present invention) oxidation inhibitor, effect are to suppress the thermal oxidative reaction of oil product in the viscosity index improver production process, and the chain rupture of ethylene-propylene copolymer is not had adverse influence.The oxidation inhibitor preferred version is for being selected from phenol type or amine type oxidation inhibitor, and the phenol type antioxidant preferred version is for being selected from 2,6 ditertiary butyl p cresol or 2, at least a in the 6-di-tert-butylphenol; Amine type oxidation inhibitor preferred version is to be selected from least a in N-phenyl-αNai An, alkyl benzene amine or the naphthylamines.The consumption of oxidation inhibitor is 0.001～1% by weight percentage, and preferable range is 0.01～0.2%, and more preferably scope is 0.03～0.15%.
Component f of the present invention) solubility promoter, its effect are ethylene-propylene copolymer, carbochain toughener, degradation of promoter and oxidation inhibitor are dissolved better and to be distributed in the base oil.The weight ratio of base oil and solubility promoter is 0.2～5: 1, and preferable range is 0.5～2: 1.The solubility promoter preferred version is a C10 aromartic, and more preferably scheme is for being selected from naphtha reforming C10 aromartic cut.
Lubricating oil viscosity index improver of the present invention can be produced in the mediation still of being furnished with whipping appts, heating unit, refrigerating unit and gas panel pipe.Production method is as follows:
A) base oil is added blending kettle, start agitator and heater switch, when being heated to 100 ℃～165 ℃, add ethylene-propylene copolymer, insulation feeds nitrogen at the bottom of still, make and keep 0～0.05MPa gauge pressure in the still;
B) treat that ethylene-propylene copolymer dissolves fully after, add oxidation inhibitor and degradation of promoter, and the nitrogen that will feed at the bottom of the still changes air into non-imposedly, slowly be warming up to 150～185 ℃, stop heating, will feed gas and change nitrogen again into;
C) treat that above-mentioned reaction mixture is cooled to 140～170 ℃, add the carbochain toughener, continue insulated and stirred and both could in 1～10 hour.
Lubricating oil viscosity index improver of the present invention is according to the method for the company standard Q/SYRH3001-2002 of PetroChina Company Ltd. regulation, both diesel fuel nozzle shear stability index SSI measuring method was measured the shear stability index of lubricating oil viscosity index improver product, according to the thickening ability of Q/SY RH3001-2002 method mensuration lubricating oil viscosity index improver, measure the colourity of lubricating oil viscosity index improver according to GB/T6540.
Lubricating oil viscosity index improver of the present invention is owing to added the carbochain toughener in the mixed system of base oil and ethylene-propylene copolymer, on the ethylene-propylene copolymer molecular chain, introduce functional groups, strengthen the easy chain rupture position of multipolymer, improved the shear stability of lubricating oil viscosity index improver; The present invention adds degradation of promoter in above-mentioned system, introduce free radical to segment, under relatively shorter time and lower temperature, impels ethylene-propylene copolymer to degrade rapidly; The present invention has added oxidation inhibitor in above-mentioned system, suppressed the thermal oxidative reaction of oil product; The concentration of ethylene-propylene copolymer is very low in the above-mentioned system of the present invention, can not influence the detergency of oil product.Therefore the shear stability index of lubricating oil viscosity index improver of the present invention and thickening capabilities and cleansing performance are taken into account simultaneously, its shear stability index of lubricating oil viscosity index improver of the present invention reaches 5～26%, thickening ability reaches 4.0～6.3 centistokes, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Conversion unit:
The stirred pot at intermittence that useful volume is 25 liters, 0.25 meter of jar internal diameter φ, 0.6 meter of height has 4 of vertical baffles, 4 of 0.1 meter of diameter phi tiltedly slurry agitators has been installed, agitator speed 120rpm on jar central stirring shaft.The built-in heating coil of jar, with the thermal cyclic carrier heating, jar outer cooling jacket that is provided with can be lowered the temperature rapidly with water coolant when the reaction end.The jar end, be provided with the gas panel pipe, uses for blowing air and nitrogen, and tank deck has fast-open type to add Jiao Kou.Safety valve is arranged at the stirred pot top, and vapor pipe is provided with pressure-regulator.
