CN112694933A - Hydraulic oil composition and manufacturing method thereof - Google Patents

Hydraulic oil composition and manufacturing method thereof Download PDF

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Publication number
CN112694933A
CN112694933A CN201911006391.7A CN201911006391A CN112694933A CN 112694933 A CN112694933 A CN 112694933A CN 201911006391 A CN201911006391 A CN 201911006391A CN 112694933 A CN112694933 A CN 112694933A
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China
Prior art keywords
monomers
acrylic acid
methyl
monomer
alkyl ester
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鱼鲲
张耀
李云鹏
李勇
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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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Priority to CN201911006391.7A priority Critical patent/CN112694933A/en
Publication of CN112694933A publication Critical patent/CN112694933A/en
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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
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate

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  • 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 provides a hydraulic oil composition and a manufacturing method thereof. The hydraulic oil composition of the present invention comprises: (A) a copolymer composition; (B) an antiwear agent; (C) a rust inhibitor; (D) a metal deactivator; (E) an antioxidant; (F) a base oil; the method for producing the copolymer composition comprises the step of adding at least two monomers to a polymerization reaction system, and subjecting the at least two monomers to addition copolymerization, wherein the at least two monomers each independently represent a compound represented by the formula (I) and/or a mixture thereof,
Figure DDA0002242901710000011
in the formula (I), the radical R1Is C1‑C18A linear or branched alkyl group; radical R2Is H or methyl. The hydraulic oil composition disclosed by the invention has excellent low-temperature performance, shear stability, thermal stability and comprehensive performance, is high in viscosity index, and can meet the use condition of hydraulic equipment in extremely cold regions.

Description

Hydraulic oil composition and manufacturing method thereof
Technical Field
The invention relates to the field of lubricating oil, in particular to a hydraulic oil composition and a manufacturing method thereof.
Background
At present, energy conservation and environmental protection become main driving forces for the development of hydraulic oil, and new requirements are provided for the viscosity, viscosity-temperature performance, low-temperature performance and the like of lubricating oil. The high-viscosity index multistage hydraulic oil can effectively reduce the friction and wear of equipment during cold start, and the application range of a wide temperature range can reduce the labor cost of oil change in winter in a low-temperature area and the loss caused by equipment stagnation. Meanwhile, the higher kinematic viscosity at high temperature is also beneficial to improving the wear resistance of the oil product. Therefore, the ultra-low temperature hydraulic oil with the ultra-high viscosity index is the first choice of the existing hydraulic equipment, in particular to the hydraulic equipment for field operation.
The ultra-high viscosity index ultra-low temperature hydraulic oil is divided into a fully synthetic type and a mineral oil type. The fully synthetic hydraulic oil usually adopts PAO or synthetic ester as base oil, has excellent viscosity-temperature performance, but has overhigh price. The mineral oil type ultra-high viscosity index ultra-low temperature hydraulic oil generally adopts a mode of adding a viscosity index improver and a pour point depressant in cooperation with hydroisomerized base oil to improve the viscosity temperature performance and low-temperature fluidity of an oil product, so that the excellent viscosity index improver is of great importance.
Although the prior polymethacrylate viscosity index improver can improve the viscosity-temperature performance of lubricating oil, the prior polymethacrylate viscosity index improver still has great room for improvement. With the development of lubricating oil, higher requirements are also put on the performance of the viscosity index improver. In view of this, there is still a need in the art for new viscosity index improvers with improved properties.
Disclosure of Invention
The invention provides a hydraulic oil composition and a manufacturing method thereof.
The hydraulic oil composition of the present invention comprises: (A) a copolymer composition; (B) an antiwear agent; (C) a rust inhibitor; (D) a metal deactivator; (E) an antioxidant; (F) a base oil;
wherein the method for producing the copolymer composition comprises the step of adding at least two monomers to a polymerization reaction system, and subjecting the at least two monomers to addition copolymerization reaction (particularly radical addition copolymerization reaction), wherein the at least two monomers each independently represent a compound represented by formula (I) and/or a mixture thereof,
Figure BDA0002242901700000021
in the formula (I), the compound represented by the formula (I),
radical R1Is C1-C18A linear or branched alkyl group;
radical R2Is H or methyl;
setting the initial time of adding the at least two monomers into the polymerization reaction system as t0The termination time is tmThen the monomer addition time of the at least two monomers is t (t ═ t)m-t0) When the monomer addition time is divided into m equal parts, the symbol m represents a closed interval [2, ∞ [ ]]An integer within (preferably representing a closed interval [5, ∞.)]Preferably the upper limit of the integer denoted by the symbol m is 20000, 10000, 5000, 1000, 500, 200, 100 or 50), at any monomer addition time txThe relative proportions of the at least two monomers added to the polymerization system being such that the average number of carbon atoms in the side chain X is the average number of carbon atoms in the NMR of a mixture of the at least two monomers in the relative proportionsxSatisfying the following relationship, the symbol x represents any integer from 0 to m,
X0<X1<…<Xj<…<Xm-1<Xm (II)
wherein the termination time t of the monomer addition is setmThe sum of the cumulative addition amounts of the at least two monomers to the polymerization reaction system within the monomer addition time is G, and is set at any monomer addition time txThe sum of the addition amounts of the at least two monomers to the polymerization reaction system is GxThe symbol x represents an arbitrary integer from 0 to m, and the following relational expression holds,
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G (III)
in formula (III), the symbol j represents a closed interval [ m/4, 3m/4 ]]An integer within (preferably representing a closed interval [ m/3, 2 m/3)]An integer within, more preferably representing a closed interval [2m/5, 3m/5]An integer of) and G)0+G1+…+Gj+…+Gm-1+Gm＝G；
Wherein the termination time t of the monomer addition is setmCumulatively adding, by mass, a group R to the polymerization system1Is C1-C7The amount of the linear chain or branched chain alkyl monomer accounts for 5 to 50 percent (preferably 7 to 45 percent) of the sum G of the cumulative addition amounts; cumulatively adding a group R to the polymerization system1Is C8-C18The amount of the linear or branched alkyl monomer is 50 to 95% (preferably 55 to 93%) of the sum G of the above-mentioned cumulative amounts.
The method for producing the copolymer composition according to the present invention, wherein XjRepresents a closed interval [9.0, 12.5]]Any value within, preferably representing a closed interval [9.5, 12.2]]Any one of the values in (b). The method for producing the copolymer composition according to the present invention, wherein the at least two monomers are selected from the group consisting of (meth) acrylic acid C1Straight-chain alkyl ester, (meth) acrylic acid C2Straight-chain alkyl ester, (meth) acrylic acid C3Straight chain/branched chain alkyl ester and (methyl) acrylic acid C4Straight chain/branched chain alkyl ester and (methyl) acrylic acid C5Straight chain/branched chain alkyl ester and (methyl) acrylic acid C6Straight chain/branched chain alkyl ester and (methyl) acrylic acid C7Straight chain/branched chain alkyl ester and (methyl) acrylic acid C8Straight chain/branched chain alkyl ester and (methyl) acrylic acid C9Straight chain/branched chain alkyl ester and (methyl) acrylic acid C10Straight chain/branched chain alkyl ester and (methyl) acrylic acid C11Straight chain/branched chain alkyl ester and (methyl) acrylic acid C12Straight chain/branched chain alkyl ester and (methyl) acrylic acid C13Straight chain/branched chain alkyl ester and (methyl) acrylic acid C14Straight chain/branched chain alkyl ester and (methyl) acrylic acid C15Straight chain/branched chain alkyl ester, (meth) propyleneAcid C16Straight chain/branched chain alkyl ester and (methyl) acrylic acid C18Straight chain \ branched chain alkyl ester.
The method for producing the copolymer composition according to the present invention, wherein X is0Represents a closed interval [6.5, 12 ]]Any value within (preferably representing a closed interval [6.8, 11.5 ]]Any one value of) the X groupmRepresents a closed interval [12.2, 18 ]]Any value within (preferably representing a closed interval [12.5, 17.5 ]]Any one of the values in (c).
The method for producing the copolymer composition according to the present invention, wherein the ratio GjG is from 20% to 75% (preferably from 25% to 65%), or the ratio G0G or the ratio Gmthe/G is from 0.01% to 20% (preferably from 0.1% to 10%).
The method for producing a copolymer composition according to the present invention, wherein the reaction temperature of the copolymerization reaction is from 50 ℃ to 180 ℃ (preferably from 55 ℃ to 165 ℃, more preferably from 60 ℃ to 150 ℃), the reaction time of the copolymerization reaction is from 1 hour to 24 hours (preferably from 1.5 hours to 20 hours), and the monomer addition time t is from 0.5 hours to 12 hours (preferably from 1 hour to 10 hours).
According to the present invention, said component (a) represents from 3% to 45% (preferably from 5% to 35%) of the total mass of said lubricating oil composition; the component (B) accounts for 0.1 to 10 percent (preferably 0.2 to 5 percent) of the total mass of the lubricating oil composition; the component (C) accounts for 0.01 to 10 percent (preferably 0.1 to 5 percent) of the total mass of the lubricating oil composition; the component (D) accounts for 0.01 to 5 percent (preferably 0.02 to 3 percent) of the total mass of the lubricating oil composition; the component (E) accounts for 0.1 to 10 percent (preferably 0.2 to 5 percent) of the total mass of the lubricating oil composition; the component (F) constitutes the main component of the lubricating oil composition.
