CN109679740A - A kind of lubricating grease and preparation method thereof - Google Patents

A kind of lubricating grease and preparation method thereof Download PDF

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Publication number
CN109679740A
CN109679740A CN201710970947.9A CN201710970947A CN109679740A CN 109679740 A CN109679740 A CN 109679740A CN 201710970947 A CN201710970947 A CN 201710970947A CN 109679740 A CN109679740 A CN 109679740A
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monomer
lubricating grease
added
integer
hours
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CN109679740B (en
Inventor
郑会
张耀
孙洪伟
刘中其
庄敏阳
刘依农
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/025—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention proposes a kind of lubricating grease and preparation method thereof.Lubricating grease of the invention includes following components: gradient copolymer, thickening agent, antioxidant, antirust agent and lubricating base oil.Lubricating grease of the invention has excellent low-temperature lubrication performance, colloid stability, anti-water drenching, can be used in the lubrication of various mechanical equipments, the lubrication especially suitable for mechanical equipment under cryogenic conditions.

Description

A kind of lubricating grease and preparation method thereof
Technical field
The present invention relates to a kind of lubricating grease more particularly to a kind of low temperature greases.
Background technique
The wide range of applications of lubricating grease can be used for lubricating the mechanical friction position of rotation, lubrication, also have protection concurrently With the effect of sealing, almost cover industrial circle, agriculture field, traffic transport industry, aerospace industry, electronic and information industry and Defence equipment.In petroleum products, various in style although specific gravity shared by the yield of lubricating grease is little, it is that national economy is each The indispensable important materials of department.
With the fast development of the modern industry, increasingly higher demands are proposed to lubriation material, northern China is most of Regional winter climate is cold, and many machinery take centralized lubricating system to be lubricated, and centralized lubrication pipeline is more up to tens meters It is exposed to outdoor, this proposes harsher requirement to the cryogenic property of lubricating grease.
It is thickening agent, III class of thickening basis that CN 103525510A, which is disclosed using 12- hydroxy lithium stearate, lithium stearate, The semi synthetic base oils that oil is mixed into Esters oil and/or PAO oil, are prepared for a kind of low temperature grease.CN 104371796 is disclosed The use of lithium soap and bentonite is thickening agent, one of thickening PAO, naphthene base crude oil, Esters oil or a variety of is prepared for a kind of low temperature Lubricating grease.CN 101649243A provides a kind of height temperature lubricating grease and preparation method thereof, and the polyurea grease of preparation is a kind of Wide temperature lubricating grease.CN 105087108A discloses a kind of resistance to height prepared using additives such as PAO, glycerolipid, synthesising sulfonates The lubricating grease of low temperature.
Summary of the invention
The invention proposes a kind of lubricating grease and preparation method thereof.
Specifically, the present invention refers at least to the content of the following aspects:
1. a kind of lubricating grease, including following components: gradient copolymer, thickening agent, antioxidant, antirust agent and lubrication base Oil；The manufacturing method of the gradient copolymer includes: that at least two monomers are added into polymerization reaction system, makes described at least two The step of addition copolymerization reaction (especially free radical addition copolyreaction) occurs for kind monomer, wherein at least two monomer is each From the formula that independently represents (I) compound represented and/or its mixture,
In formula (I),
Group R1Represent H orIt is preferred that H is represented,
Group R2Represent H or C1-4Linear or branched alkyl group preferably represents H or methyl,
Symbol a represents 0 or 1, preferably represents 1,
Group R' represents H or group R3, preferably represent group R3,
Group R3Represent C1-C30Linear or branched alkyl group preferably represents C6-C24Linear or branched alkyl group more preferably represents C6-C20Straight chained alkyl,
If the initial time that at least two monomer is added into the polymerization reaction system is t0, end time tm, Then the monomer addition time of at least two monomer is t (t=tm-t0), the monomer addition time is being divided into m etc. When part, symbol m represents an integer in closed interval [5, ∞], preferably represents an integer in closed interval [8, ∞], preferably The upper limit of integer representated by the symbol m is 20000,10000,5000,1000,500,200,100 or 50, in any list Body adds moment tx, the relative scale that at least two monomer is added into the polymerization reaction system make by it is described at least The nuclear magnetic resonance method side chain average carbon atom number X for the mixture that two kinds of monomers are constituted according to the relative scalexMeet with ShiShimonoseki It is formula, symbol x represents the arbitrary integer from 0 to m,
X0<X1<…<Xm-1<Xm (V)
It is preferred that from X0To XmIt is gradually increased, more preferably from X0To XmIt is linear to increase.
2. manufacturing method described in any preceding aspect, wherein being located at the end time t of the monomer additionm, it is described extremely Accumulative additive amount the sum of of few two kinds of monomers within the monomer addition time into the polymerization reaction system is G, and is set Moment t is added in any monomerx, the sum of the additive amount of at least two monomer into the polymerization reaction system is Gx, symbol X represents the arbitrary integer from 0 to m, and following relationship is set up,
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G (VI)
In formula (VI), symbol j represents an integer in closed interval [m/4,3m/4], preferably represent closed interval [m/3, 2m/3] in an integer, more preferably represent an integer in closed interval [2m/5,3m/5], and G0+G1+…+Gj+…+Gm-1 +Gm=G,
It is preferred that from G0/ G to Gj/ G is gradually increased, more preferably from G0/ G to Gj/ G linearly increases, or from Gj/ G to Gm/ G by It gradually reduces, more preferably from Gj/ G to Gm/ G linear reduction,
More preferable Gx/ G and XxMeet following relationship,
In formula (VII), symbol μ represents any one numerical value in open interval (12.5,14.2), preferably represents open interval Any one numerical value in (12.6,13.8), symbol σ represent any one numerical value in open interval (0.5,2).
3. manufacturing method described in any preceding aspect, wherein group R3Represent C10-C18Linear or branched alkyl group it is described Formula (I) compound represented account for whole monomer dosages ratio (by mole be in terms of) for from 40% to 95%, preferably from 55% to 95%.
4. manufacturing method described in any preceding aspect, wherein the X0It represents any in closed interval [6.5,12.5] One numerical value preferably represents any one numerical value or the X in closed interval [7.8,12.0]mRepresent closed interval [13.8, 19.5] any one numerical value in preferably represents any one numerical value in closed interval [14.5,18.2].
5. manufacturing method described in any preceding aspect, wherein ratio Gj/ G be from 20% to 75%, preferably from 25% to 65% or ratio G0/ G or ratio Gm/ G is from 0.01% to 20%, preferably from 0.1% to 10%.
6. manufacturing method described in any preceding aspect, wherein the reaction temperature of the copolyreaction is from 50 DEG C to 180 DEG C, preferably from 55 DEG C to 165 DEG C, more preferably from 60 DEG C to 150 DEG C, the reaction time of the copolyreaction is from 1 hour to 24 Hour, preferably from 1.5 hours to 20 hour, the monomer addition time t be from 0.5 hour to 12 hour, preferably from 1 hour to 10 hours.
7. lubricating grease described in any preceding aspect, on the basis of lubricating grease total weight, wherein the gradient copolymer accounts for 0.01%~10% (preferably 0.5%~2%) of lubricating grease total weight；The thickening agent account for lubricating grease total weight 1%~ 30% (preferably 5%~25%)；The antioxidant accounts for 0.1%~10% (preferably 0.5%-2%) of lubricating grease gross mass；It is described Antirust agent accounts for 0.1%~10% (preferably 0.5%-2%) of lubricating grease gross mass；The lubricating base oil constitutes the master of lubricating grease Want ingredient.
8. lubricating grease described in any preceding aspect, the thickening agent is selected from lithium base thickening agent, calcium base thickening agent, anhydrous calcium One of base thickening agent, sodium base thickening agent and barium base thickening agent are a variety of；The antioxidant is phenol type antioxidant；The antirust Agent is one of esters antirust agent, organic amine antirust agent, sulfur heterocyclic ring or nitrogen-containing heterocycle class antirust agent or a variety of；The profit Sliding base oil is selected from one of I class of API, II class, III class, IV class and V class base oil or a variety of.