The production of lubricating oil viscosity index improver:
(1) pour base oil into stirred pot, warming while stirring when temperature reaches 150 ℃, opens to add Jiao Kou, adds to be cut into blocky ethylene-propylene copolymer in jar, feeds nitrogen with the speed of 100 ml/min at the bottom of jar, and making the still internal pressure is the 0.02MPa gauge pressure; With about 4 ℃/hour speed slowly heat up, colloidal sol, temperature rises to 165 ℃, colloidal sol finishes.
(2) the carbochain toughener is added in the jar, kept 1 hour for 165 ℃, be cooled to 110 ℃, discharging, barrelling.
(3),, measure colourity according to GB/T6540 according to Q/SYRH3001-2002 standard test diesel fuel nozzle shear stability index and thickening ability in the filling exit sampling.
Each component and weight content thereof see Table 1 in the lubricating oil viscosity index improver, its relevant characters and see Table 2 with the contrast of the thickening ability-shear stability index of the Q/SYRH3001-2002 of PetroChina Company Ltd. standard RHY series product.
[embodiment 2]
The production of lubricating oil viscosity index improver:
(1) base oil is poured into the stirred pot in [embodiment 1], warming while stirring is when temperature reaches 140 ℃, open and add Jiao Kou, add in jar and be cut into blocky ethylene-propylene copolymer, feed nitrogen with the speed of 100 ml/min at the bottom of jar, making the still internal pressure is the 0.04MPa gauge pressure; With about 4 ℃/hour speed slowly heat up, colloidal sol, temperature rises to 165 ℃, colloidal sol finishes.
(2) add degradation of promoter, and will feed the gas at jar end and change air into, air feeding amount is 300 ml/min, slowly heats up, and keeps 5 ℃ of/hour heat-up rates, degrades 3 hours, and temperature reaches 180 ℃, stops to heat, and will lead to the popularity structural reform is nitrogen.
(3) temperature descends and remains on 145 ℃, and the carbochain toughener is added in the jar, keeps 5 hours, continues to be cooled to 110 ℃, discharging, barrelling.
(4),, measure colourity according to GB/T6540 according to Q/SY RH3001-2002 standard test diesel fuel nozzle shear stability index and thickening ability in the filling exit sampling.
Each component and weight content thereof see Table 1 in the lubricating oil viscosity index improver, its relevant characters and see Table 2 with the contrast of the thickening ability-shear stability index of the Q/SYRH3001-2002 of PetroChina Company Ltd. standard RHY series product.
[embodiment 3]
The production of lubricating oil viscosity index improver:
(1) base oil is poured into the stirred pot in [embodiment 1], warming while stirring is when temperature reaches 120 ℃, open and add Jiao Kou, add in jar and be cut into blocky ethylene-propylene copolymer, feed nitrogen with the speed of 100 ml/min at the bottom of jar, making the still internal pressure is the 0MPa gauge pressure; With about 4 ℃/hour speed slowly heat up, colloidal sol, temperature rises to 165 ℃, colloidal sol finishes.
(2) add oxidation inhibitor.
(3) the carbochain toughener is added in the jar, kept 4 hours for 165 ℃, be cooled to 110 ℃, discharging, barrelling.
(4) sampling, analytical study.In the filling exit sampling,, measure colourity according to GB/T6540 according to Q/SY RH3001-2002 standard test diesel fuel nozzle shear stability index and thickening ability.
Each component and weight content thereof see Table 1 in the lubricating oil viscosity index improver, its relevant characters and see Table 2 with the contrast of the thickening ability-shear stability index of the Q/SYRH3001-2002 of PetroChina Company Ltd. standard RHY series product.
[embodiment 4～8]
The production of lubricating oil viscosity index improver:
(1) base oil is poured into stirred pot in [embodiment 1], warming while stirring is when temperature reaches 110 ℃, open and add Jiao Kou, add in jar and be cut into blocky ethylene-propylene copolymer, feed nitrogen with the speed of 100 ml/min at the bottom of jar, making the still internal pressure is the 0.02MPa gauge pressure; With about 4 ℃/hour speed slowly heat up, colloidal sol, temperature rises to 140 ℃, colloidal sol finishes.
(2) add oxidation inhibitor and degradation of promoter, and will feed the gas at jar end and change oxygen into, oxygen feeding amount is 150 ml/min, slowly heats up, and keeps 5 ℃ of/hour heat-up rates, and temperature reaches 180 ℃, stops to heat, and will lead to the popularity structural reform is nitrogen.
(3) with the warm water cooling, temperature descends and remains on 170 ℃, and the carbochain toughener is added in the jar, keeps 1 hour, continues to be cooled to 110 ℃, discharging, barrelling.