According to the invention, the component (B) is preferably selected from one or more of polysulfide compound, phosphate ester, sulfur phosphate ester and sulfur nitrogen phosphorus type extreme pressure antiwear agent, more preferably from composite antiwear agent containing polysulfide, phosphate ester and sulfur nitrogen phosphorus type extreme pressure antiwear agent, wherein the polysulfide accounts for 30% -60%, preferably 40% -50% of the total mass of the composite antiwear agent, the phosphate ester accounts for 15% -40%, preferably 20% -40% of the total mass of the composite antiwear agent, and the sulfur nitrogen phosphorus type extreme pressure antiwear agent accounts for 5% -30%, preferably 10% -30% of the total mass of the composite antiwear agent. Common commercial products of the polysulfides include TPS32, T321, T323, preferably T323, common commercial products of the phosphate esters include T306, T304, preferably T306; common commercial products of the thiophosphornitrogen-type extreme pressure antiwear agent include T305, T307, T308, preferably T307 and T308.
According to the present invention, the component (C) is preferably selected from one or more of sulfonate, alkenyl succinic acid, alkenyl succinic anhydride and alkenyl succinic acid ester, more preferably sulfonate, and common commercial products include T705, T746, T747, preferably T705.
According to the present invention, said component (D) is preferably selected from benzotriazole derivatives and/or thiadiazole derivatives, more preferably benzotriazole derivatives, common commercial products including T706, T551, T561, preferably T706.
According to the present invention, the component (E) is preferably selected from one or more of thiophenol type, hindered phenol type, hindered amine type and phenolic ester type antioxidants, for example, thiophenol type antioxidants may be selected from T535, L115, L118, hindered phenol type antioxidants may be selected from one or more of 2, 6-di-T-butyl- α -dimethylamino-p-cresol, 2, 6-di-T-butyl-p-cresol, 4-methylenebis (2, 6-di-T-butylphenol) and 2, 6-di-T-butyl-4-alkoxyphenol, common commercial products include T501, hindered amine type antioxidants may be selected from one or more of alkylated aniline, alkylated diphenylamine and phenyl- α -naphthylamine, common commercial products include IRGANOX L-01, IRGANOX L-57, T534, LZ5150A, VANLUBE NA, VANLUBE 961, VANLUBE 81, RC7001, N438L, the phenolic ester antioxidant can be selected from hydroxy phenyl carboxylate with molecular weight of 200-500, and common commercial products include IRGANOX L-135 and T512. The component (E) is more preferably a composite antioxidant containing a thiophenol antioxidant and a hindered phenol antioxidant, wherein the thiophenol antioxidant accounts for 50-90 percent of the total mass of the composite antioxidant, preferably 55-70 percent of the total mass of the composite antioxidant, and the hindered phenol antioxidant accounts for 10-50 percent of the total mass of the composite antioxidant, preferably 30-45 percent of the total mass of the composite antioxidant.
According to the invention, said component (F) is preferably selected from more than one of the group consisting of API group II, group III and group IV base oilsMore preferably a low viscosity naphthenic base oil and/or a low viscosity polyalphaolefin synthetic base oil. The low-viscosity naphthenic base oil is preferably 1mm in viscosity at 40 DEG C2·s-1～10mm2·s-1Naphthenic base oils with pour points below-40 ℃, such as the common commercial products including NS3, Gravex 915, and low viscosity polyalphaolefin synthetic base oils preferably having a viscosity at 40 ℃ of 1mm2·s-1～10mm2·s-1And polyalphaolefin synthetic base oils having pour points below-40 deg.C, such as the common commercial products including PAO-2, PAO-4, PAO-6, and PAO-8.
The method for preparing the hydraulic oil composition of the present invention as described above comprises the step of mixing the components.
The hydraulic oil composition has excellent low-temperature performance, shear stability, thermal stability and comprehensive performance, has high viscosity index, and can meet the use conditions of hydraulic equipment in extremely cold regions (particularly hydraulic equipment requiring instant start). The hydraulic oil composition disclosed by the invention can meet the specification requirements of HV and HS hydraulic oil in GB11118.1-2011, and the viscosity index and the pour point of the hydraulic oil composition are far higher than the specification requirements.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
Unless defined otherwise, all technical and scientific terms used herein or in the specification have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present invention, the term "(meth) acrylic acid" refers to either acrylic acid or methacrylic acid.
In the context of the present invention, unless otherwise specified, the expression "at least two", "two or more", or the like, or the expression "a plurality" or the like used alone, generally means 2 or more, such as from 2 to 15, or from 3 to 10, such as from 5 to 8.
In the context of the present invention, the number average molecular weight Mn and the molecular weight distribution Mw/Mn are determined by Gel Permeation Chromatography (GPC), unless otherwise specified. Here, the measurement conditions of the Gel Permeation Chromatography (GPC) are: the measuring instrument is a gel permeation chromatograph model 1515 produced by Waters corporation in the United states; the detector is a Waters2414 refractive index detector; the solvent used for preparing the standard substance is chromatographic pure tetrahydrofuran produced by Acros company; the chromatographic column is provided by Waters company and is formed by connecting 3 silica gel columns with different pore diameters in series, and the specific specification is (1) Waters
Figure BDA0002242901700000051
HR 0.5THF, relative molecular weight measurement range 1-1000 (7.8X 300mm), (2) Waters
Figure BDA0002242901700000052
HR 1THF, relative molecular weight measurement range of 100-
Figure BDA0002242901700000053
HR 3THF, relative molecular weight measurement range 5000-; the mobile phase is tetrahydrofuran, the flow rate of the mobile phase is 1.0mL/min, the column temperature is 35 ℃, the detector temperature is 35 ℃, the sample injection amount is 200 mu L, the sample concentration is 0.05mmol/L, and the polymer standard sample is polybutylmethacrylate.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
In the context of the present invention, any two or more of the aspects described in this specification may be combined arbitrarily, and the resulting combination forms part of the original description of the specification, and falls within the scope of the present invention without new aspects.
According to one aspect, the present invention relates to a method of making a copolymer composition. Here, the prepared copolymer composition may comprise or may consist of the m polymer components, preferably the m polymer components.
According to one aspect of the invention, the m polymer components produced each independently represent an addition polymer of monomers of formula (I) (hereinafter referred to as polymer A), in particular a free radical addition polymer. The polymer A may be a homopolymer of a single monomer represented by the formula (I) or a copolymer of two or more monomers represented by the formula (I). Specific examples of the copolymer include a random copolymer, a block copolymer, and an alternating copolymer. Furthermore, mixtures of two or more of these polymers A may also be used as the polymer component. In view of this, it is also possible for one or more of the m polymer components to represent a mixture of two or more of the polymers A.
According to one aspect of the invention, the resulting copolymer composition has a number average molecular weight Mn of from 1 to 100 ten thousand, preferably from 1 to 50 ten thousand, more preferably from 1 to 20 ten thousand.
According to one aspect of the invention, the molecular weight distribution Mw/Mn of the copolymer composition produced is from 1.2 to 3.5, preferably from 1.5 to 3.3.
According to one aspect of the present invention, as the monomer represented by the formula (I), there may be mentioned, for example, (meth) acrylic acid C1-C18A linear alkyl ester. These monomers may be used singly or in combination in any ratio.
According to an aspect of the present invention, as the (meth) acrylic acid C1-C18Straight-chain or branched alkyl esters, such as methyl (meth) acrylateEthyl (meth) acrylate, C (meth) acrylic acid3Straight chain/branched chain alkyl ester and (methyl) acrylic acid C4Straight chain/branched chain alkyl ester and (methyl) acrylic acid C5Straight chain/branched chain alkyl ester and (methyl) acrylic acid C6Straight chain/branched chain alkyl ester and (methyl) acrylic acid C7Straight chain/branched chain alkyl ester and (methyl) acrylic acid C8Straight chain/branched chain alkyl ester and (methyl) acrylic acid C9Straight chain/branched chain alkyl ester and (methyl) acrylic acid C10Straight chain/branched chain alkyl ester and (methyl) acrylic acid C11Straight chain/branched chain alkyl ester and (methyl) acrylic acid C12Straight chain/branched chain alkyl ester and (methyl) acrylic acid C13Straight chain/branched chain alkyl ester and (methyl) acrylic acid C14Straight chain/branched chain alkyl ester and (methyl) acrylic acid C15Straight chain/branched chain alkyl ester and (methyl) acrylic acid C16Straight chain/branched chain alkyl ester and (methyl) acrylic acid C18Straight chain \ branched chain alkyl ester. These (meth) acrylic acids C1-C18The linear or branched alkyl esters may be used singly or in combination in any ratio.
In the context of the present invention, the term "side chain" particularly denotes the group R in said formula (I)1。
In the context of the present invention, the expression "average number of carbon atoms in side chains by nuclear magnetic resonance method" or "average number of carbon atoms in side chains" refers to the group R of the target substance obtained by the nuclear magnetic resonance analysis method described below1Average number of carbon atoms.