The antioxidant is phenol type antioxidant, can be 2,6- toluene di-tert-butyl phenol, beta naphthal, the tertiary fourth of 2,6- bis- In base-alpha, alpha-dimethyl amino paracresol, 4,4- di-2-ethylhexylphosphine oxide (2,6- di-tert-butylphenol) and 2,6- di-t-butyl -4- alkoxy phenol It is one or more.The antirust agent is esters antirust agent, organic amine antirust agent, sulfur heterocyclic ring or nitrogen-containing heterocycle class antirust agent One of or it is a variety of, can be lanolin calcium, lanolin magnesium, petroleum oxidate ester barium soap, department benzene -80, N- oleoylsarcosine One of octadecylamine salt, 17 alkenyl imidazoline of 2- amino-ethyl, dodecenylsuccinic acid, benzotriazole are a variety of.Institute Stating lubricating base oil preferably 100 DEG C of dynamic viscosities is 2-60mm2The base oil of/s, more preferable 100 DEG C of dynamic viscosities are 3-30mm2/ The lubricating base oil of s.
9. preparation of greases method described in any preceding aspect, comprising: thickening agent and lubricating base oil are uniformly mixed, It is refined in 100-200 DEG C of constant temperature, it is cooling, the gradient copolymer, antioxidant and antirust agent is added, is ground into rouge.
Lubricating grease of the invention has excellent low-temperature lubrication performance, colloid stability, anti-water drenching, can be used in various The lubrication of mechanical equipment, the lubrication especially suitable for mechanical equipment under cryogenic conditions.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.
In the context of the present invention, term " (methyl) acrylic acid " refers to acrylic acid or methacrylic acid.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
According to an aspect of the present invention, the side chain average carbon number X of the gradient copolymer is generally from 5 to 20, preferably From 11.5 to 17, preferably from 11.5 to 16.2, more preferably from 12.2 to 15.7, more preferably from 12.2 to 15.5.
According to an aspect of the present invention, generally from 5 to 20 the side chain average carbon number X of the n kind polymers compositions, it is excellent Choosing from 11.5 to 17, preferably from 11.5 to 16.2, more preferably from 12.2 to 15.7, more preferably from 12.2 to 15.5.
According to an aspect of the present invention, the symbol n represents an integer in closed interval [5, ∞], preferably represents and closes An integer in section [8, ∞].Here, the symbol n represents an integer, lower limit can be 5 perhaps 8 or can also To be 10 or 20.As the upper limit of integer representated by the symbol n, ∞ can be, or be also possible to 20000, 10000,5000,1000,500,200,100 or 50.
According to an aspect of the present invention, the gradient copolymer can by following one or more manufacturing methods into Row manufacture.In the context of this specification, any not retouched in detail or specifically for the manufacturing method for the sake of simplifying length In the content stated, such as type of reactor, the usage mode of various additives, the pretreatment of charging, the separation of reaction product etc. Hold, it can be directly referring to corresponding contents known in the art.
According to an aspect of the present invention, the manufacturing method includes at least two list of addition into polymerization reaction system Body makes at least two monomer that the step of addition copolymerization reacts occur.
According to an aspect of the present invention, the implementation of addition copolymerization reaction for convenience, at least two monomer Sometimes it is added in the form of incoming mixture in the polymerization reaction system.Here, as the incoming mixture, in addition to packet Except at least two monomer, solvent, diluent, initiator, molecular weight can also be generally further included as needed Conventional use of one or more additives for addition copolymerization reaction such as regulator, polymerization catalyst.Moreover, these add The type of agent and dosage is added to be referred to the related request of the prior art, the present invention is not particularly limited this.
According to an aspect of the present invention, in the polymerization reaction system, it is double that carbon carbon occurs at least two monomer The addition copolymerization of key reacts, and especially free radical addition copolyreaction can be obtained a kind of gradient copolymer.The gradient copolymerization Object includes the gradient copolymer of the invention described in the various aspects of this specification.
According to an aspect of the present invention, the reaction temperature of addition copolymerization reaction is generally from 50 DEG C to 180 DEG C, It is preferred that from 55 DEG C to 165 DEG C, more preferably from 60 DEG C to 150 DEG C.
According to an aspect of the present invention, the reaction time of addition copolymerization reaction generally from 1 hour to 24 hour, It is preferred that from 1.5 hours to 20 hour.
According to an aspect of the present invention, the addition copolymerization reaction can be poly- according to bulk polymerization, polymerisation in solution, lotion The either types such as conjunction, suspension polymerisation carry out, preferably polymerisation in solution.
According to an aspect of the present invention, in order to which the raising for being conducive to monomer conversion has after monomer addition terminates When addition copolymerization reaction can also be made to continue 0.5-2 hours, or as needed further added initiator, After polymerization catalyst or diluent etc., the temperature of the polymerization reaction system is risen to 100-150 DEG C, is further continued for reacting 0.5-5 hours.These reactive modes are known to the skilled in the art.
According to an aspect of the present invention, as the initiator, can be used it is those of commonly used in the art, especially It is radical polymerization initiator, is not particularly limited.As the initiator, azo initiation specifically can be such as enumerated Agent, peroxide type initiators and redox type initiators.These initiators can be used alone, or with arbitrary Ratio is applied in combination a variety of.In addition, there is no particular limitation for dosage of the present invention to the initiator, it is normal this field can be applicable in Those of known to rule, for example as overall consumption of the initiator in the entire addition copolymerization reaction, generally 0.01- 2.5 parts by weight, preferably 0.05-2 parts by weight, more preferable 0.1-1.5 parts by weight, relative to the total dosage of 100 weight parts monomers.
According to an aspect of the present invention, as the diluent, can be used it is those of commonly used in the art, especially It is flux oil, is not particularly limited.
According to an aspect of the present invention, as the molecular weight regulator, commonly used in the art that can be used A bit, it is not particularly limited.As the molecular weight regulator, lauryl mercaptan or 2- mercapto specifically can be such as enumerated Base ethyl alcohol.These molecular weight regulators can be used alone, or is applied in combination with arbitrary ratio a variety of.In addition, this There is no particular limitation for dosage of the invention to the molecular weight regulator, can be applicable in those of conventionally known in the art.
According to an aspect of the present invention, as the polymerization catalyst, can be used it is those of commonly used in the art, It is not particularly limited.As the polymerization catalyst, catalysts for radical polymerization specifically can be such as enumerated, especially together Ge Le-Natta catalyst.These polymerization catalysts can be used alone, or is applied in combination with arbitrary ratio a variety of. In addition, there is no particular limitation for dosage of the present invention to the polymerization catalyst, can be applicable in those of conventionally known in the art.
According to an aspect of the present invention, the addition copolymerization reaction usually carries out in an inert atmosphere.Here, so-called lazy Property atmosphere, refers to the non-active gas atmosphere not chemically reacted with reactants and products.As the non-active gas, For example nitrogen and inert gas can be enumerated etc..As the method for keeping the inert atmosphere, for example can enumerate to described poly- Close the method that the inert gas is continually fed into reaction system.
According to an aspect of the present invention, at least two monomer is independently represented each other formula (I) compound represented. One of described at least two monomer a variety of can also be rendered as monomer mixture sometimes.In this case, according to this This aspect of invention, the two or more monomer compound that the monomer mixture is included are independently represented each other formula (I) institute The compound shown.
According to an aspect of the present invention, in formula (I), group R1Represent H orIt is preferred that generation Table H.Here, group R' represents H or group R3, preferably represent group R3。
According to an aspect of the present invention, in formula (I), group R2Represent H or C1-4Linear or branched alkyl group, preferably Represent H or methyl.
According to an aspect of the present invention, in formula (I), symbol a represents 0 or 1, preferably represents 1.
According to an aspect of the present invention, in formula (I), group R3Represent C1-C30Linear or branched alkyl group preferably represents C6-C24Linear or branched alkyl group more preferably represents C6-C20Straight chained alkyl or C8-C24Straight chained alkyl.
According to an aspect of the present invention, it is preferred that group R3Represent C10-C18The formula of linear or branched alkyl group (I) compound represented account for whole monomer dosages (overall consumption of at least two monomer) ratio (by mole be in terms of) one As be from 40% to 95%, preferably from 55% to 95%.
According to an aspect of the present invention, as the formula (I) compound represented, fumaric acid specifically can such as be enumerated Single C1-C30Linear or branched alkyl group ester, two C of fumaric acid1-C30Linear or branched alkyl group ester, C3-C30Linear chain or branched chain alpha-olefin and (methyl) acrylic acid C1-C30Linear or branched alkyl group ester more specifically can such as enumerate fumaric acid list C8-C24Linear chain or branched chain alkane Base ester, two C of fumaric acid8-C24Linear or branched alkyl group ester, C6-C20Linear chain or branched chain alpha-olefin and (methyl) acrylic acid C6-C20 Linear or branched alkyl group ester more specifically can such as enumerate fumaric acid list C8-C24Straight chained alkyl ester, two C of fumaric acid8-C24Straight chain Arrcostab, C6-C20Linear alpha-olefin and (methyl) acrylic acid C6-C20Straight chained alkyl ester.These monomers can be used alone one Kind, or be applied in combination with arbitrary ratio a variety of.