(4) sampling, analytical study.In the filling exit sampling,, measure colourity according to GB/T6540 according to Q/SY RH3001-2002 standard test diesel fuel nozzle shear stability index and thickening ability.
Each component and weight content thereof see Table 1 in the lubricating oil viscosity index improver, its relevant characters and see Table 2 with the contrast of the thickening ability-shear stability index of the Q/SYRH3001-2002 of PetroChina Company Ltd. standard RHY series product.
Can see that by table 1 and table 2 product of shear stable similar temperament, the thickening ability of product of the present invention are higher than Q/SYRH3001-2002 standard RHY series product.And the close product of thickening ability, the shear stability of product of the present invention is much better than Q/SYRH3001-2002 standard RHY series product.Simultaneously, product of the present invention is because service temperature is low, and the reaction times is short, and colourity obviously is better than Q/SYRH3001-2002 standard RHY series product.
Claims (10)
1. lubricating oil viscosity index improver comprises following component by weight percentage:
A) 1～25% ethylene-propylene copolymer;
B) 0.0001～1.0% carbochain toughener;
C) base oil of surplus;
Wherein ethylene-propylene copolymer is the copolymer of ethene and copolymerization of propylene, the weight-average molecular weight M of ethylene-propylene copolymer
w=1.0 * 10
5～2.5 * 10
5, weight-average molecular weight M
wWith number-average molecular weight M
nRatio M
w/ M
n=0.5～2.5; The carbochain toughener is selected from least a in halohydrocarbon, fragrant nitrile or the aromatic nitrile halide; The kinematic viscosity v of base oil under 100 ℃
100Be 2.5～10.0 centistokes.
2. according to the described lubricating oil viscosity index improver of claim 1, it is characterized in that by weight percentage,
A) amount ranges of ethylene-propylene copolymer is 3～20%;
B) amount ranges of carbochain toughener is 0.0005～0.5%;
Wherein said ethylene-propylene copolymer weight-average molecular weight M
wWith number-average molecular weight M
nRatio M
w/ M
n=1.5～1.8; Described halohydrocarbon is selected from halogenated aryl hydrocarbon; Described fragrant nitrile is selected from least a in cyanobenzene, phthalonitrile, Isophthalodinitrile or the para-Phthalonitrile; Described aromatic nitrile halide is selected from o-Cyanochlorobenzene, p-Cyanochlorobenzene, 2, at least a in 6-dichlorobenzonitrile, 2,4 dichloro benzene formonitrile HCN or the 4-6-chlorophenyl nitrile; The kinematic viscosity v of described base oil under 100 ℃
100Be 4.5～8.0 centistokes; Also comprise in the lubricating oil viscosity index improver by weight percentage and be selected from d) 0.0001～0.5% degradation of promoter, e) 0.001～1% oxidation inhibitor or f) at least a in the solubility promoter; Wherein said degradation of promoter is the superoxide of aromatic hydrocarbons; Described solubility promoter is the C10 aromartic cut, and the weight ratio of base oil and solubility promoter is 0.2～5: 1.
3. according to the described lubricating oil viscosity index improver of claim 2, it is characterized in that by weight percentage,
A) amount ranges of ethylene-propylene copolymer is 5～15%;
B) amount ranges of carbochain toughener is 0.001～0.05%;
Wherein said halogenated aryl hydrocarbon is selected from least a in bromobenzene or the chlorinated benzene; The kinematic viscosity v of described base oil under 100 ℃
100Be 4.5～6.0 centistokes.
4. according to the described lubricating oil viscosity index improver of claim 3, it is characterized in that the kinematic viscosity v of base oil under 40 ℃
40Be 15～40 centistokes.
5. according to the described lubricating oil viscosity index improver of claim 4, it is characterized in that the kinematic viscosity v of base oil under 40 ℃
40Be 20～32 centistokes.
6. according to the described lubricating oil viscosity index improver of claim 3, it is characterized in that described base oil is selected from least a in HVI100, MVI100, HVI150, MVI150 neutral oil, No. 40 transformer oil, No. 20 turbine oils or No. 20 machinery oil.
7. according to the described lubricating oil viscosity index improver of claim 6, it is characterized in that described base oil is a HVI150 neutral oil.