According to one aspect of the invention, the target substance may comprise a group R1A plurality of structural units of said formula (I) which differ in particular in the number of carbon atoms of their alkyl groups, and the relative proportions of these structural units (or monomers) may also differ for different target substances. Thus, in general, the target substance comprises the group R1The number of carbon atoms of (a) is suitably described by an average value. In view of this, for example, the side chain average carbon number X can reflect not only the number of kinds of the structural unit represented by the formula (I) in the target substance but also these different kinds of structural units(or monomers) relative ratio therebetween.
Nuclear magnetic resonance analysis method
Operating the instrument: INOVA 500MHz NMR spectrometer, solid dual resonance probe (5mm), manufactured by Varian, USA.
The operating conditions are as follows: the operating temperature is room temperature, the number of scans nt is 1000, the chemical shift calibration δ tetramethylsilane is 0, the decoupling mode dm is nny (inverse gated decoupling), and the water lock field is heavy.
And (3) analyzing: subjecting the sample to1And H-NMR characterization, namely analyzing a nuclear magnetic spectrum obtained correspondingly and calculating the average carbon number X of the side chain of the sample. The more specific analysis process and calculation method are referred to the corresponding contents in the embodiments of the present specification.
According to one aspect of the present invention, when performing the nmr analysis, the target substance may be a single substance, including a pure substance or a compositionally homogeneous mixture, such as a polymer component, a homogeneous mixture of polymer components, a monomer, a homogeneous mixture of monomers, a copolymer composition, or a homogeneous mixture of copolymer compositions, and the target substance is directly used as a sample for the corresponding characterization and analysis. Alternatively, the target substance may be a plurality of independently present substances, such as the m polymer components, which are in a state of being independently present from each other, respectively, as described above in the present specification, and not previously mixed together to be a single substance, or such as at least two monomers added to the polymerization reaction system at a monomer addition timing, which will be described later in the present specification, which are likely to be in a state of being independently present from each other at the monomer addition timing (such as by being separately added to the polymerization reaction system), and not previously mixed together to be a single substance. Therefore, if the target substance is a plurality of substances independently present, a sample required for nmr analysis can be prepared in accordance with the following sample preparation procedure before the nmr analysis.
A sample preparation step: the plurality of independently present substances are mixed in a predetermined ratio until homogeneous to obtain a mixture, and then the mixture is used as a sample.
According to an aspect of the present invention, in the sample preparation step, the predetermined ratio refers to a relative ratio which the plurality of independently present substances originally have as a component of the mixture (hypothetical mixture) when they are assumed to be in a state of being mixed with each other. As a specific example, for the m polymer components, the predetermined ratio refers to the relative proportion of the polymer components in the copolymer composition containing or consisting of them; alternatively, the predetermined ratio for the at least two monomers means the relative proportion of the at least two monomers added to the polymerization reaction system at the time of the monomer addition.
According to one aspect of the invention, the average number of carbon atoms in the nmr side chains of the copolymer composition is from 6 to 16, preferably from 6.5 to 15.3, preferably from 7.2 to 15, more preferably from 7.6 to 14.6, more preferably from 7.8 to 13.6.
According to one aspect of the invention, the symbol m represents an integer within the closed interval [2, ∞ ], preferably an integer within the closed interval [5, ∞ ]. Here, the symbol m represents an integer, and the lower limit thereof may be 5 or 8, or may be 10 or 20. The upper limit of the integer represented by the symbol m may be ∞, or 20000, 10000, 5000, 1000, 500, 200, 100, or 50.
According to an aspect of the present invention, the larger the value of the integer represented by the symbol m, the more the kinds of the polymer components contained in the copolymer composition are indicated, and when the value of the integer represented by the symbol m is sufficiently large, such as the upper limit value thereof reaches ∞, it does not mean that the upper limit value actually reaches ∞ in terms of value, but means that the difference in structure and/or composition (particularly, the difference in the average carbon number X of the side chain) between the m polymer components has reached the extent of continuous or stepless smooth change. For example, in the case ofWhen m is ∞, the number of average carbon atoms in the side chain is from X0To XmIt no longer appears as a finite incremental progression of changes, but as a continuous incremental change, in particular as an infinite or smooth incremental change.
According to one aspect of the present invention, the number of the average carbon number X of the side chain is from X as shown in the formula (II)0To XmPresent as an incremental change, such as a gradual incremental change or a linear incremental change. The increment amplitude (also called step size) between any two adjacent X in the incremental change is not particularly limited by the invention, as long as the effective increment is considered by the person skilled in the art. The incremental change may be an equal-step incremental change or an unequal-step incremental change, and is not particularly limited. The step size may be, for example, any value in the range of 0.01 to 4.00 or any value in the range of 0.05 to 1.5, but the present invention is not limited thereto.
According to an aspect of the present invention, as said X0It represents the starting and minimum values of the overall incremental change, and may be, for example, any value in the range from 6 to 12.0, or any value in the range from 6.8 to 11.5, although the invention is not limited thereto. In addition, as the XmIt represents the endpoints and maxima of the entire incremental change, and may be, for example, any value within the range of from 12.2 to 18, or any value within the range of from 12.5 to 17.5, although the invention is not limited thereto.
According to one aspect of the present invention, let the weight percentage (hereinafter sometimes simply referred to as component ratio) of the i-th polymer component to the total weight of the m polymer components (or the copolymer composition) be YiThe symbol i represents an arbitrary integer from 0 to m, and the following relational expression holds.
Y0<Y1<…<Yj>…>Ym-1>Ym(III)
According to one aspect of the invention, in said formula (III), the symbol j represents a closed interval [ (m +1)/4, 3(m + 1)/4)]An integer within, preferably representing a closed regionM [ (m +1)/3, 2(m +1)/3]An integer within (2), more preferably a closed interval of [2(m +1)/5, 3(m +1)/5]An integer of (a), and Y0+Y1+…+Yj+…+Ym-1+Ym＝100％。
According to one aspect of the invention, where Xj represents any value within the closed interval [9.0, 12.5], preferably any value within the closed interval [9.5, 12.2 ].
According to one aspect of the invention, the component proportion Y is given a value from Y0To YjPresent as an incremental change, such as a gradual incremental change or a linear incremental change. The increment amplitude (also called step size) between any two adjacent Y in the incremental change is not particularly limited by the invention, as long as the effective increment is considered by the person skilled in the art. The incremental change may be an equal-step incremental change or an unequal-step incremental change, and is not particularly limited. The step size may be, for example, any value in the range of 0.05% to 20% or any value in the range of 0.1% to 5%, but the present invention is not limited thereto.
According to an aspect of the present invention, as said Y0It represents the starting and minimum values of the whole of said incremental variation, and can be, for example, any value ranging from 0.01% to 20% or any value ranging from 0.1% to 10%, but the invention is not limited thereto. In addition, as the YjIt represents the endpoints and maximum values of the entire incremental change, and may range, for example, from any value in the range of 20% to 75%, or from any value in the range of 25% to 65%, although the invention is not limited thereto.
According to one aspect of the invention, the component proportion Y is given a value from YjTo YnPresenting a decreasing change, such as a gradual decreasing change or a linear decreasing change. The present invention does not specifically limit the decreasing amplitude (also called step size) between any two adjacent Y in the decreasing change, as long as the person skilled in the art considers that the decreasing amplitude (also called step size) has been reachedThe degree of diminishing effect is sufficient. The decrement change may be an equal-step decrement change or an unequal-step decrement change, and is not particularly limited. The step size may be, for example, any value in the range of 0.05% to 20% or any value in the range of 0.1% to 5%, but the present invention is not limited thereto.
According to an aspect of the present invention, as said YjAs previously stated in this specification, it represents the starting and maximum values of the overall decreasing variation, which may be, for example, any value in the range from 20% to 75%, or any value in the range from 25% to 65%, but the invention is not limited thereto. In addition, as the YmIt represents the endpoints and minima of the overall said decreasing variation, and may for example be any value within the range from 0.01% to 20%, or any value within the range from 0.1% to 10%, although the invention is not limited thereto.
According to one aspect of the invention, said Y ismAnd said Y1They may be the same or different and are not particularly limited.
According to one aspect of the present invention, the method of manufacturing the copolymer composition may be one or more of the following manufacturing methods. In the following of the present description, for the sake of simplicity, any matter not described in detail or specifically with respect to the manufacturing process, such as the type of reactor, the way of using various additives, the pretreatment of the feed, the separation of the reaction products, etc., may be directly referred to the corresponding matter known in the art.
According to one aspect of the present invention, the production method comprises a step of adding at least two monomers to a polymerization reaction system to cause addition copolymerization of the at least two monomers. Hereinafter, the above-mentioned production method may be referred to as production method a.
According to an aspect of the present invention, by at least two monomers, it is possible to refer to at least two monomer compounds, and also to at least two monomer mixtures, wherein the monomer mixture comprises two or more monomer compounds, and also to combinations thereof. It follows that one or more of the at least two monomers may sometimes also be present as a monomer mixture. In view of this, in the context of the present invention, the term "monomer" includes in its meaning both monomer compounds and monomer mixtures, unless otherwise specified.