According to an aspect of the present invention, as two C of fumaric acid8-C24Linear or branched alkyl group ester, specifically such as may be used To enumerate two C of fumaric acid8Straight chained alkyl ester, two C of fumaric acid10Straight chained alkyl ester, two C of fumaric acid12Straight chained alkyl ester, fumaric acid two C14Straight chained alkyl ester, two C of fumaric acid16Straight chained alkyl ester, two C of fumaric acid18Straight chained alkyl ester, two C of fumaric acid20Straight chained alkyl ester, Two C of fumaric acid22Two C of straight chained alkyl ester and fumaric acid24Straight chained alkyl ester.Two C of these fumaric acid8-C24Linear or branched alkyl group ester It can be used alone, or be applied in combination with arbitrary ratio a variety of.
According to an aspect of the present invention, as the C6-C20Linear chain or branched chain alpha-olefin specifically can such as enumerate 1- Hexene, 1- octene, 1- decene, 1- dodecylene, tetradecene, cetene, 1- octadecene and 1- eicosylene.This A little C6-C20Linear chain or branched chain alpha-olefin can be used alone, or is applied in combination with arbitrary ratio a variety of.
According to an aspect of the present invention, as (methyl) the acrylic acid C6-C20Linear or branched alkyl group ester, it is specific to compare (methyl) acrylic acid C can such as be enumerated6Straight chained alkyl ester, (methyl) acrylic acid C8Straight chained alkyl ester, (methyl) acrylic acid C10Directly Alkane base ester, (methyl) acrylic acid C12Straight chained alkyl ester, (methyl) acrylic acid C14Straight chained alkyl ester, (methyl) acrylic acid C16Directly Alkane base ester, (methyl) acrylic acid C18Straight chained alkyl ester and (methyl) acrylic acid C20Straight chained alkyl ester.These (methyl) acrylic acid C6-C20Linear or branched alkyl group ester can be used alone, or is applied in combination with arbitrary ratio a variety of.
According to an aspect of the present invention, formula (I) compound represented can be commercially available, and can also be used Existing known various methods are manufactured.For concrete example, (methyl) the acrylic acid C6-C20Linear or branched alkyl group ester (methyl) acrylic acid and C can be passed through6-C20The esterification of linear chain or branched chain alkanol and obtain, (methyl) third can also be passed through E pioic acid methyl ester and C6-C20The ester exchange reaction of linear chain or branched chain alkanol and obtain, be not particularly limited.
According to an aspect of the present invention, if the starting that at least two monomer is added into the polymerization reaction system Moment is t0, end time tm, then the monomer addition time of at least two monomer is t (t=tm-t0).In order to as far as possible Monomer conversion is improved, or depending on the monomer addition manner of at least two monomer, the monomer addition time is usual Reaction time than the copolyreaction is short.For example, the monomer addition time is generally small from 0.5 hour to 12 When, preferably from 1 hour to 10 hour.
According to an aspect of the present invention, when monomer addition time t is divided into m equal portions, in any monomer Add moment txIf the side chain average carbon number of at least two monomer is Xx, following relationship establishment.In other words, in office One monomer adds moment tx, the relative scale that at least two monomer is added into the polymerization reaction system makes by described The nuclear magnetic resonance method side chain average carbon atom number X of (imagination) mixture that at least two monomers are constituted according to the relative scalex Meet following relationship.Here, symbol x represents the arbitrary integer from 0 to m.
X0<X1<…<Xm-1<Xm (V)
According to an aspect of the present invention, the side chain average carbon number X of so-called at least two monomerx, above such as this specification It is described, refer to the side chain average carbon number of (imagination) mixture being made of at least two monomer according to predetermined ratio, Described in predetermined ratio refer to any monomer add moment tx, at least two monomer is into the polymerization reaction system The relative scale of addition.
According to an aspect of the present invention, moment t is added in the monomer at least two monomerxGather to described There is no particular limitation for the relative scale added in conjunction reaction system, and the relative scale can be any number, as long as its energy Enough so that the side chain average carbon number X of the imagination mixturexMeet the regulation of the formula (V).For simple example, it is assumed that At least two monomer represents two kinds of monomers, i.e. monomer A and monomer B, wherein the side chain average carbon number of the monomer A is greater than institute State the side chain average carbon number of monomer B.In order to meet the regulation of the formula (V), from described two monomers to the polymerization reaction body The initial time t added in system0To end time tm, the additive amount of the monomer B can be maintained constant, and gradually increase described The additive amount of monomer A, or maintain the additive amount of the monomer A constant, and the additive amount of the monomer B is gradually decreased, or Both change simultaneously, as long as making the additive amount of the monomer B is opposite compared with the additive amount of the monomer A to reduce.
According to an aspect of the present invention, can be added using regulation or program auto-control monomer A and monomer B manually Dosage, to realize the additive amount constant variation of monomer A and monomer B, and total addition level constantly changes.Simple example and Speech: in the initial time t of polymerization reaction0To end time tm, maintain the additive amount of the monomer B constant, pass through m control of setting It is processed, constantly regulate and control the adding rate of monomer A manually in a manner of intermittent, so that discontinuity realizes the additive amount of the monomer B It is opposite compared with the additive amount of the monomer A to reduce.Program can also be controlled by setting, which is that industry personnel is easy out Hair is grasped, and controls program, the continuous adding rate for realizing regulation monomer A, to meet the regulation of formula (V) by this.
According to an aspect of the present invention, the symbol m represents an integer in closed interval [5, ∞], preferably represents and closes An integer in section [8, ∞].Here, the symbol m represents an integer, lower limit can be 5 perhaps 8 or can also To be 10 or 20.As the upper limit of integer representated by the symbol m, ∞ can be, or be also possible to 20000, 10000,5000,1000,500,200,100 or 50.
According to an aspect of the present invention, the value of integer representated by the symbol m is bigger, shows that two neighboring monomer adds The variation that added-time carves is more continuous, while also implying that the variation of the side chain average carbon number at two neighboring monomer addition moment more connects It is continuous.The value of the integer representated by the symbol m is sufficiently large, for example when its upper limit value reaches ∞, this is not meant to this certainly Upper limit value has numerically actually reached ∞, but means to add the consecutive variations at moment, the side chain with the monomer Average carbon number has been also up to the degree of continuous or stepless smooth change.For example, in m=∞, the side chain is average The numerical value of carbon number is from X0To Xm, be no longer presented as the variation of finite ascending series, but be rendered as being increased continuously variation, especially without Differential or smooth incremental variations.
According to an aspect of the present invention, as shown in the formula (V), the numerical value of the side chain average carbon number X is from X0To Xm Incremental variations are rendered as, such as gradually incremental variations or linear increment variation.The present invention is to any phase in the incremental variations There is no particular limitation for incremental amplitude (also referred to as step-length) between two X of neighbour, as long as those skilled in the art think Effectively incremental degree is reached.Moreover, the incremental variations can be unique step incremental variations, it is also possible to not equal step Long incremental variations, are not particularly limited.As the step-length, generally such as can be in from 0.01 to 4.00 range Any value in any value, or from 0.05 to 1.5 range, but the present invention is not limited thereto.
According to an aspect of the present invention, as the X0, it represents at least two monomer described at least two The initial time t that kind monomer is added into the polymerization reaction system0Side chain average carbon number, also represent entire described be incremented by The starting point and minimum value of variation, for example can be any value in from 6.5 to 12.5 ranges, or from 7.8 to 12.0 models Interior any value is enclosed, but the present invention is not limited thereto.In addition, as the Xm, it represents at least two monomer and exists The end time t that at least two monomer is added into the polymerization reaction systemmSide chain average carbon number, also represent whole The terminal and maximum value of a incremental variations, for example can be any value in from 13.8 to 19.5 ranges, or from Any value in 14.5 to 18.2 ranges, but the present invention is not limited thereto.
According to an aspect of the present invention, it is located at the end time t of the monomer additionm, at least two monomer exists The sum of accumulative additive amount in from the monomer addition time t to the polymerization reaction system is G, and is located at any monomer and adds Added-time carves tx, at least two monomer to the sum of additive amount of the polymerization reaction system be Gx, symbol x representative is from 0 to m's Arbitrary integer, following relationship are set up.Below sometimes by ratio Gx/ G is referred to as additive amount ratio.
