CN110452335A - Viscosity index improver and preparation method thereof - Google Patents
Viscosity index improver and preparation method thereof Download PDFInfo
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- CN110452335A CN110452335A CN201810432404.6A CN201810432404A CN110452335A CN 110452335 A CN110452335 A CN 110452335A CN 201810432404 A CN201810432404 A CN 201810432404A CN 110452335 A CN110452335 A CN 110452335A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/54—Amines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/26—Amines
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Abstract
The invention provides a viscosity index improver and a preparation method thereof. The preparation method of the viscosity index improver comprises the following steps: s1, mixing a grafting initiator, an acrylic compound, an ethylene-propylene rubber polymer and a solvent, and carrying out grafting reaction to obtain a first solution of an ethylene-propylene copolymer grafted by the acrylic compound; and S2, mixing the first solution with an amine compound and carrying out amination reaction to obtain the viscosity index improver. Because the acrylic acid compound belongs to organic acid and the amine compound belongs to organic amine, acid-base neutralization reaction is easy to occur, so that the preparation process of the ethylene-propylene copolymer viscosity index improver can be carried out at low temperature, and experiments prove that the ethylene-propylene copolymer viscosity index improver prepared by the preparation method has low-temperature stability, high-temperature thickening capacity and shear stability reaching the level of T-615.
Description
Technical field
The present invention relates to petrochemical industries, in particular to a kind of viscosity index improver and preparation method thereof.
Background technique
Viscosity index improver is called tackifier, is mainly used for I. C. engine oil, hydraulic oil, automatic transmission fluid and gear oil
In, its dosage is only second to detersive and dispersing agent within the scope of lube oil additive.Viscosity index improver is oil-soluble chain
High-molecular compound is soluble in the hydrocarbon base oils for lubricant, the high score sub-line of viscosity index improver in low temperature
Circle is shunk, smaller thus also relatively small to the viscosity influence of oil product to the interior frictional influence of base oil；Viscosity refers at high temperature
The high score subcoil of number modifier is swollen stretching, extension, and hydrodynamic volume and surface area increase, and increases the interior friction of base oil significantly
Add, Basic oil Viscosity increases, and so as to improve the high temperature lubricating of base oil, reached improves oil viscosity at different temperatures
The purpose of performance.
Viscosity index improver can not only be thickened base oil, and can change the viscous warm nature of oil product, have oil product good
Good high temperature lubricating and low temperature flow can also reduce the consumption of fuel and lubricating oil, realize oil product generalization.In addition,
Viscosity index improver is not required nothing more than, apparent adverse effect is not generated to anti-oxidative stability, the detergency of oil product, also require
Thickened oil viscosity loss appropriateness under mechanical shearing effect.In practical applications, a kind of good viscosity index improver is not only wanted
Ask the big shear stability of thickening ability good, at the same it is also desirable to have good cryogenic property, thermal oxidation stability and with it is other
Oil dope (such as: pour-point depressant) has good compatibility.Thus, in the development and production process of lubricating oil, to infuse
Meaning chooses viscosity index improver.
Common viscosity index improver has plus hydrogen styrene diene (styrene-isoprene) polymer (HSD), gather it is different
Butylene (PIB), ethylene-propylene copolymer (OCP), four major class of polymethacrylates (PMA).Since ethylene-propylene copolymer viscosity refers to
Number modifier (OCP) engine showed in high comprehensive performance, it is cheap the advantages that, therefore obtain extensively send out application
And development.Ethylene-propylene copolymer can be obtained by two kinds of approach, one is by the higher EP rubbers of molecular weight by thermal oxide,
Mechanical degradation meets requirement to certain molecular weight；The second is direct polymerization obtain the suitable polymer of molecular weight or
The EP rubbers chemical degradation of higher molecular weight is functionalized processing again to obtain.