According to an aspect of the present invention, the at least two monomers, specifically, such as two monomers, are added to the polymerization reaction system. For example, as a mode of monomer addition, the two monomers are generally added simultaneously to the polymerization reaction system, that is, the two monomers are added to the polymerization reaction system simultaneously at the beginning and at the same time at the end. Further, the two monomers may be added to the polymerization reaction system separately at a predetermined ratio, or may be mixed with each other at a predetermined ratio to form a monomer mixture and then added to the polymerization reaction system, for example, as a further monomer addition method, which is not particularly limited. Here, the addition is usually a continuous addition, but may be a stepwise or intermittent addition at predetermined time intervals as the case may be, and among them, a continuous addition is preferable. In addition, in the case where the kind of the monomer exceeds two, for example, three or more, these monomers may be added to the polymerization reaction system in a similar manner to the case of two monomers. Specifically, for example, when the kinds of the monomers are more than two, for example, three kinds of the monomers a, B and C, as the monomer addition method, in addition to the foregoing addition methods similar to the case of the two monomers, one possible addition method includes: and simultaneously adding the monomer A and the monomer B into the polymerization reaction system, then stopping adding the monomer B at a certain moment, starting adding the monomer C at the moment, and finally simultaneously stopping adding the monomer A and the monomer C. Of course, the three monomers may be added as three separate feeds, or may be mixed with each other to form a monomer mixture and then added as one feed, or two of them may be mixed to form a monomer mixture and then added as two separate feeds with the third monomer, and there is no particular limitation. When the number of the monomers is more than three, these monomers may be added to the polymerization reaction system in an addition manner similar to the case of three monomers, or may be added in various other monomer addition manners which may occur to those skilled in the art, and are not particularly limited. For example, when the types of the monomers are four, such as monomer a, monomer B, monomer C, and monomer D, one possible way of adding other monomers includes: and simultaneously adding the monomer A and the monomer B into the polymerization reaction system, then stopping adding the monomer A and the monomer B at a certain moment, simultaneously adding the monomer C and the monomer D at the moment, and finally simultaneously stopping adding the monomer C and the monomer D.
According to one aspect of the present invention, in order to facilitate the implementation of the addition copolymerization reaction, the at least two monomers are sometimes added to the polymerization reaction system in the form of a feed mixture. Here, as the feed mixture, in addition to the at least two monomers, one or more additives conventionally used for addition copolymerization such as a solvent, a diluent, an initiator, a molecular weight modifier, a polymerization catalyst and the like may be further generally contained as necessary. Furthermore, the type and amount of these additives can be determined by the requirements of the prior art, and the present invention is not particularly limited thereto.
According to one aspect of the present invention, in the polymerization reaction system, the at least two monomers undergo an addition copolymerization reaction, particularly a radical addition copolymerization reaction, of carbon-carbon double bonds, to obtain a copolymer composition. The copolymer composition includes the copolymer composition of the present invention described in various aspects of the present specification.
According to one aspect of the present invention, the reaction temperature of the addition copolymerization reaction is generally from 50 ℃ to 180 ℃, preferably from 55 ℃ to 165 ℃, more preferably from 60 ℃ to 150 ℃.
According to an aspect of the present invention, the reaction time of the addition copolymerization reaction is generally from 1 hour to 24 hours, preferably from 1.5 hours to 20 hours.
According to an aspect of the present invention, the addition copolymerization reaction may be carried out in any manner of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc., preferably solution polymerization.
According to an aspect of the present invention, in order to facilitate the improvement of the monomer conversion, it is also possible to continue the addition copolymerization reaction for 0.5 to 2 hours after the end of the monomer addition, or to raise the temperature of the polymerization reaction system to 100 ℃ and 150 ℃ and continue the reaction for 0.5 to 5 hours after further addition of an initiator, a polymerization catalyst, a diluent, or the like, as necessary. These reaction modes are known to those skilled in the art.
According to an aspect of the present invention, as the initiator, those conventionally used in the art, particularly, radical polymerization initiators can be used, and there is no particular limitation. Specific examples of the initiator include azo initiators, peroxide initiators, and redox initiators. Specific examples of the azo initiator include dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile. Specific examples of the peroxide initiator include hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, lauroyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide-t-butyl peroxide, t-butyl peroxypivalate, cyclohexanone peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxydicarbonate. Specific examples of the redox initiator include sulfate-sulfite, persulfate-thiourea, persulfate-organic salt, and ammonium persulfate-fatty amine. These initiators may be used singly or in combination in any ratio. In addition, the amount of the initiator used in the present invention is not particularly limited, and those conventionally known in the art can be applied, for example, as the total amount of the initiator used in the whole addition copolymerization reaction, generally 0.01 to 2.5 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, relative to 100 parts by weight of the total amount of the monomers.
According to an aspect of the present invention, as the diluent, those conventionally used in the art, particularly diluent oil, may be used, without particular limitation. Specific examples of the diluent oil include diesel oil, kerosene, mineral oil, aromatic hydrocarbon solvent, white oil, mineral oil base oil, and synthetic oil, preferably white oil, mineral oil base oil, and synthetic oil, and more preferably mineral oil base oil. The diluent oil may be commercially available, for example, as a 100N diluent oil available from Dilongjie corporation. The diluent oil may or may not be separated from the copolymer composition after the completion of the addition copolymerization reaction. These diluent oils may be used singly or in combination in any ratio. In addition, the amount of the diluent oil used in the present invention is not particularly limited, and those conventionally known in the art can be applied, for example, as the total amount of the diluent oil used in the whole addition copolymerization reaction, 10 to 150 parts by weight, preferably 50 to 100 parts by weight, more preferably 60 to 80 parts by weight, relative to 100 parts by weight of the total amount of the monomers used.
According to an aspect of the present invention, as the molecular weight regulator, those conventionally used in the art can be used, and there is no particular limitation. Specific examples of the molecular weight modifier include dodecyl mercaptan and 2-mercaptoethanol. These molecular weight regulators may be used singly or in combination of two or more in any ratio. In addition, the amount of the molecular weight regulator used in the present invention is not particularly limited, and those conventionally known in the art can be applied.
According to an aspect of the present invention, as the polymerization catalyst, those conventionally used in the art can be used, and there is no particular limitation. Specific examples of the polymerization catalyst include radical polymerization catalysts. These polymerization catalysts may be used singly or in combination in any ratio. In addition, the amount of the polymerization catalyst used in the present invention is not particularly limited, and those conventionally known in the art can be applied.
According to one aspect of the present invention, the addition copolymerization reaction is generally carried out in an inert atmosphere. Here, the inert gas atmosphere refers to an inert gas atmosphere that does not chemically react with the reactant and the product. Examples of the inert gas include nitrogen gas and an inert gas. The inert gas atmosphere may be maintained by, for example, continuously introducing the inert gas into the polymerization reaction system.
According to one aspect of the invention, the at least two monomers each independently represent a compound of formula (I). As previously described herein, one or more of the at least two monomers may also sometimes be present as a mixture of monomers. In this case, according to this aspect of the present invention, the two or more monomer compounds contained in the monomer mixture each independently represent a compound represented by formula (I).
Figure BDA0002242901700000131
According to one aspect of the present invention, as the monomer represented by the formula (I), there may be mentioned, for example, (meth) acrylic acid C1-C18Linear or branched alkyl esters. These monomers may be used singly or in combination in any ratio.
According to an aspect of the present invention, as the (meth) acrylic acid C1-C18Examples of the linear or branched alkyl ester include C (meth) acrylate1Straight-chain alkyl ester, (meth) acrylic acid C2Straight-chain alkyl ester, (meth) acrylic acid C3Straight chain/branched chain alkyl ester and (methyl) acrylic acid C4Straight chain/branched chain alkyl ester and (methyl) acrylic acid C5Straight chain/branched chain alkyl ester and (methyl) acrylic acid C6Straight chain/branched chain alkyl ester and (methyl) acrylic acid C7Straight chain/branched chain alkyl ester and (methyl) acrylic acid C8Straight chain/branched chain alkyl ester and (methyl) acrylic acid C9Straight chain/branched chain alkyl ester and (methyl) acrylic acid C10Straight chain/branched chain alkyl ester, (meth) propyleneAcid C11Straight chain/branched chain alkyl ester and (methyl) acrylic acid C12Straight chain/branched chain alkyl ester and (methyl) acrylic acid C13Straight chain/branched chain alkyl ester and (methyl) acrylic acid C14Straight chain/branched chain alkyl ester and (methyl) acrylic acid C15Straight chain/branched chain alkyl ester and (methyl) acrylic acid C16Straight chain/branched chain alkyl ester and (methyl) acrylic acid C18Linear/branched alkyl esters, (meth) acrylic acid. These (meth) acrylic acids C1-C18The linear or branched alkyl esters may be used singly or in combination in any ratio.
According to one aspect of the present invention, the compound represented by the formula (I) may be commercially available or may be manufactured by various methods known in the art. As a specific example, the (meth) acrylic acid C1-C18The linear or branched alkyl ester may be prepared by reacting (meth) acrylic acid with C1-C18Obtained by esterification of a linear or branched alkanol, optionally with methyl (meth) acrylate and C1-C18The ester interchange reaction of the linear or branched alkyl alcohol is not particularly limited.