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G (VI)
According to an aspect of the present invention, in the formula (VI), symbol j represents one in closed interval [m/4,3m/4] A integer preferably represents an integer in closed interval [m/3,2m/3], more preferably represents one in closed interval [2m/5,3m/5] A integer, and G0+G1+…+Gj+…+Gm-1+Gm=G.
According to an aspect of the present invention, moment t is added in any monomerx, institute is added in Xiang Suoshu polymerization reaction system At least two monomers are stated, are indicated with q kind monomer.Here, symbol q represents monomeric species number involved in the manufacturing method, For example it can be the arbitrary integer of from 2 to 100 arbitrary integer or from 2 to 20 arbitrary integer, especially from 2 to 5.? This, if each monomer adds moment t in the monomerxIndependent additive amount (absolute value) into the polymerization reaction system For gs, arbitrary integer of the symbol behalf from 1 to q, then the summation of these independent additive amounts is equal to the Gx, and these individually add Ratio between dosage is at least two monomer in monomer addition moment txAdd into the polymerization reaction system The relative scale added.If this specification is described previously, moment t is added in any monomerx, it is desirable that the relative scale makes described The side chain average carbon number X of imaginary mixturexMeet the regulation of the formula (V).This is these for being directed at least two monomer The relative value of independent additive amount and requirement.This aspect according to the present invention, for these of at least two monomer There is no particular limitation for the respective absolute value of independent additive amount, as long as its summation reaches the Gx, and further such that the GxOr G described in personx/ G meets the regulation of the formula (VI).For simple example, it is assumed that at least two monomer represents two kinds Monomer, i.e. monomer A and monomer B, wherein the side chain average carbon number of the monomer A is greater than the side chain average carbon number of the monomer B.For Make the independent additive amount of described two monomers while meeting the regulation of the formula (V) and the regulation of the formula (VI), from The initial time t that described two monomers are added into the polymerization reaction system0Moment t is added to monomerj, maintain the monomer B Additive amount it is constant, and gradually increase the additive amount of the monomer A, then add moment t from the monomerjAdd to the monomer The end time t addedm, the additive amount of the monomer B is gradually decreased, and maintain the additive amount of the monomer A constant.
According to an aspect of the present invention, as shown in the formula (VI), the numerical value of the additive amount ratio is from G0/ G to Gj/ G is in It is now incremental variations, such as gradually incremental variations or linear increment variation.The present invention is to arbitrary neighborhood in the incremental variations There is no particular limitation for incremental amplitude (also referred to as step-length) between two values, as long as those skilled in the art think Effectively incremental degree is reached.Moreover, the incremental variations can be unique step incremental variations, it is also possible to not equal step Long incremental variations, are not particularly limited.As the step-length, generally such as can be in from 0.05% to 20% range Any value, or any value in from 0.1% to 5% range, but the present invention is not limited thereto.
According to an aspect of the present invention, as the additive amount ratio G0/ G, it is represented at least two monomer The initial time t added into the polymerization reaction system0, (instantaneous) the overall additive amount of at least two monomer relative to The ratio of overall additive amount G of at least two monomer in the entire monomer addition time t, also represents entire described The starting point and minimum value of incremental variations, for example can be any value in from 0.01% to 20% range, or from 0.1% Any value to 10% range, but the present invention is not limited thereto.In addition, as the additive amount ratio Gj/ G, it is represented Moment t is added in the monomerj, (instantaneous) the overall additive amount of at least two monomer is relative to the overall additive amount G Ratio, also represent the terminal and maximum value of the entire incremental variations, for example can be in from 20% to 75% range Any value in any value, or from 25% to 65% range, but the present invention is not limited thereto.
According to an aspect of the present invention, as shown in the formula (VI), the numerical value of the additive amount ratio is from Gj/ G to Gm/ G is in It is now variation of successively decreasing, such as gradually successively decrease variation or linear decrease variation.The present invention is to arbitrary neighborhood in the variation of successively decreasing There is no particular limitation for amplitude of successively decreasing (also referred to as step-length) between two values, as long as those skilled in the art think The degree effectively successively decreased is reached.Successively decrease variation moreover, the variation of successively decreasing can be unique step, is also possible to not equal step Long variation of successively decreasing, is not particularly limited.As the step-length, generally such as can be in from 0.05% to 20% range Any value, or any value in from 0.1% to 5% range, but the present invention is not limited thereto.
According to an aspect of the present invention, as the additive amount ratio Gj/ G, it, which is represented, adds the moment in the monomer tj, ratio of (instantaneous) the overall additive amount of at least two monomer relative to the overall additive amount G also represents entire The starting point and maximum value of the variation of successively decreasing, for example can be any value in from 20% to 75% range, or from Any value in 25% to 65% range, but the present invention is not limited thereto.In addition, as the additive amount ratio Gm/ G, its generation End time t from least two monomer to the polymerization reaction system that added in of tablem, at least two monomer Ratio of (instantaneous) the totality additive amount relative to the overall additive amount G, also represent the entire variation of successively decreasing terminal and Minimum value, for example can be any value in from 0.01% to 20% range, or appointing in from 0.1% to 10% range One numerical value, but the present invention is not limited thereto.
According to an aspect of the present invention, the additive amount ratio Gm/ the G and additive amount ratio G0/ G can be identical, can also be with Difference is not particularly limited.
According to an aspect of the present invention, as shown in the formula (VI), the numerical value of the additive amount ratio is from G0/ G to Gm/ G table Reveal the high distribution in the low centre in both sides, is very similar to Gaussian Profile.Therefore, according to embodiment of the present invention, In the state of ideal, using the numerical value of the additive amount ratio as ordinate, using the numerical value of side chain average carbon number X as horizontal seat Mark, and the initial time t added from least two monomer into the polymerization reaction system0It is changed to described at least two The end time t that kind monomer is added into the polymerization reaction systemmWhen, the relationship of the two meets or substantially conforming to Gauss Distribution, such as shown in formula (VII).Here, so-called " substantially conforming to ", refers to relationship and the formula (VII) institute of the two The Gaussian Profile shown is slightly offset, but the deviation is within the acceptable amplitude of those skilled in the art.
According to an aspect of the present invention, in the formula (VII), symbol x represents the arbitrary integer from 0 to m, symbol μ Any one numerical value in open interval (12.5,14.2) is represented, any one number in open interval (12.6,13.8) is preferably represented Value, symbol σ represent any one numerical value in open interval (0.5,2).π is pi, can generally take 3.141592654 or 3.14, e be natural constant, can generally take 2.718281828 or 2.72.
Embodiment
Hereinafter the present invention is illustrated using embodiment in further detail, but is not limited to these examples.
In embodiment and comparative example below, each monomer in copolymer and the respective content of flux oil and copolymer Content is calculated according to inventory.
In the context of the present invention, it is included in embodiment and comparative example below, each measurement method and calculation method It proceeds as follows.
Gel permeation chromatography 1. (GPC) Split Method
Operate instrument: 1515 type gel permeation chromatographs of Waters, US's production.Detector is Waters 2414 Differential refraction detector.Solvent used in configuration standard product is the chromatography pure tetrahydrofuran produced by Acros company.Chromatographic column by Waters company provides, and is 3 different pore size silicagel column series connection, and concrete specification is as follows:
(1)Waters HR 0.5THF, relative molecular weight measurement range 1-1000 (7.8 × 300mm),
(2)Waters HR 1THF, relative molecular weight measurement range 100-5000 (7.8 × 300mm),
(3)Waters HR 3THF, relative molecular weight measurement range 5000-600,000 (7.8 × 300mm)。
Operating condition: mobile phase is tetrahydrofuran, and flow rate of mobile phase 1.0mL/min, column temperature is 35 DEG C, detector temperature Degree is 35 DEG C, and sample volume is 200 μ L.
Splitting step: 0.02 to 0.2g sample being dissolved in 10mL tetrahydrofuran, is shaken up, and obtains homogeneous solution.Then will The solution carries out gpc analysis on the operation instrument under the operating conditions.There is chromatography from gel chromatography spectrogram Peak starts until the chromatographic peak terminates, and is divided into n based on the accumulation appearance time of the chromatographic peak using volumetric flask Section collects the efflux of detector outflux respectively.The n sections of efflux is respectively labeled as L1、L2、…、Ln.It repeats above-mentioned Operation 10 times merges each section of efflux collected every time.Then, tetrahydro is removed from each section of efflux respectively by 80 DEG C of distillations Furans obtains n sections of fractionation components, weighs respectively.Measure the number-average molecular weight Mn and molecular weight distribution Mw/ of every section of fractionation component Mn, and calculate every section and split the weight percent that component accounts for whole n sections of fractionation component weights, i.e. component accounting Y.