EP rubbers chemical degradation technique is that polymer is dissolved in base oil, free radical chain rupture is carried out again, finally draws
Enter functionalized species, major defect: one is polymer solution temperature is high, needing longer dissolution time and higher energy consumption；
The second is base oil and the third polymer viscosity of second vary with temperature larger, free radical grafting technique is caused to be also required in higher temperature
Degree is lower to carry out；The third is functionalized species and reaction residue matter must remove under high temperature and vacuum condition；The fourth is product
In contain base oil, to it is different using producer for, due to the difference in base oil source, lead to the adjustment using technique.
Summary of the invention
The main purpose of the present invention is to provide a kind of viscosity index improvers and preparation method thereof, to solve existing second
The high problem of energy consumption caused by needing to carry out at high temperature in the preparation process of propylene copolymer viscosity index improver.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of preparation of viscosity index improver
Method, comprising the following steps: graft initiator, acrylic compounds, EP rubbers polymer and solvent are mixed and gone forward side by side by S1
Row graft reaction, obtain include acrylic compounds grafting ethylene-propylene copolymer the first solution；S2, by the first solution and amine
Class compound mixes and carries out aminating reaction, obtains viscosity index improver.
Further, the dosage of acrylic compounds is the 0.2~3.0% of EP rubbers polymer volume.
Further, acrylic compounds are selected from acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, first
Base methyl acrylate and butyl methacrylate are any one or more of.
Further, EP rubbers polymer is ethylene, propylene copolymer, and wherein ethylene corresponding molecule chain element contains
Amount is 48~70%, and the Mooney viscosity of preferably EP rubbers polymer is 5~60, the weight of preferably EP rubbers polymer is second
The 4~20% of third rubber polymer and solvent total weight.
Further, graft initiator is peroxide, and preferably graft initiator includes benzoyl peroxide and/or peroxide
Change diisopropylbenzene (DIPB), the preferably dosage of graft initiator is the 0.01~2.0% of EP rubbers polymer weight.
Further, solvent includes that aromatic hydrocarbons, cycloalkane and linear paraffin class are any one or more of, linear paraffin
Class includes that hexane, heptane and octane are any one or more of, and preferred solvent is hexane.
Further, in step sl, the reaction temperature of graft reaction be 80~120 DEG C, reaction pressure be 0.1~
0.2MPa, reaction time are 1.0~4.0h.
Further, the solid content of the first solution is 5~40%.
Further, aminated compounds N, N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine and/or N- (1,3- dimethylbutyl)-
N'- phenyl-Isosorbide-5-Nitrae-phenylenediamine, the preferably dosage of aminated compounds are the 0.05~0.2% of EP rubbers polymer weight.
Further, step S2 includes following procedure: S21, and the first solution is heated to the first temperature, preferably the first temperature
It is 80~120 DEG C；Aminated compounds is added dropwise into the first solution after heating under agitation in S22 so that the first solution with
Aminated compounds mixes and carries out aminating reaction, obtain include viscosity index improver the second solution, preferred aminating reaction
Reaction pressure is 0.1~0.2MPa, and the reaction time is 2~4h.
Further, after process S22, step S2 further includes the separating-purifying viscosity index improver from the second solution
The step of；Preferable separate purification step includes: that the second solution is carried out falling film evaporation, to obtain viscosity index improver.
According to another aspect of the present invention, a kind of viscosity index improver, viscosity index improver CH are provided3-
(CH2CH2)a-(CH2CH(CH3))b-CH2It is 500~1200, a:b is 0.9~1.5:1, R that CRCOOR ', a, which are 500~1000, b,
For H or CH3, R ' is N, N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine and/or N- (1,3- dimethylbutyl)-N'- phenyl-Isosorbide-5-Nitrae-benzene two
Amine.
Further, a is 700~900；It is preferred that b is 700~1000；It is preferred that a:b is 0.95~1.2:1.