According to one aspect of the present invention, the addition of the at least two monomers to the polymerization system is initiated at time t0The termination time is tmThen the monomer addition time of the at least two monomers is t (t ═ t)m-t0). In order to increase the monomer conversion as much as possible, or depending on the manner of monomer addition of the at least two monomers, the monomer addition time is generally shorter than the reaction time of the copolymerization reaction. For example, the monomer addition time is generally from 0.5 to 12 hours, preferably from 1 to 10 hours.
According to one aspect of the invention, when dividing the monomer addition time t into m equal parts, at any monomer addition time txLet the average carbon number of the side chains of the at least two monomers be XxThe following relational expression holds. In other words, at any monomer addition time txThe relative proportions of the at least two monomers added to the polymerization system being such thatAverage number of carbon atoms X of side chains of a (hypothetical) mixture of said at least two monomers in said relative proportions by NMRxThe following relational expression is satisfied. Here, the symbol x represents an arbitrary integer from 0 to m.
X0<X1<…<Xj<…<Xm-1<Xm (V)
According to one aspect of the invention, the average number of carbons X in the side chains of the at least two monomersxAs previously stated in the present specification, refers to the average carbon number of the side chains of a (fictitious) mixture of said at least two monomers in a predetermined ratio, wherein said predetermined ratio refers to the time t at which any one of the monomers is addedxThe relative proportions of the at least two monomers added to the polymerization system.
According to one aspect of the invention, the at least two monomers are added at the monomer addition time txThe relative proportion to be added to the polymerization reaction system is not particularly limited, and may be any value as long as it enables the side chain average carbon number X of the hypothetical mixturexThe formula (V) may be satisfied. For simplicity, it is assumed that the at least two monomers represent two monomers, monomer a and monomer B, wherein the average carbon number of the side chain of monomer a is greater than the average carbon number of the side chain of monomer B. In order to satisfy the regulation of the formula (V), the starting time t of the addition of the two monomers to the polymerization system0To the end time tmThe amount of the monomer B may be gradually increased while maintaining the amount of the monomer B, gradually decreased while maintaining the amount of the monomer a, or both may be changed so that the amount of the monomer B is relatively decreased as compared with the amount of the monomer a.
According to one aspect of the invention, the addition amounts of the monomer A and the monomer B can be manually regulated or automatically regulated by a program, so that the addition amount proportion of the monomer A and the monomer B is continuously changed, and the total addition amount is continuously changed. For example, the simple example: at the initial moment t of the polymerization0To the end time tmAnd manually and continuously regulating and controlling the addition rate of the monomer A in an intermittent manner by setting m control points so as to discontinuously realize the relative reduction of the addition amount of the monomer B compared with the addition amount of the monomer A. It is also possible to set a control program which is easily developed and grasped by those skilled in the art, and by this control program, the addition rate of monomer A is continuously regulated and controlled so as to satisfy the regulation of formula (V).
According to one aspect of the invention, the symbol m represents an integer within the closed interval [5, ∞ ], preferably an integer within the closed interval [8, ∞ ]. Here, the symbol m represents an integer, and the lower limit thereof may be 5 or 8, or may be 10 or 20. The upper limit of the integer represented by the symbol m may be ∞, or 20000, 10000, 5000, 1000, 500, 200, 100, or 50.
According to an aspect of the present invention, a larger value of the integer represented by the symbol m indicates a more continuous change in the addition timing of two adjacent monomers, and also means a more continuous change in the average carbon number of the side chain at the addition timing of two adjacent monomers. When the value of the integer represented by the symbol m is sufficiently large, for example, the upper limit value thereof reaches ∞, this does not mean that the upper limit value actually reaches ∞ in terms of value, but means that the average carbon number of the side chain has reached the extent of continuous or stepless smooth change with continuous change in the monomer addition timing. For example, when m ∞, the number of average carbon numbers of the side chains is from X0To XmIt no longer appears as a finite incremental progression of changes, but as a continuous incremental change, in particular as an infinite or smooth incremental change.
According to one aspect of the present invention, the number of the average carbon number X of the side chain is from X as shown in the formula (V)0To XmPresent as an incremental change, such as a gradual incremental change or a linear incremental change. The increment amplitude (also called step length) between any two adjacent X in the incremental change is not particularly limited by the invention, as long as the effective increment distance is considered to be reached by the person skilled in the artAnd (5) measuring. The incremental change may be an equal-step incremental change or an unequal-step incremental change, and is not particularly limited. The step size may be, for example, any value in the range of 0.01 to 4.00 or any value in the range of 0.05 to 1.5, but the present invention is not limited thereto.
According to an aspect of the present invention, as said X0It represents the starting time t of the addition of the at least two monomers to the polymerization system0The average carbon number of the side chain of (a) also represents the starting point and the minimum value of the whole incremental change, and may be, for example, any value ranging from 6.5 to 12 or any value ranging from 6.8 to 11.5, but the present invention is not limited thereto. In addition, as the XmIt represents the termination time t of the addition of said at least two monomers to said polymerization systemmAlso represents the end point and maximum of the overall said incremental change, such as any value in the range from 12.2 to 18, or any value in the range from 12.5 to 17.5, but the invention is not limited thereto.
According to one aspect of the invention, the termination time t of the monomer addition is setmThe sum of the cumulative addition amounts of the at least two monomers to the polymerization reaction system within the monomer addition time t is G, and is set at any monomer addition time txThe sum of the addition amounts of the at least two monomers to the polymerization reaction system is GxThe symbol x represents an arbitrary integer from 0 to m, and the following relational expression holds. The ratio G is sometimes described belowxThe term,/G is simply referred to as the addition amount ratio.
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G(VI)
According to one aspect of the invention, in said formula (VI), the symbol j represents a closed interval [ m/4, 3m/4 ]]An integer within, preferably representing a closed interval [ m/3, 2m/3]An integer within, more preferably representing a closed interval [2m/5, 3m/5]An integer of (a), and G0+G1+…+Gj+…+Gm-1+Gm＝G。
According to one aspect of the invention, at any monomer addition time txAnd adding the at least two monomers to the polymerization reaction system, wherein the at least two monomers are represented by q monomers. Here, the symbol q represents the number of kinds of monomers involved in the production method a, and may be, for example, any integer from 2 to 100 or any integer from 2 to 20, particularly any integer from 2 to 5. Here, let us say that each monomer is added at the monomer addition time txThe amount (absolute value) added alone to the polymerization reaction system was gsAnd the symbol s represents any integer from 1 to q, the sum of these individual addition amounts is equal to said GxThe ratio between these individual addition amounts is the time t at which the at least two monomers are addedxRelative proportions added to the polymerization system. At any monomer addition time t, as described earlier in this specificationxThe relative proportions are required so that the side chain average carbon number X of the hypothetical mixturexSatisfies the specification of the formula (V). This is a requirement set forth for the relative amounts of these separate additions of the at least two monomers. According to this aspect of the present invention, there is no particular limitation on the absolute value of each of these individual addition amounts of the at least two monomers, as long as the sum thereof reaches the GxAnd further causing said GxOr the GxIt is sufficient that/G satisfies the specification of the formula (VI). For simplicity, it is assumed that the at least two monomers represent two monomers, monomer a and monomer B, wherein the average carbon number of the side chain of monomer a is greater than the average carbon number of the side chain of monomer B. In order that the amounts of the two monomers added individually satisfy both the regulation of the formula (V) and the regulation of the formula (VI), the starting time t of the addition of the two monomers to the polymerization reaction system0To the moment of monomer addition tjGradually increasing the amount of the monomer A while maintaining the amount of the monomer B added, and then starting from the monomer addition time tjTo the end of the monomer additionmGradually decreasing the amount of the monomer B added, andthe amount of the monomer A added was kept constant.
According to one aspect of the invention, the value of the addition ratio is from G, as shown in the formula (VI)0G to Gjthe/G is presented as an incremental change, such as a gradual incremental change or a linear incremental change. The increment (also called step size) between any two adjacent values in the incremental change is not particularly limited by the present invention, as long as the effective increment is considered by those skilled in the art. The incremental change may be an equal-step incremental change or an unequal-step incremental change, and is not particularly limited. The step size may be, for example, any value in the range of 0.05% to 20% or any value in the range of 0.1% to 5%, but the present invention is not limited thereto.
According to an aspect of the present invention, the addition amount ratio G is0(iv)/G, which represents the starting time t at which the at least two monomers are added to the polymerization system0The ratio of the (instantaneous) total addition amount of the at least two monomers with respect to the total addition amount G of the at least two monomers over the entire monomer addition time t also represents the starting point and the minimum value of the entire incremental change, and may be, for example, any value in the range from 0.01% to 20%, or any value in the range from 0.1% to 10%, but the present invention is not limited thereto. The addition amount ratio G is defined asjG, which represents the time t at which the monomer is addedjThe ratio of the (instantaneous) total addition amount of the at least two monomers with respect to the total addition amount G also represents the end point and the maximum value of the entire incremental change, and may be, for example, any value in the range from 20% to 75%, or any value in the range from 25% to 65%, but the present invention is not limited thereto.