8. according to the described lubricating oil viscosity index improver of claim 2, it is characterized in that described degradation of promoter is selected from least a in peroxidation benzene, peroxidation toluene, dicumyl peroxide or the dicumyl peroxide, its amount ranges is 0.001～0.1% by weight percentage; Described oxidation inhibitor is phenol type or amine type oxidation inhibitor; Wherein phenol type antioxidant is selected from 2,6 ditertiary butyl p cresol or 2, at least a in the 6-di-tert-butylphenol; Amine type oxidation inhibitor is selected from least a in N-phenyl-αNai An, alkyl benzene amine or the naphthylamines; The oxidation inhibitor amount ranges is 0.01～0.2% by weight percentage.
9. described according to Claim 8 lubricating oil viscosity index improver is characterized in that described degradation of promoter amount ranges is 0.005～0.05% by weight percentage; The amount ranges of described oxidation inhibitor is 0.03～0.15% by weight percentage.
10. according to the described lubricating oil viscosity index improver of claim 2, it is characterized in that described solubility promoter is a naphtha reforming C10 aromartic cut, the weight ratio of base oil and solubility promoter is 0.5～2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100287204A CN100400630C (en) | 2006-07-07 | 2006-07-07 | Lubricating oil viscosity index improver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100287204A CN100400630C (en) | 2006-07-07 | 2006-07-07 | Lubricating oil viscosity index improver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1876780A CN1876780A (en) | 2006-12-13 |
| CN100400630C true CN100400630C (en) | 2008-07-09 |
Family
ID=37509340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100287204A Expired - Fee Related CN100400630C (en) | 2006-07-07 | 2006-07-07 | Lubricating oil viscosity index improver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100400630C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392207B (en) * | 2008-10-13 | 2011-12-07 | 深圳海润德石化技术有限公司 | lubricating oil viscosity index improver |
| WO2020109184A1 (en) | 2018-11-26 | 2020-06-04 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079501A (en) * | 1993-04-06 | 1993-12-15 | 陆东祥 | Viscosity improver for lubricating oil and its preparation |
-
2006
- 2006-07-07 CN CNB2006100287204A patent/CN100400630C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079501A (en) * | 1993-04-06 | 1993-12-15 | 陆东祥 | Viscosity improver for lubricating oil and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1876780A (en) | 2006-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2000060032A1 (en) | Viscosity regulator for lubricating oil and lubricating oil composition | |
| CN102482365B (en) | Two-stage process and system for forming high viscosity poly-alpha-olefins | |
| JP4634300B2 (en) | Lubricating oil composition and lubricating oil for internal combustion engine | |
| CN101240220A (en) | Densification type high temperature chain lubricating agent composition | |
| CN100400631C (en) | Lubricating oil viscosity index improver production method | |
| JP2011190377A (en) | Lubricating oil composition | |
| CN100549148C (en) | A kind of ethylene-propylene copolymer viscosity index improver and preparation thereof and application | |
| CN109593930A (en) | A kind of novel quenching oil and its manufacturing method | |
| CN101812356A (en) | Thickening type high-temperature chain lubricant combination | |
| CN100400630C (en) | Lubricating oil viscosity index improver | |
| CN111269745A (en) | Synthetic industrial gear oil and preparation method thereof | |
| CN101812358A (en) | High-temperature chain oil composition of mixed base oil | |
| JP5122114B2 (en) | Hydraulic fluid and hydraulic system using the same | |
| CN105886073B (en) | A kind of preparation method of the lubricant tackifier of high shear performance | |
| JP2017511396A (en) | Lubricating oil viscosity modifier, lubricating oil additive composition, and lubricating oil composition | |
| CN107488482A (en) | A kind of low temperature hydraulic oil composition and its application | |
| CN105132081A (en) | Preparation method for ethylene-propylene copolymer viscosity index improver | |
| JP4620966B2 (en) | Drive system lubricating oil composition | |
| CN107245365A (en) | Engine motor oil composition and preparation method thereof | |
| CN110484340A (en) | A kind of environment-friendly type energy-saving diesel engine oil and preparation method thereof | |
| CN101392207B (en) | lubricating oil viscosity index improver | |
| CN104342231A (en) | Lubricating-oil viscosity index improver and preparation method thereof | |
| CN107418651B (en) | Carboxylated triheptyl citrate calcium salt lubricating oil detergent and preparation method thereof | |
| CN115368958A (en) | Lubricating oil for transmission system of engineering machinery and production method | |
| CN115678646A (en) | Diesel engine oil with ultralow-temperature starting performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080709 Termination date: 20150707 |
|
| EXPY | Termination of patent right or utility model |