2. nuclear magnetic resonance analytic method
Operate instrument: Varian company, the U.S. production INOVA 500MHz nuclear magnetic resonance chemical analyser (1H-NMR), solid Double resonance probe (5mm).
Operating condition: operation temperature is room temperature, scanning times nt=1000, and tetramethylsilane=0 δ is calibrated in chemical shift, Mode of uncoupling dm=nny (inverted gated decoupling), heavy water lock field.
Analyzing step: sample is carried out1H-NMR characterization calculates the sample by parsing the nuclear magnetic spectrogram accordingly obtained Side chain average carbon number X.
Individually below with methacrylate polymers, acrylate polymer, fumarate polymer and alpha-olefines polymerization For closing object, the resolving of the nuclear magnetic spectrogram and the calculation method of the side chain average carbon number X, but this hair are illustrated Bright to be not limited to this, other polymer are also referred to the content and carry out similar parsing and calculate.
Only as an example, the methacrylate polymers or the acrylate polymer generally comprise following institute The structural unit shown.
According to1The notable difference of H-NMR spectrum can will be in its structural unit for methacrylate polymers Hydrogen atom is roughly divided into the H as shown in structural formulaA、HB、HC、HDFour regions, there are relationships shown in formula (1) in these regions.By In HCLocating chemical shift is by HBIt is covered, and HDLocate more difficult integral, it can be by HB、HCAnd HDJoint account.It therefore, can be by formula (1) formula (2) are transformed to, and are further derived as formula (3).
In these formula, X represents the side chain average carbon number of methacrylate polymers.
It is similar with the parsing of methacrylate polymers, the hydrogen atom in its structural unit can be roughly divided into such as structure H shown in formulaA、HB、HDThree regions can equally calculate the side chain average carbon number X of acrylate polymer, such as formula (4) It is shown.
Only as an example, the fumarate polymer generally comprises structural unit as follows.
Similar with the parsing of methacrylate polymers, the side chain that can equally calculate fumarate polymer is average Carbon number X, as shown in formula (5).
Only as an example, the alpha-olefine polymers generally comprise structural unit as follows.
Similar with the parsing of methacrylate polymers, the side chain that can equally calculate alpha-olefine polymers is averaged carbon Number X, as shown in formula (6).
For concrete example, if a certain methacrylate polymers have shown in nuclear magnetic spectrogram and integration data, Then the side chain average carbon number X=14.86 it is found that the methacrylate polymers is calculated by formula (3).
In embodiment and comparative example below, the property of lube base oil A to F is as in Table A.
Table A
Base oil number A B C
Rank API-Ⅱ6 API-Ⅲ6 150SN
100 DEG C of viscosity 5.67 5.54 5.46
/ (viscous m degree m2 refers to s- number 1) 112 121 90
Pour point/DEG C -18 -15 -15
Embodiment A
Under nitrogen protection, (Shuan Long company, board are purchased to equipped with addition 113kg flux oil in churned mechanically reaction kettle Number be 100N, similarly hereinafter), 83-91 DEG C is heated to, by 270kg the first monomer (decyl-octyl methacrylate/lauryl Base ester/methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/octadecyl methacrylate mixture, Wherein C10=61%, C12=20%, C14=12%, C16=5%, C18=2%, X=11.1), 1.35kg benzoyl peroxide It is added dropwise in reaction kettle with the mixture A of 1.08kg lauryl mercaptan, while by 150kg second comonomer (methacrylic acid ten Tetraalkyl ester/methacrylic acid cetyl ester/octadecyl methacrylate/methacrylic acid eicosane base ester mixing Object, wherein C14=27 weight %, C16=42%, C18=24%, C20=7 weight %, X=16.0), 0.75kg benzoyl peroxide first The mixture B of acyl and 0.6kg lauryl mercaptan is added dropwise in reaction kettle.In the initial time of dropwise addition, the dripping quantity of mixture A The ratio between the dripping quantity (kg/ hours) of (kg/ hours) and mixture B A/B is 4:1, and sum of the two is 20kg/ hours, then A/B It gradually decreases, sum of the two gradually increases, until A/B reaches 5:3, and it is small that sum of the two reaches 80kg/ at the time of dropwise addition 3 hours When.Then, A/B is gradually decreased, and sum of the two gradually decreases, until A/B reaches 1:2, sum of the two at the time of dropwise addition 6 hours Reach 15kg/ hours, completion of dropwise addition.Then, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.3kg peroxidating is then added Benzoyl and 113kg flux oil, being warming up to after being kept for 2 hours at 103 DEG C terminates polymerization reaction, obtains gradient copolymer J1.? This, the monomer conversion of the polymerization reaction is 99.1%, and the number-average molecular weight Mn of gradient copolymer J1 is 47120, and side chain is flat Equal carbon number X is 12.5.It using gradient copolymer J1 as sample, is split by GPC, obtains 5 sections of fractionation components.Described 5 sections are torn open Grouping point measures respectively, the results are shown in Table 1.
Table 1
Project 1 2 3 4 5
Component accounting Y/% 7.1 16.7 50 16.7 9.5
Side chain average carbon number X 12.21 12.42 12.80 13.71 14.13
Number-average molecular weight Mn 21542 35411 48214 54525 65214
Embodiment B
Under nitrogen protection, (Shuan Long company, board are purchased to equipped with addition 113kg flux oil in churned mechanically reaction kettle Number be 100N, similarly hereinafter), 83-91 DEG C is heated to, by the first monomer of 50kg (hexyl methacrylate/2-Propenoic acid, 2-methyl-, octyl ester/first The mixture of base decyl acrylate, wherein C6=71%, C8=21%, C10=8%, X=6.6), 0.32kg benzoyl peroxide first The mixture A of acyl and 0.21kg lauryl mercaptan is added dropwise in reaction kettle, while by 370kg second comonomer (methacrylic acid Dodecyl ester/methacrylic acid tetradecane base ester/methacrylic acid cetyl ester mixture, wherein C12=55 weights Measure %, C14=17 weight %, C16=28 weight %, X=13.3), 1.8kg benzoyl peroxide and 1.5kg lauryl mercaptan Mixture B be added dropwise in reaction kettle.In the initial time of dropwise addition, the dripping quantity (kg/ hours) of mixture A is with mixture B's The ratio between dripping quantity (kg/ hours) A/B is 7:1, and sum of the two is 12kg/ hours, and then A/B is gradually decreased, and sum of the two is gradually Increase, until A/B reaches 1:10, and sum of the two reaches 150kg/ hours at the time of dropwise addition 3 hours.Then, A/B is gradually decreased, Sum of the two gradually decreases, until A/B reaches 1:20, and sum of the two reaches 20kg/ hours at the time of dropwise addition 6 hours, is added dropwise Terminate.Then, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.3kg benzoyl peroxide and 113kg flux oil is then added, Being warming up to after being kept for 2 hours at 103 DEG C terminates polymerization reaction, obtains gradient copolymer J2.Here, the monomer of the polymerization reaction Conversion ratio is 98.3%, and the number-average molecular weight Mn of gradient copolymer J2 is 45975, and side chain average carbon number X is 12.0.It is total with gradient Polymers J2 is split as sample by GPC, obtains 8 sections of fractionation components.8 sections of fractionations component is measured respectively, as a result It is shown in Table 2.