According to one aspect of the invention, the value of the addition ratio is from G, as shown in the formula (VI)jG to Gmthe/G is presented as a decreasing change, such as a gradual decreasing change or a linear decreasing change. The invention reduces the descending amplitude between any two adjacent numerical values in the descending change (Also referred to as step size) is not particularly limited, as long as the person skilled in the art considers that an effective decrement has been achieved. The decrement change may be an equal-step decrement change or an unequal-step decrement change, and is not particularly limited. The step size may be, for example, any value in the range of 0.05% to 20% or any value in the range of 0.1% to 5%, but the present invention is not limited thereto.
According to an aspect of the present invention, the addition amount ratio G isjG, which represents the time t at which the monomer is addedjThe ratio of the (instantaneous) total addition amount of the at least two monomers with respect to the total addition amount G also represents the starting point and the maximum value of the overall decreasing change, and may be, for example, any value in the range from 20% to 75%, or any value in the range from 25% to 65%, but the present invention is not limited thereto. The addition amount ratio G is defined asm(iv)/G, which represents the end time t at which the addition of the at least two monomers to the polymerization system is terminatedmThe ratio of the (instantaneous) total addition amount of the at least two monomers with respect to the total addition amount G also represents the end point and the minimum value of the overall decreasing variation, and may be, for example, any value in the range from 0.01% to 20%, or any value in the range from 0.1% to 10%, but the present invention is not limited thereto.
According to an aspect of the invention, the addition amount ratio GmThe ratio G of the amount of addition to the amount of0The groups represented by the formula are not particularly limited, and may be the same or different.
According to an aspect of the invention, wherein the termination time t of the monomer addition is setmCumulatively adding, by mass, a group R to the polymerization system1Is C1-C7The amount of monomers of linear or branched alkyl groups is 5 to 50% (preferably 7 to 45%) of the sum G of the cumulative added masses; cumulatively adding a group R to the polymerization system1Is C8-C18The amount of the linear or branched alkyl monomer accounts for 50-95% of the sum G of the cumulative addition amounts% (preferably 55% to 93%).
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
In the following examples and comparative examples, the respective contents of the copolymer and the diluent oil and the respective monomer contents in the copolymer were calculated in terms of the charged amounts.
In the context of the present invention, including in the following examples and comparative examples, the respective measuring methods and calculation methods were carried out as follows.
1. Gel Permeation Chromatography (GPC) analysis method
Operating the instrument: model 1515 gel permeation chromatograph manufactured by Waters corporation, usa. The detector was a Waters2414 refractive index detector. The solvent used for preparing the standard was chromatographically pure tetrahydrofuran manufactured by Acros corporation. The chromatographic column is provided by Waters company and is formed by connecting 3 silica gel columns with different pore diameters in series, and the specific specifications are as follows:
(1)Waters
Figure BDA0002242901700000181
HR 0.5THF, a relative molecular weight measurement ranging from 1 to 1000 (7.8X 300mm),
(2)Waters
Figure BDA0002242901700000182
HR 1THF, a relative molecular weight measurement range of 100-,
(3)Waters
Figure BDA0002242901700000183
HR 3THF, relative molecular weight measurement range 5000-.
The operating conditions are as follows: the mobile phase is tetrahydrofuran, the flow rate of the mobile phase is 1.0mL/min, the column temperature is 35 ℃, the detector temperature is 35 ℃, and the sample injection amount is 200 mu L.
And (3) an analysis step: during the reaction, samples were continuously taken from the reaction vessel, 0.02 to 0.2g of the sample was weighed out and dissolved in 10mL of tetrahydrofuran, shaken up to obtain a homogeneous solution, and then the solution was subjected to GPC analysis on the operating instrument under the operating conditions. The number average molecular weight Mn and the molecular weight distribution Mw/Mn of the samples were measured over different time periods.
2. Nuclear magnetic resonance analysis method
Operating the instrument: INOVA 500MHz NMR spectrometer manufactured by Varian corporation of America (1H-NMR), solid dual resonance probe (5 mm).
The operating conditions are as follows: the operating temperature is room temperature, the number of scans nt is 1000, the chemical shift calibration δ tetramethylsilane is 0, the decoupling mode dm is nny (inverse gated decoupling), and the water lock field is heavy.
And (3) analyzing: subjecting the sample to1And H-NMR characterization, namely analyzing a nuclear magnetic spectrum obtained correspondingly and calculating the average carbon number X of the side chain of the sample.
Hereinafter, the procedure of analyzing the nuclear magnetic spectrum and the method of calculating the average carbon number X of the side chain will be described specifically by taking a methacrylate polymer as an example, but the present invention is not limited thereto, and other polymers may be similarly analyzed and calculated with reference to the contents.
By way of example only, the methacrylate polymer or the acrylate polymer generally comprises structural units as shown in the following formula.
Figure BDA0002242901700000191
According to1The obvious difference of H-NMR spectrum, aiming at the methacrylate polymer, the hydrogen atoms in the structural unit of the methacrylate polymer can be roughly divided into H shown in the formulaA、HB、HC、HDFour regions, and these regions have the relationship shown in formula (1). Due to HCIs at chemical shift HBIs covered with and HDWhere it is more difficult to integrate, H can beB、HCAnd HDAnd (6) combining and calculating. Therefore, the formula (1) can be transformed into the formula (2) and further derived as the formula (3).
Figure BDA0002242901700000192
Figure BDA0002242901700000193
Figure BDA0002242901700000194
In these formulas, X represents the side chain average carbon number of the methacrylate polymer.
Similar to the analysis of the methacrylate ester polymer, the hydrogen atom in the structural unit thereof can be roughly classified into H represented by the above formulaA、HB、HDIn the three regions, the average carbon number X of the side chain of the acrylate polymer can be calculated as shown in formula (4).
Figure BDA0002242901700000201
Specifically, for example, if a certain methacrylate polymer has a nuclear magnetic spectrum and integral data shown in formula (T-1), the average carbon number X of the side chain of the methacrylate polymer is 14.86 as calculated by formula (3).
Example A
113kg of a diluent oil (from Dilongyu, 100N, same below) was charged into a mechanically stirred reactor under nitrogen, heated to 83-91 ℃ and 270kg of a first monomer (mixture of ethyl methacrylate/hexyl methacrylate/isooctyl methacrylate/dodecyl methacrylate, where C is C)220% by weight, C620% by weight, C810% by weight, C1050% by weight of a mixture A of X6.5, 1.35kg of benzoyl peroxide and 1.08kg of dodecylmercaptan are added dropwise to the reaction vessel, 150kg of a second monomer (a mixture of decyl methacrylate/dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate, whereC1030% by weight, C12＝33％，C14＝20％，C1617% by weight, X12.2), 0.75kg of benzoyl peroxide and 0.6kg of dodecyl mercaptan are added dropwise to the reactor. At the initial time of the dropping, the ratio A/B of the amount (kg/hr) of the mixture A to the amount (kg/hr) of the mixture B dropped was 1:0, and then, A/B was gradually decreased until the time of 6 hours of the dropping, A/B reached 0:1, and the dropping was completed. Then, the reaction vessel was kept at 95 ℃ for 1 hour, and then 0.3kg of benzoyl peroxide and 113kg of diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ and kept for 2 hours, to obtain copolymer composition J1. Here, the monomer conversion of the polymerization reaction was 98.8%, the number average molecular weight Mn of the copolymer composition J1 was 55132, and the average carbon number X of the side chain was 8.1. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were made on the samples, the results of which are shown in table 1.
TABLE 1
Item 1 2 3 4 5 J1
Average carbon number of side chain X 6.8 7.2 8.1 10.7 12.2 8.1
Number average molecular weight Mn 42981 50372 56738 54836 55437 55132
Example B
113kg of a diluent oil (from Doxolon, 100N, same below) was charged into a mechanically stirred reactor under nitrogen, heated to 83-91 ℃ and 100kg of a first monomer (a mixture of methyl methacrylate/propane methacrylate/isooctyl methacrylate/dodecyl methacrylate, where C is C)125% by weight, C320% by weight, C815% by weight, C10A mixture a of 40 wt%, X4.7), 0.5kg benzoyl peroxide and 0.36kg dodecyl mercaptan was added dropwise to the kettle while 320kg of a second monomer (a mixture of nonyl methacrylate/dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate/octadecyl methacrylate, where C is920% by weight, C12＝20％，C14＝55％，C163% by weight, C182% by weight of a mixture B of X13.5), 1.5kg of benzoyl peroxide and 1.4kg of dodecylmercaptan are added dropwise to the reactor. At the initial time of the dropping, the ratio A/B of the amount (kg/hr) of the mixture A to the amount (kg/hr) of the mixture B dropped was 1:1, and then, A/B was gradually decreased until the time of 6 hours of the dropping, A/B reached 1:5, and the dropping was completed. The reactor was then held at 95 ℃ for a further 1 hourThen, 0.3kg of benzoyl peroxide and 113kg of a diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ and the mixture was held for 2 hours, to obtain a copolymer composition J2. Here, the monomer conversion of the polymerization reaction was 99.8%, the number average molecular weight Mn of the copolymer composition J2 was 49983, and the average carbon number X of the side chain was 9.3. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were made on the samples, the results of which are shown in table 2.