It applies the technical scheme of the present invention, provides a kind of preparation method of viscosity index improver, first will include connecing
Branch initiator, acrylic compounds, EP rubbers polymer and solvent raw material mix and carry out graft reaction, including
First solution of the ethylene-propylene copolymer of acrylic compounds grafting, the first solution then mixed and carried out with aminated compounds
Aminating reaction obtains viscosity index improver.Since acrylic compounds belong to organic acid, aminated compounds belongs to organic
Amine, it is easy to acid-base neutralization reaction occur, so that the preparation process of above-mentioned ethylene-propylene copolymer viscosity index improver be enable to exist
It carries out, and is experimentally confirmed under low temperature, the ethylene-propylene copolymer viscosity index improver obtained using above-mentioned preparation method, low temperature
Stability, high temperature thickening ability, shear stability can reach T-615 level.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
In order to enable those skilled in the art to better understand the solution of the present invention, right below in conjunction with the embodiment of the present invention
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only the present invention one
Partial embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, should fall within the scope of the present invention.
It should be noted that the term " first ", " second " etc. in description and claims of this specification are to be used for
Similar object is distinguished, without being used to describe a particular order or precedence order.It should be understood that the data used in this way are suitable
It can be interchanged in the case of, so as to the embodiment of the present invention described herein.In addition, term " includes " and " having " and they
Any deformation, it is intended that cover it is non-exclusive include, for example, containing the process, method of a series of steps or units, being
System, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include be not clearly listed or
For the intrinsic other step or units of these process, methods, product or equipment.
It can be seen from background technology that it is urgent to provide one kind to have high thickening ability, low sheraing stability index in the prior art
EP rubbers lubricating oil viscosity index improver.The present inventor studies regarding to the issue above, provides one kind
The preparation method of viscosity index improver, comprising the following steps: S1, by graft initiator, acrylic compounds, EP rubbers
Polymer and solvent mix and carry out graft reaction, obtain include acrylic compounds grafting ethylene-propylene copolymer it is first molten
Liquid；First solution is mixed with aminated compounds and is carried out aminating reaction, obtains viscosity index improver by S2.
The ethylene-propylene copolymer viscosity index improver product obtained using above-mentioned preparation method, low-temperature stability, high temperature are thick
Change ability, shear stability can reach T-615 level；Above-mentioned preparation method can be carried out directly on existing process units
Transformation, increased graft reaction and aminating reaction equipment belong to common chemical industry equipment, and operating condition is not also harsh, eliminates original
Glue high temperature flash concentrate, extruding and pelletizing process, enormously simplify practical operation difficulty；Above-mentioned preparation method is able to use two
The transition material generated during first EP rubbers grade transition, can not only make full use of raw material resources, can also be greatly
The added value of this partial material is promoted, significantly lifting device creates efficiency power；Also, aminating reaction technique can generate a certain amount of
Waste liquid containing acrylic compounds, phenylenediamine can get rid of the organic impurities in waste liquid by the technique of acid-base neutralization,
Recycling use can satisfy production requirement.
The exemplary reality of the preparation method of the viscosity index improver provided according to the present invention is provided
Apply mode.However, these illustrative embodiments can be implemented by many different forms, and it is not construed as only
It is limited to embodiments set forth herein.It should be understood that thesing embodiments are provided so that disclosure herein
It is thoroughly and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
Firstly, executing step S1: graft initiator, acrylic compounds, EP rubbers polymer and solvent are mixed
And carry out graft reaction, obtain include acrylic compounds grafting ethylene-propylene copolymer the first solution.Above-mentioned solvent includes
Aromatic hydrocarbons, cycloalkane and linear paraffin class are any one or more of, and linear paraffin class includes in hexane, heptane and octane
Any one or more, preferred solvent is hexane, those skilled in the art can according to the prior art to the type of above-mentioned solvent into
Row Rational choice.Preferably, above-mentioned solvent makes full use of hexane using EP rubbers polymer hexane solution as raw material for hexane
Polymer is fully extended the feature lower with system viscosity in solution, can carry out under lower reaction temperature and pressure anti-
It answers, avoids high-temperature operation condition.