Table 2
Project 1 2 3 4 5 6 7 8
Component accounting Y/% 4.2 5.9 8.5 9.6 43.1 14.4 8.4 6.0
Side chain average carbon number X 7.30 9.84 11.17 11.82 12.44 12.65 12.70 12.89
Number-average molecular weight Mn 19542 25057 31124 38512 44215 47045 50215 59021
Comparative example A
Gradient copolymer is prepared according to the method for embodiment A, unlike, the first monomer and second comonomer are uniformly mixed It is added dropwise in reaction system with constant rate of speed again later, specifically:
Under nitrogen protection, to equipped with 113kg flux oil is added in churned mechanically reaction kettle, it is heated to 83-91 DEG C, it will The first monomer of 270kg (decyl-octyl methacrylate/lauryl methacrylate/methacrylic acid tetradecane base ester/methyl Aliphatic acrylate/octadecyl methacrylate mixture, wherein C10=61%, C12=20%, C14= 12%, C16=5%, C18=2%, X=11.1), 150kg second comonomer (methacrylic acid tetradecane base ester/methacrylic acid Cetyl ester/octadecyl methacrylate/methacrylic acid eicosane base ester mixture, wherein C14=27 weights Measure %, C16=42%, C18=24%, C20=7 weight %, X=16.0), 2.1kg benzoyl peroxide and 1.68kg 12 The mixture of alkyl hydrosulfide was added dropwise in reaction kettle with 70kg/ hours constant rate of speed, and time for adding is 6 hours, completion of dropwise addition When, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.3kg benzoyl peroxide and 113kg flux oil is then added, is warming up to Reaction was completed after being kept for 2 hours at 103 DEG C, obtains copolymer DJ1.Here, the monomer conversion of the polymerization reaction is The number-average molecular weight Mn of 99.3%, copolymer DJ1 are 41768, and side chain average carbon number X is 12.5.Using copolymer DJ1 as sample Product are split by GPC, obtain 5 sections of fractionation components.5 sections of fractionations component is measured respectively, the results are shown in Table 3.
Table 3
Project 1 2 3 4 5
Component accounting Y/% 13.2 17.5 30.0 21.1 18.2
Side chain average carbon number X 12.41 12.54 12.54 12.47 12.40
Number-average molecular weight Mn 32154 39024 45145 52153 59213
Embodiment C
Under nitrogen protection, (Shuan Long company, board are purchased to equipped with addition 113kg flux oil in churned mechanically reaction kettle Number be 100N, similarly hereinafter), 83-91 DEG C is heated to, by 150kg the first monomer (decyl-octyl methacrylate/lauryl The mixture of base ester, wherein C10=50%, C12=50%, X=10.9), 0.75kg benzoyl peroxide and 0.7kg dodecane The mixture A of base mercaptan is added dropwise in reaction kettle, and first 4 hours, the charging rate of the first monomer mixture was maintained at 10kg/ hours It is at the uniform velocity added dropwise, while by the (lauryl methacrylate/methacrylic acid tetradecane base ester mixing of 100kg second comonomer Object, wherein C12=70 weight %, C14=30%, X=12.5), 0.6kg benzoyl peroxide and 0.55kg lauryl mercaptan Mixture B be added dropwise in reaction kettle.In the initial time of dropwise addition, the dripping quantity (kg/ hours) of mixture A is with mixture B's The ratio between dripping quantity (kg/ hours) A/B is 2:1, and sum of the two is 15kg/ hours, and then B is gradually increased, and sum of the two gradually increases Add, until A/B reaches 1:3 at the time of dropwise addition 4 hours, sum of the two reaches 80kg/ hours, and second comonomer charging at this time terminates, This moment, by the Third monomer of 170kg (methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/methacrylic acid ten The mixture of eight alkyl ester mixtures, wherein C14=64 weight %, C16=25%, C18=11%, X=14.8), 0.8kg peroxide The mixture C for changing benzoyl and 0.7kg lauryl mercaptan is added dropwise in reaction kettle, at this point, (kg/ is small for the dripping quantity of mixture A When) it with the ratio between the dripping quantity (kg/ hour) of mixture C A/C is 1:2, sum of the two is 100kg/ hours, and then A is gradually decreased, Sum of the two gradually decreases, until A/C reaches 1:3, and sum of the two reaches 10kg/ hours at the time of continuing to be added dropwise 5 hours, drop Add end.Then, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.5kg benzoyl peroxide and 113kg dilution is then added Oil, being warming up to after being kept for 2 hours at 103 DEG C terminates polymerization reaction, obtains gradient copolymer J3.Here, the polymerization reaction Monomer conversion is 99.6%, and the number-average molecular weight Mn of gradient copolymer J3 is 52120, and side chain average carbon number X is 11.8.With ladder Copolymer J3 is spent as sample, is split by GPC, is obtained 5 sections of fractionation components.5 sections of fractionations component is measured respectively, It the results are shown in Table 4.
Table 4
Project 1 2 3 4 5
Component accounting Y/% 8.2 24.5 38.8 22.4 6.1
Side chain average carbon number X 11.70 11.91 12.36 13.68 13.90
Number-average molecular weight Mn 20023 35289 50317 62527 74924
Embodiment D
Prepare 5 kinds of different methacrylic acid straight chained alkyl ester monomer mixture A to E, the composition of each mixture such as 5 institute of table Show.
Table 5
Under nitrogen protection, (Shuan Long company, board are purchased to equipped with addition 113kg flux oil in churned mechanically reaction kettle Number it is 100N, similarly hereinafter), it is heated to the 92-100 DEG C of initial time in dropwise addition, mixture A was with 10kg/ hour constant airspeed drops Add and closely enters in reaction kettle, meanwhile, mixture B was added dropwise with 5kg/ hours speed, and the charging rate of mixture B gradually increases, when When reaching 2h, mixture A and mixture B charging terminate, and then mixture C and mixture D are added dropwise to reaction kettle, mixture C The ratio between the dripping quantity (kg/ hours) of dripping quantity (kg/ hours) and mixture D C/D is 3:1, and sum of the two is 60kg/ hours, so C is gradually decreased afterwards, and mixture D gradually increases, and sum of the two gradually increases, until C/D reaches 1:1 at the time of dropwise addition 5 hours, Sum of the two reaches 130kg/ hours, at this point, mixture C completion of dropwise addition, is then added dropwise to reaction kettle for mixture E, mixes at this time Closing the ratio between the dripping quantity (kg/ hours) of object D and the dripping quantity (kg/ hours) of mixture E D/E is 10:1, and sum of the two is 130kg/ hours, then D was gradually decreased, and sum of the two gradually decreases, until D/E reaches 1:1, the two at the time of dropwise addition 7 hours The sum of reach 13kg/ hours, completion of dropwise addition.Then, reaction kettle continues to be kept for 1 hour at 100 DEG C, and 0.3kg is then added Benzoyl peroxide and 113kg flux oil terminate polymerization reaction after being warming up to 103 DEG C of holdings 2 hours, obtain gradient copolymer J4.Here, the monomer conversion of the polymerization reaction is 99.2%, the number-average molecular weight Mn of gradient copolymer J4 is 39120, side Chain average carbon number X is 12.14.It using gradient copolymer J4 as sample, is split by GPC, obtains 8 sections of fractionation components.To described 8 Section splits component and measures respectively, the results are shown in Table 6.
Table 6
Project 1 2 3 4 5 6 7 8
Component accounting Y/% 3.2 6.3 11.9 15.1 26.2 23.8 11.1 2.4
Side chain average carbon number X 8.00 9.64 12.05 12.00 12.23 13.16 13.50 14.13
Number-average molecular weight Mn 18154 25124 30147 34987 37651 40154 49872 58326
According to additional amount as defined in table 7, gradient copolymer J1 to J4 and copolymer DJ1 is added in base oil respectively.Respectively The dosage of copolymer, the type of base oil and gained pour point depression test result are shown in Table 7.
Table 7
By comparative example and comparative example acquired results it is found that the gradient copolymer that obtains of the present invention is to various kinds of lubricating oil Base oil shows excellent depression effeCt.Moreover, even if additive amount is few, under the pour point of lube base oil is still obvious Drop, the gradient copolymer for showing that the present invention obtains also have significant depression effeCt.
Embodiment E
Under nitrogen protection, (Shuan Long company, board are purchased to equipped with addition 113kg flux oil in churned mechanically reaction kettle Number it is 100N, similarly hereinafter), it is heated to 83-91 DEG C, with 50kg/ hours stabilized speeies by 270kg the first monomer [methacrylic acid Last of the ten Heavenly stems ester/lauryl methacrylate/methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/metering system Sour stearyl (C10=28%, C12=32%, C14=28%, C16=8%, C18=4%), X=12.3], 1.35kg The mixture A of benzoyl peroxide and 1.08kg lauryl mercaptan is added dropwise in reaction kettle, is stablized charging 3 hours, is then dripped Rate of acceleration linearly reduces, so that flow-reduction was to 30kg/ hours when the combined feed time was to 6 hours.Simultaneously with 10kg/ hours Initial velocity be added dropwise 150kg second comonomer [methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/methyl-prop Olefin(e) acid stearyl/methacrylic acid eicosane base ester (C14=38%, C16=20%, C18=25%, C20=17%, X= 16.2], the mixture B of 0.75kg benzoyl peroxide and 0.6kg lauryl mercaptan is added dropwise in reaction kettle, at mixture B Additive amount be linearly increasing so that flow increases to 30kg/ hours, then keeps the stream when the combined feed time was to 3 hours Amount charging 3 hours.A, when the equal completion of dropwise addition of B mixture, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.3kg mistake is then added Benzoyl Oxide and 113kg flux oil, are warming up to after being kept for 2 hours at 103 DEG C that reaction was completed, obtain pour depressant for lubricating oil J5, Wherein, monomer conversion is 99.1% in pour depressant for lubricating oil J5, and the number-average molecular weight of gradient copolymer J5 is 40120, side chain Average carbon number X is 13.5.It using gradient copolymer J5 as sample, is split by GPC, obtains 5 sections of fractionation components.To described 5 sections It splits component to measure respectively, the results are shown in Table 8.