TABLE 2
Item 1 2 3 4 5 J2
Average carbon number of side chain X 7.5 8.2 9.8 10.7 12.3 9.3
Number average molecular weight Mn 40123 43012 42753 50223 48094 49983
Comparative example A
A gradient copolymer was prepared as in example A, except that the first monomer and the second monomer were mixed uniformly and then added dropwise to the reaction system at a constant rate, specifically:
113kg of diluent oil are introduced into a mechanically stirred reactor under nitrogen, heated to 83-91 ℃ and 270kg of a first monomer (mixture of ethyl methacrylate/hexyl methacrylate/isooctyl methacrylate/dodecyl methacrylate, where C is220% by weight, C620% by weight, C810% by weight, C1050% by weight, X6.5), 150kg of a second monomer (mixture of decyl methacrylate/dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate, where C is1030% by weight, C12＝33％，C14＝20％，C1617% by weight, X12.2), 2.1kg of benzoyl peroxide and 1.68kg of dodecylmercaptan were added dropwise at a constant rate of 70 kg/h, over a period of 6 hours, after which the autoclave was kept at 95 ℃ for 1 hour, 0.3kg of benzoyl peroxide and 113kg of diluent oil were added, and the reaction was terminated after heating to 103 ℃ for 2 hours, giving a copolymer composition DJ 1. Here, the monomer conversion of the polymerization reaction was 99.0%, the number average molecular weight Mn of the copolymer composition DJ1 was 48976, and the average carbon number X of the side chain was 8.1. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were made on the samples, the results of which are shown in table 3.
TABLE 3
Item 1 2 3 4 5 DJ1
Average carbon number of side chain X 8.1 8.0 8.1 8.1 8.1 8.1
Number average molecular weight Mn 47564 48930 50031 49046 47774 48976
Example C
Under nitrogen protection, 113kg of diluent oil (obtained from Dilon corporation under the trademark 100N, the same applies below) was charged into a mechanically stirred reactor, heated to 83-91 deg.C, and 50kg of the first monomer (hexane methacrylate/propylene methacrylate)Mixtures of octyl alkyl esters of acids/of dodecyl methacrylate, where C620% by weight, C830% by weight, C1050% by weight of a mixture a of X8.4), 0.15kg of benzoyl peroxide and 0.10kg of dodecylmercaptan was added dropwise to the reaction vessel, while 370kg of a second monomer (a mixture of dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate, where C is C, were added dropwise to the reaction vessel13＝19％，C14＝38％，C1643% by weight of a mixture B of 14.6% X, 1.0kg of benzoyl peroxide and 1.1kg of dodecylmercaptan are added dropwise to the reactor. At the initial time of the dropping, the ratio A/B of the amount (kg/hr) of the mixture A to the amount (kg/hr) of the mixture B dropped was 2:1, and then, A/B was gradually decreased until the time of 6 hours of the dropping, A/B reached 0:1, and the dropping was completed. Then, the reaction vessel was kept at 95 ℃ for 1 hour, and then 0.3kg of benzoyl peroxide and 113kg of diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ and kept for 2 hours, to obtain copolymer composition J3. Here, the monomer conversion of the polymerization reaction was 99.5%, the number average molecular weight Mn of the copolymer composition J3 was 82129, and the average carbon number X of the side chain was 13.6. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were carried out on the samples, the results of which are shown in Table 4.
TABLE 4
Item 1 2 3 4 5 J1
Average carbon number of side chain X 9.9 10.7 12.4 13.5 14.0 13.6
Number average molecular weight Mn 79863 78349 84090 81097 76433 82129
Example D
5 different linear alkyl methacrylate monomer mixtures A to E were prepared, and the compositions of the respective mixtures are shown in Table 5.
TABLE 5
Figure BDA0002242901700000231
Under the protection of nitrogen, 113kg of diluent oil (purchased from Bilongong company, brand 100N, the same applies hereinafter) was added to a reaction kettle equipped with a mechanical stirrer, heated to 92-100 ℃ at the initial time of the dropwise addition, mixture A was constantly added dropwise into the reaction kettle at a rate of 15 kg/hr, and at the same time, mixture B was added dropwise at a rate of 70 kg/hr, the feed rate of mixture B was gradually increased, when 2 hours were reached, the feed of mixture A and mixture B was terminated, then mixture C and mixture D were added dropwise into the reaction kettle, the ratio C/D of the amount of dropwise addition (kg/hr) of mixture C to the amount of dropwise addition (kg/hr) of mixture D was 3:1, then C was gradually decreased, mixture D was gradually increased until the time of dropwise addition for 5 hours, C/D reached 1:1, at which the dropwise addition of mixture C was terminated, then, the mixture E was added dropwise to the reaction vessel so that the ratio D/E of the amount (kg/hr) of the mixture D added dropwise to the amount (kg/hr) of the mixture E added dropwise was 10:1, and then D was gradually decreased until 7 hours from the time of dropwise addition, D/E reached 1:1, and the dropwise addition was completed. Then, the reaction vessel was kept at 100 ℃ for 1 hour, and then 0.3kg of benzoyl peroxide and 113kg of diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ and kept for 2 hours, to obtain copolymer composition J4. Here, the monomer conversion of the polymerization reaction was 99.5%, the number average molecular weight Mn of the copolymer composition J4 was 45812, and the average carbon number X of the side chain was 8.8. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were carried out on the samples, the results of which are shown in Table 6.
TABLE 6
Item 1 2 3 4 5 6 J4
Average carbon number of side chain X 6.5 6.9 8.3 10.4 12.3 13.8 8.8
Number average molecular weight Mn 44586 43294 45693 50384 51034 50004 45812
Example E
113kg of diluent oil (from Dilongyuan, 100N, same below) was charged into a mechanically stirred tank reactor under nitrogen, heated to 83-91 deg.C, and 185kg of a first monomer (a mixture of methyl methacrylate/pentyl methacrylate/isooctyl methacrylate, where C is C135% by weight, C541% by weight, C8A mixture a of 32 wt%, X3.8), 0.8kg benzoyl peroxide and 0.80kg dodecyl mercaptan was added dropwise to the kettle while 235kg of a second monomer (a mixture of dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate/octadecyl methacrylate, where C is12＝25％，C14＝40％，C1623% by weight, C1812% by weight, a mixture B of 14.3% X), 1.0kg of benzoyl peroxide and 0.9kg of dodecyl mercaptan is added dropwise to the reaction vessel. At the initial time of the dropping, the ratio A/B of the amount (kg/hour) of the mixture A dropped to the amount (kg/hour) of the mixture B dropped was 3:2, and then A/B was gradually decreasedAnd (4) until the dropping time is 7 hours, the ratio of A to B is 1:8, and the dropping is finished. Then, the reaction vessel was kept at 100 ℃ for 1 hour, and then 0.3kg of benzoyl peroxide and 113kg of diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ and kept for 2 hours, to obtain copolymer composition J5. Here, the monomer conversion of the polymerization reaction was 99.3%, the number average molecular weight Mn of the copolymer composition J5 was 63436, and the average carbon number X of the side chain was 7.8. Samples were taken at different reaction times and at different final polymer times, and GPC measurements were carried out on the samples, the results of which are shown in Table 7.
TABLE 7
Item 1 2 3 4 5 J5
Average carbon number of side chain X 6.5 6.8 7.9 11.7 13.5 7.8
Number average molecular weight Mn 59003 61472 68940 62158 60239 63436
Comparative example B
A copolymer composition was prepared according to the method of example E, except that the first monomer and second monomer were in different proportions, specifically:
113kg of a diluent oil (from Dilongyu, 100N, same below) was charged into a mechanically stirred tank reactor under nitrogen, heated to 83-91 deg.C, and 280kg of a first monomer (a mixture of methyl methacrylate/pentyl methacrylate/isooctyl methacrylate, where C is C135% by weight, C541% by weight, C8A mixture a of 32 wt%, X3.8), 1.2kg benzoyl peroxide and 1.2kg dodecyl mercaptan was added dropwise to the kettle while 140kg of a second monomer (a mixture of dodecyl methacrylate/tetradecyl methacrylate/hexadecyl methacrylate/octadecyl methacrylate, where C is C, was added dropwise to the kettle12＝25％，C14＝40％，C1623% by weight, C1812% by weight, X14.3), 0.6kg of benzoyl peroxide and 0.5kg of dodecyl mercaptan are added dropwise to the reactor. At the initial time of the dropping, the ratio A/B of the amount (kg/hr) of the mixture A to the amount (kg/hr) of the mixture B dropped was 5:2, and then, A/B was gradually decreased until the time of 7 hours of the dropping, A/B reached 1:8, and the dropping was completed. Then, the reaction vessel was kept at 100 ℃ for 1 hour, and then 0.3kg of benzoyl peroxide and 113kg of diluent oil were added thereto, and the polymerization was terminated after the temperature was raised to 103 ℃ for 2 hours, to obtain copolymer composition DJ 2. Here, the monomer conversion of the polymerization reaction was 98.7%, the number average molecular weight Mn of the copolymer composition DJ2 was 67490, and the side chain average carbon number X was 5.9. Are respectively different inSamples were taken at the reaction time and the final polymer and GPC measurements were made on the samples as shown in Table 8.