Table 8
Project 1 2 3 4 5
Component accounting Y/% 17.0 19.5 28.4 18.2 16.8
Side chain average carbon number X 12.90 13.21 13.54 13.83 14.01
Number-average molecular weight Mn 25987 34561 41250 48647 57854
Embodiment F
Under nitrogen protection, to equipped with 113kg flux oil is added in churned mechanically reaction kettle, it is heated to 83-91 DEG C, with 40kg/ hours initial velocities are by the first monomer of 171kg [methacrylic acid octyl ester/methacrylic acid decane base ester/methyl-prop Olefin(e) acid dodecyl ester/methacrylic acid tetradecane base ester (C8=12%, C10=15%, C12=48%, C14=25%), X =11.5], the mixture A of 0.9kg benzoyl peroxide and 0.7kg lauryl mercaptan is added in reaction kettle, then linear Slowly reduce, so that flow-reduction was to 32kg/ hour, then linear quickly reduction when the combined feed time was to 3 hours, so that When the combined feed time was to 6 hours, flow-reduction was to 10kg/ hours.Simultaneously in the initial velocity dropwise addition with 20kg/ hours 255kg second comonomer [methacrylic acid tetradecane base ester/methacrylic acid cetyl ester/octadecyl methacrylate/ Methacrylic acid eicosane base ester (C14=38%, C16=20%, C18=25%, C20=17%, X=16.2], 0.9kg mistake The mixture B of Benzoyl Oxide and 0.7kg lauryl mercaptan is added in reaction kettle, set at feed inlet B pump flow as It is linearly increasing, so that flow increases to 50kg/ hours when the combined feed time was to 3 hours, then keep flow charging 3 small When.A, at the end of the addition of B mixture, reaction kettle continues to be kept for 1 hour at 95 DEG C, and 0.3kg benzoyl peroxide is then added It with 113kg flux oil, is warming up to after being kept for 2 hours at 103 DEG C that reaction was completed, obtains pour depressant for lubricating oil J6, wherein lubricating oil Monomer conversion is 99.4% in pour-point depressant J6, number-average molecular weight 41702, and side chain average carbon number X is 14.0.It is total with gradient Polymers J6 is split as sample by GPC, obtains 5 sections of fractionation components.5 sections of fractionations component is measured respectively, is tied Fruit is shown in Table 9.
Table 9
Project 1 2 3 4 5
Component accounting Y/% 18.8 16.5 25.3 20.3 19.2
Side chain average carbon number X 12.81 13.30 14.00 14.86 15.10
Number-average molecular weight Mn 23781 34217 41702 51514 59248
Raw materials used source is shown in Table 10 in the present invention.
Table 10
Preparation of greases
Embodiment 1
Material component: (100 DEG C of viscosity are 10.2mm to Yanshan Petrochemical 500SN base oil 900kg2/s)；Lithium hydroxide 9.88kg；12- hydroxy stearic acid 68.63kg；Benzotriazole 20kg；2,6- toluene di-tert-butyl phenol 5kg；The copolymerization of J1 gradient Object 5kg.
The preparation of lithium base grease:
First the 12- hydroxy stearic acid of 650kg base oil, 68.63kg are added in rouge kettle processed, heating stirring.Temperature rises to Lithium hydroxide aqueous solution 29.88kg (wherein 9.88kg containing lithium hydroxide, water 20kg) saponification 60min is added at 95 DEG C, after It is continuous to be warming up to 220 DEG C of progress high temperature refining 20min；After addition 250kg base oil cools to 100 DEG C, 2,6- di-t-butyl is added The J1 gradient copolymer of p-cresol 5kg, 20kg benzotriazole, 5kg, stirs evenly；3 times are ground into rouge by three-roller.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: 7 weight of 12- hydroxy lithium stearate Measure %；90 weight % of lubricating base oil；0.5 weight % of J1 gradient copolymer；2,6- toluene di-tert-butyl phenol, 0.5 weight %, Benzotriazole weight 2%.
Embodiment 2
Material component: (100 DEG C of viscosity are 5.5mm to double dragon 150N base oil 700kg2/s)；Sodium hydroxide 3.36kg；It is stearic Sour 23.20kg；Beta naphthal 20kg；N- oleoylsarcosine octadecylamine salt 10kg；J2 gradient copolymer 10kg.
The preparation of sodium base grease:
First the stearic acid of 500kg lubricating base oil, 23.20kg are added in rouge kettle processed, heating stirring.Temperature rises to 85 DEG C When be added sodium hydrate aqueous solution 13.36kg (wherein 3.36kg containing sodium hydroxide, water 10kg) saponification 40min, after of continuing rising Temperature to 190 DEG C of progress high temperature refine 5min；After addition 200kg lubricating base oil cools to 120 DEG C, the N- oleoyl of 10kg is added The J2 gradient copolymer of base sarcosine octadecylamine salt, beta naphthal 20kg, 10kg, stirs evenly；By three-roller grind 3 times at Rouge.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: 25 weight % of odium stearate；Profit Sliding 70 weight % of base oil；1 weight % of gradient copolymer, 2 weight %, N- oleoylsarcosine octadecylamine salt of beta naphthal, 1 weight Measure %.
Embodiment 3
Material component: Mobil 500N base oil 1392kg (100 DEG C of viscosity are 10.5mm2/s)；Calcium hydroxide 20kg；It is stearic Sour 150kg；2- naphthylamines 8kg；Lanolin calcium 32kg；J3 gradient copolymer 8kg.
The preparation of anhydrous calcium-base grease:
1100kg base oil and stearic acid 150kg are added in rouge kettle processed, heating stirring, when temperature rises to 95 DEG C, 20kg calcium hydroxide and 50kg water is added, carries out saponification 0.6h；15min is kept after being warming up to 145 DEG C after having reacted；It is added 32kg lanolin calcium is added in 292kg base oil when being cooled to 110 DEG C, the J3 gradient copolymer of 2- naphthylamines 8kg, 8kg, stirring is It is even；3 times are ground into rouge by three-roller.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: 10 weight % of calcium stearate；Profit Sliding 87 weight % of base oil；0.5 weight %, 2- naphthylamines of J3 gradient copolymer 0.5 weight %, 2 weight % of lanolin calcium.
Embodiment 4
Material component: (100 DEG C of viscosity are 7.5mm to shell 250N base oil 1320kg2/s)；Calcium hydroxide 28.62kg； 12- hydroxy stearic acid 225.72kg；2,6- toluene di-tert-butyl phenol 16kg；17 alkenyl imidazoline 8kg of 2- amino-ethyl；J4 Gradient copolymer 16kg.
The preparation of anhydrous calcium-base grease:
1000kg base oil and 12- hydroxy stearic acid 225.72kg are added in rouge kettle processed, heating stirring, when temperature liter When to 95 DEG C, 28.62kg calcium hydroxide and 50kg water is added, carries out saponification 1h；It is kept after being warming up to 145 DEG C after having reacted 10min；It is added when 320kg base oil is cooled to 110 DEG C and 2,6- toluene di-tert-butyl phenol 16kg, 2- amino-ethyl 17 is added The J4 gradient copolymer of alkenyl imidazoline 8kg, 16kg, stir evenly；3 times are milled into rouge by three-roller.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: 15 weight of 12- hydroxy stearic acid calcium Measure %；82.5 weight % of lubricating base oil；1 weight % of J4 gradient copolymer, 2,6- toluene di-tert-butyl phenol 1 weight %, 2- 17 alkenyl imidazoline of amino-ethyl, 0.5 weight %.
Comparative example 1
Material component: in addition to without gradient copolymer, remaining is the same as embodiment 1.Comparative example is prepared with 1 method of embodiment 1 lubricating grease.
Comparative example 2
Material component: in addition to gradient copolymer is DJ1, remaining is the same as embodiment 2.Comparison is prepared with 2 method of embodiment The lubricating grease of example 2.
Comparative example 3
Material component: in addition to without gradient copolymer, remaining is the same as embodiment 3.Comparative example is prepared with 3 method of embodiment 3 lubricating grease.
Comparative example 4
Material component: in addition to gradient copolymer is DJ1, remaining is the same as embodiment 4.Comparison is prepared with 4 method of embodiment The lubricating grease of example 4.
Dropping point, cone penetration, Stencil oil-dividing, low temperature have been carried out to the lubricating grease of embodiment and comparative example obtained above respectively Torque, the qualification test of similar viscosity, water leaching number of dropouts.Test method are as follows: dropping point uses 3498 method of GB/T, and cone penetration is adopted With 269 method of GB/T, Stencil oil-dividing uses 0324 method of SH/T, and low temperature torque uses 0338 method of SH/T, and similar viscosity is adopted With 0048 method of SH/T, water drenches number of dropouts and uses 0109 method of SH/T.Assessment of performance the results are shown in Table 11.
The assessment of performance of 11 lubricating grease of table

Claims (9)

1. a kind of lubricating grease, including following components: gradient copolymer, thickening agent, antioxidant, antirust agent and lubricating base oil；Institute The manufacturing method for stating gradient copolymer includes: that at least two monomers are added into polymerization reaction system, makes at least two list The step of addition copolymerization reaction (especially free radical addition copolyreaction), occurs for body, wherein at least two monomer is respectively only Formula (I) compound represented and/or its mixture are on the spot represented,
In formula (I),
Group R1Represent H orIt is preferred that H is represented,
Group R2Represent H or C1-4Linear or branched alkyl group preferably represents H or methyl,
Symbol a represents 0 or 1, preferably represents 1,
Group R' represents H or group R3, preferably represent group R3,
Group R3Represent C1-C30Linear or branched alkyl group preferably represents C6-C24Linear or branched alkyl group more preferably represents C6-C20 Straight chained alkyl,
If the initial time that at least two monomer is added into the polymerization reaction system is t0, end time tm, then institute The monomer addition time for stating at least two monomers is t (t=tm-t0), when the monomer addition time is divided into m equal portions, Symbol m represents an integer in closed interval [5, ∞], preferably represents an integer in closed interval [8, ∞], the preferably described symbol The upper limit of integer representated by number m is 20000,10000,5000,1000,500,200,100 or 50, is added in any monomer Moment tx, the relative scale that at least two monomer is added into the polymerization reaction system makes single by described at least two The nuclear magnetic resonance method side chain average carbon atom number X for the mixture that body is constituted according to the relative scalexMeet following relationship, accords with Number x represents the arbitrary integer from 0 to m,
X0<X1<…<Xm-1<Xm (V)
It is preferred that from X0To XmIt is gradually increased, more preferably from X0To XmIt is linear to increase.
2. lubricating grease described in accordance with the claim 1, which is characterized in that be wherein located at the end time t of the monomer additionm, institute The sum of the accumulative additive amount of at least two monomers within the monomer addition time into the polymerization reaction system is stated as G, and And it is located at any monomer addition moment tx, the sum of the additive amount of at least two monomer into the polymerization reaction system is Gx, Symbol x represents the arbitrary integer from 0 to m, and following relationship is set up,
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G (VI)
In formula (VI), symbol j represents an integer in closed interval [m/4,3m/4], preferably represents closed interval [m/3,2m/3] An interior integer more preferably represents an integer in closed interval [2m/5,3m/5], and G0+G1+…+Gj+…+Gm-1+Gm= G,
It is preferred that from G0/ G to Gj/ G is gradually increased, more preferably from G0/ G to Gj/ G linearly increases, or from Gj/ G to Gm/ G gradually drops It is low, more preferably from Gj/ G to Gm/ G linear reduction,
More preferable Gx/ G and XxMeet following relationship,
In formula (VII), symbol μ represents any one numerical value in open interval (12.5,14.2), preferably represents open interval Any one numerical value in (12.6,13.8), symbol σ represent any one numerical value in open interval (0.5,2).
3. lubricating grease according to claim 2, which is characterized in that wherein group R3Represent C10-C18Linear or branched alkyl group The formula (I) compound represented account for whole monomer dosages ratio (by mole be in terms of) for from 40% to 95%, preferably from 55% to 95%.
4. lubricating grease described in accordance with the claim 3, which is characterized in that the wherein X0It represents in closed interval [6.5,12.5] Any one numerical value preferably represents any one numerical value or the X in closed interval [7.8,12.0]mRepresent closed interval Any one numerical value in [13.8,19.5] preferably represents any one numerical value in closed interval [14.5,18.2].
5. lubricating grease according to claim 4, which is characterized in that wherein ratio Gj/ G be from 20% to 75%, preferably from 25% to 65% or ratio G0/ G or ratio Gm/ G is from 0.01% to 20%, preferably from 0.1% to 10%.
6. lubricating grease according to claim 5, which is characterized in that wherein the reaction temperature of the copolyreaction is from 50 DEG C To 180 DEG C, preferably from 55 DEG C to 165 DEG C, more preferably from 60 DEG C to 150 DEG C, the reaction time of the copolyreaction is from 1 hour To 24 hours, preferably from 1.5 hours to 20 hour, the monomer addition time t be from 0.5 hour to 12 hour, it is preferably small from 1 Up to 10 hours.
7. according to lubricating grease described in one of claim 1-6, which is characterized in that on the basis of lubricating grease total weight, wherein The gradient copolymer accounts for 0.01%~10% (preferably 0.5%~2%) of lubricating grease total weight；The thickening agent accounts for lubricating grease 1%~30% (preferably 5%~25%) of total weight；The antioxidant accounts for the 0.1%~10% of lubricating grease gross mass (preferably 0.5%-2%)；The antirust agent accounts for 0.1%~10% (preferably 0.5%-2%) of lubricating grease gross mass；The lubrication base Oil constitutes the main component of lubricating grease.
8. according to lubricant oil composite described in one of claim 1-6, which is characterized in that it is thick that the thickening agent is selected from lithium base One of agent, calcium base thickening agent, anhydrous calcium base thickening agent, sodium base thickening agent and barium base thickening agent are a variety of；The antioxygen Agent is phenolic antioxidant；The antirust agent is esters antirust agent, organic amine antirust agent, sulfur heterocyclic ring or nitrogen-containing heterocycle class antirust One of agent is a variety of；The lubricating base oil is selected from one of I class of API, II class, III class, IV class and V class base oil Or it is a variety of.
9. a kind of preparation of greases method, comprising: mix thickening agent described in one of claim 1-8 and lubricating base oil It closes uniformly, is refined in 100-200 DEG C of constant temperature, it is cooling, gradient copolymer, antioxidant described in one of claim 1-8 is added And antirust agent, it is ground into rouge.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1193024A (en) * 1997-02-27 1998-09-16 罗姆和哈斯公司 Process for preparing copolymer of continuously changeable components
EP1086964A2 (en) * 1999-09-22 2001-03-28 Ethyl Corporation (Meth) acrylate copolymer pour point depressants
WO2001040333A1 (en) * 1999-11-30 2001-06-07 Rohmax Additives Gmbh Gradient copolymers and method for the production thereof and their use
CN104371796A (en) * 2014-10-25 2015-02-25 中国石油化工股份有限公司 Low-temperature lubricating grease composition and preparation method thereof
CN105585657A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Lubricant oil pour point depressant and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1193024A (en) * 1997-02-27 1998-09-16 罗姆和哈斯公司 Process for preparing copolymer of continuously changeable components
EP1086964A2 (en) * 1999-09-22 2001-03-28 Ethyl Corporation (Meth) acrylate copolymer pour point depressants
WO2001040333A1 (en) * 1999-11-30 2001-06-07 Rohmax Additives Gmbh Gradient copolymers and method for the production thereof and their use
CN1382166A (en) * 1999-11-30 2002-11-27 罗麦斯添加剂有限公司 Gradient copolymers and method for producing and use thereof
CN105585657A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Lubricant oil pour point depressant and preparation method thereof
CN104371796A (en) * 2014-10-25 2015-02-25 中国石油化工股份有限公司 Low-temperature lubricating grease composition and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
樱井俊男: "《石油产品添加剂》", 30 November 1980, 石油工业出版社 *

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