TABLE 8
Item 1 2 3 4 5 DJ2
Average carbon number of side chain X 5.5 5.7 6.0 9.3 12.7 5.9
Number average molecular weight Mn 76389 73459 69004 66043 65892 67490
Comparative example C
The copolymer composition was prepared according to the method of example 11 in US 6712991, giving copolymer composition DJ 3. The monomer conversion of this polymerization reaction was 97.9%, the number average molecular weight Mn of the copolymer composition DJ3 was 47550, and the average number of carbons X in the side chain was 11.0. The polymer was sampled at different reaction times and reaction end points, respectively, and GPC measurements were made on the samples, and the results are shown in Table 9.
TABLE 9
Item 1 2 3 4 5 DJ3
Average carbon number of side chain X 10.9 11.0 11.0 11.1 11.0 11.0
Number average molecular weight Mn 46543 46730 47605 46808 47120 47550
Copolymer compositions J1 to J5 and copolymer compositions DJ1 to DJ3 were added to API III 150N base oil, respectively, at the addition amounts specified in table 10. The amounts of each copolymer composition used and the results of the performance tests are shown in Table 10.
Watch 10
Figure BDA0002242901700000251
Examples 1 to 5 and comparative examples 1 to 3 of ultra-low temperature hydraulic oil compositions with ultra-high viscosity index
The formulations of examples 1 to 5 and comparative examples 1 to 3 of the ultra-low temperature hydraulic oil composition with ultra-high viscosity index are shown in table 11, and the components are respectively added into a blending container and stirred for 1 hour at 50 ℃ under normal pressure to prepare the ultra-low temperature hydraulic oil composition with ultra-high viscosity index and viscosity grade of HS 32. The hydraulic fluids of examples 1-5 and comparative examples 1-3 were evaluated for their performance according to the test methods including GB/T265, GB/T1995, GB/T3535, SH/T0189, SH/T0301, SH/T0209, and the test results are shown in Table 12.
TABLE 11
Figure BDA0002242901700000261
TABLE 12
Figure BDA0002242901700000271

Claims (10)

1. A hydraulic oil composition comprising:
(A) a copolymer composition; (B) an antiwear agent; (C) a rust inhibitor; (D) a metal deactivator; (E) an antioxidant; (F) a base oil;
the method for producing the copolymer composition comprises the step of adding at least two monomers to a polymerization reaction system, and subjecting the at least two monomers to addition copolymerization reaction (particularly radical addition copolymerization reaction), wherein the at least two monomers each independently represent a compound represented by formula (I) and/or a mixture thereof,
Figure FDA0002242901690000011
in the formula (I), the radical R1Is C1-C18A linear or branched alkyl group; radical R2Is H or methyl;
setting the initial time of adding the at least two monomers into the polymerization reaction system as t0The termination time is tmThen the monomer addition time of the at least two monomers is t (t ═ t)m-t0) When the monomer addition time is divided into m equal parts, the symbol m represents a closed interval [2, ∞ [ ]]An integer within (preferably representing a closed interval [5, ∞.)]Preferably the upper limit of the integer denoted by the symbol m is 20000, 10000, 5000, 1000, 500, 200, 100 or 50), at any monomer addition time txThe relative proportions of the at least two monomers added to the polymerization system being such that the average number of carbon atoms in the side chain X is the average number of carbon atoms in the NMR of a mixture of the at least two monomers in the relative proportionsxSatisfying the following relationship, the symbol x represents any integer from 0 to m,
X0<X1<…<Xj<…<Xm-1<Xm (II)
wherein the termination time t of the monomer addition is setmThe sum of the cumulative addition amounts of the at least two monomers to the polymerization reaction system within the monomer addition time is G, and is set at any monomer addition time txSaid at least two monomers being reacted to said polymerizationThe sum of the addition amounts in the system is GxThe symbol x represents an arbitrary integer from 0 to m, and the following relational expression holds,
G0/G<G1/G<…<Gj/G>…>Gm-1/G>Gm/G (III)
in formula (III), the symbol j represents a closed interval [ m/4, 3m/4 ]]An integer within (preferably representing a closed interval [ m/3, 2 m/3)]An integer within, more preferably representing a closed interval [2m/5, 3m/5]An integer of) and G)0+G1+…+Gj+…+Gm-1+Gm＝G；
Wherein the termination time t of the monomer addition is setmCumulatively adding, by mass, a group R to the polymerization system1Is C1-C7The amount of the linear chain or branched chain alkyl monomer accounts for 5 to 50 percent (preferably 7 to 45 percent) of the sum G of the cumulative addition amounts; cumulatively adding a group R to the polymerization system1Is C8-C18The amount of the linear or branched alkyl monomer is 50 to 95% (preferably 55 to 93%) of the sum G of the above-mentioned cumulative amounts.
2. The hydraulic fluid composition of claim 1, wherein X isjRepresents a closed interval [9.0, 12.5]]Any value within, preferably representing a closed interval [9.5, 12.2]]Any one of the values in (b).
3. The hydraulic fluid composition of claim 1, wherein the at least two monomers are selected from the group consisting of C (meth) acrylic acid1Straight-chain alkyl ester, (meth) acrylic acid C2Straight-chain alkyl ester, (meth) acrylic acid C3Straight chain/branched chain alkyl ester and (methyl) acrylic acid C4Straight chain/branched chain alkyl ester and (methyl) acrylic acid C5Straight chain/branched chain alkyl ester and (methyl) acrylic acid C6Straight chain/branched chain alkyl ester and (methyl) acrylic acid C7Straight chain/branched chain alkyl ester and (methyl) acrylic acid C8Straight chain/branched chain alkyl ester and (methyl) acrylic acid C9Straight chain/branched chain alkyl ester, (methyl) propyl esterOlefine acid C10Straight chain/branched chain alkyl ester and (methyl) acrylic acid C11Straight chain/branched chain alkyl ester and (methyl) acrylic acid C12Straight chain/branched chain alkyl ester and (methyl) acrylic acid C13Straight chain/branched chain alkyl ester and (methyl) acrylic acid C14Straight chain/branched chain alkyl ester and (methyl) acrylic acid C15Straight chain/branched chain alkyl ester and (methyl) acrylic acid C16Straight chain/branched chain alkyl ester and (methyl) acrylic acid C18Straight chain \ branched chain alkyl ester.
4. The hydraulic fluid composition as recited in claim 1, wherein X is0Represents a closed interval [6.5, 12 ]]Any value within (preferably representing a closed interval [6.8, 11.5 ]]Any one value of) the X groupmRepresents a closed interval [12.2, 18 ]]Any value within (preferably representing a closed interval [12.5, 17.5 ]]Any one of the values in (c).
5. The hydraulic fluid composition of claim 1, wherein the ratio GjG is from 20% to 75% (preferably from 25% to 65%), or the ratio G0G or the ratio Gmthe/G is from 0.01% to 20% (preferably from 0.1% to 10%).
6. The hydraulic fluid composition of claim 1, wherein the reaction temperature of the copolymerization reaction is from 50 ℃ to 180 ℃ (preferably from 55 ℃ to 165 ℃, more preferably from 60 ℃ to 150 ℃), the reaction time of the copolymerization reaction is from 1 hour to 24 hours (preferably from 1.5 hours to 20 hours), and the monomer addition time t is from 0.5 hours to 12 hours (preferably from 1 hour to 10 hours).
7. The hydraulic oil composition according to any one of claims 1 to 6, wherein the component (A) accounts for 3 to 45% of the total mass of the lubricating oil composition; the component (B) accounts for 0.1 to 10 percent of the total mass of the lubricating oil composition; the component (C) accounts for 0.01 to 10 percent of the total mass of the lubricating oil composition; the component (D) accounts for 0.01 to 5 percent of the total mass of the lubricating oil composition; the component (E) accounts for 0.1 to 10 percent of the total mass of the lubricating oil composition; the component (F) constitutes the main component of the lubricating oil composition.
8. The hydraulic fluid composition as recited in any one of claims 1 to 6, wherein the component (B) is one or more selected from the group consisting of polysulfide, phosphate, thiophosphate and thiophosphornitrogen type extreme pressure antiwear agent; the component (C) is selected from one or more of sulfonate, alkenyl succinic acid, alkenyl succinic anhydride and alkenyl succinic acid ester; the component (D) is selected from benzotriazole derivatives and/or thiadiazole derivatives; the component (E) is selected from one or more of thiophenol type, hindered phenol type, hindered amine type and phenolic ester type antioxidants; the component (F) is selected from one or more of API group II, group III and group IV base oils.
9. The hydraulic oil composition as recited in any one of claims 1 to 6, wherein the component (B) is selected from the group consisting of a composite antiwear agent comprising a polysulfide, a phosphate ester, and a sulfur-nitrogen-phosphorus type extreme pressure antiwear agent; said component (C) is selected from sulfonates; the component (D) is selected from benzotriazole derivatives; the component (E) is selected from a composite antioxidant containing a thiophenol antioxidant and a hindered phenol antioxidant; the component (F) is selected from a low viscosity naphthenic base oil and/or a low viscosity polyalphaolefin synthetic base oil.
10. A method for preparing a hydraulic oil composition as defined in any one of claims 1 to 9, comprising the step of mixing the respective components.
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