In above-mentioned steps S1, it is preferable that the weight of acrylic compounds be EP rubbers polymer weight 0.2~
3.0%.By the way that the weight of acrylic compounds to be limited in above-mentioned preferred range, suitable acrylic compounds can be grafted
Compound, so that low-temperature stability, height can be obtained after the ethylene-propylene copolymer aminating reaction being grafted to acrylic compounds
Warm thickening ability, shear stability reach the viscosity index improver of T-615 level.Those skilled in the art can be according to existing
There is technology to carry out Rational choice to the type of above-mentioned acrylic compounds, it is excellent in order to improve the performance of viscosity index improver
Selection of land, above-mentioned acrylic compounds are selected from acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, methacrylic acid
Methyl esters and butyl methacrylate are any one or more of.
In above-mentioned steps S1, EP rubbers polymer is ethylene, propylene copolymer, it is preferable that EP rubbers polymer
The content of the corresponding molecule chain element of middle ethylene is 48~70%, and the corresponding molecule chain element of above-mentioned ethylene refers to that vinyl monomer passes through
After polymerization in macromolecular chain corresponding structure content；It is further preferable that the Mooney viscosity ML of EP rubbers polymer1+4 100℃
Weight for 5~60, polymer is the 4~20% of EP rubbers polymer and solvent total weight.By by ethylene contents, Mooney
Viscosity and polymer content are limited in above-mentioned preferred range, can guarantee that suitable acrylic compounds are grafted on second
It on propylene copolymer, and then ensure that after the ethylene-propylene copolymer aminating reaction being grafted to acrylic compounds, obtained viscosity
Index improver has excellent performance.
It is excellent in order to improve grafting efficiency of the acrylic compounds on EP rubbers polymer in above-mentioned steps S1
Selection of land, graft initiator are peroxide, it is further preferable that above-mentioned graft initiator includes benzoyl peroxide and/or peroxide
Change diisopropylbenzene (DIPB).Also, in order to avoid graft initiator weight it is excessive caused by waste, it is preferable that above-mentioned graft initiator
Weight be EP rubbers polymer weight 0.01~2.0%.
In a preferred embodiment, in step sl, the reaction temperature of graft polymerization reaction is 80~120 DEG C,
Reaction pressure is 0.1~0.2MPa, and the reaction time is 1.0~4.0h.Specifically, by above-mentioned graft initiator and above-mentioned acrylic acid
Class compound is added in the solution containing EP rubbers polymer, reaction temperature be 80~120 DEG C, reaction pressure 0.1~
Graft reaction is carried out under conditions of 0.2MPa, the reaction time is that 1.0~4.0h is obtained containing acrylic compounds after completion of the reaction
Close the first solution of the ethylene-propylene copolymer intermediate product of object grafting.
In above-mentioned preferred embodiment, after completion of the reaction, above-mentioned first solution can be obtained by flash distillation, in order to mention
The process efficiency of high subsequent aminating reaction, it is preferable that by flash process obtain that solid content is 5~40% it is above-mentioned first molten
Liquid.Those skilled in the art can carry out reasonable set according to process conditions of the prior art to above-mentioned flash distillation, no longer superfluous herein
It states.
After executing the step S1, step S2 is executed: by the above-mentioned Propylene polymerization containing acrylic compounds grafting
First solution of object mixes with aminated compounds and carries out aminating reaction, obtains viscosity index improver.Those skilled in the art
Rational choice can be carried out to the type of above-mentioned aminated compounds according to the prior art, in order to improve obtain after aminating reaction it is viscous
Spend low-temperature stability, high temperature thickening ability and the shear stability of index improver, it is preferable that above-mentioned aminated compounds is N,
N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine (C12H20N2) and/or N- (1,3- dimethylbutyl)-N'- phenyl -1,4- phenylenediamine
(C18H24N2)；It is further preferable that the weight of above-mentioned aminated compounds is the 0.05~0.2% of EP rubbers polymer weight.
Above-mentioned steps S2 may include: S21, and above-mentioned first solution is heated to the first temperature；S22, under agitation
Aminated compounds is added dropwise into the first solution after heating, so that the first solution is mixed with aminated compounds and to carry out amination anti-
Answer, obtain include viscosity index improver the second solution.In order to make the second third that acrylic compounds are grafted in the first solution
Copolymer can sufficiently carry out aminating reaction with aminated compounds, and improve the efficiency of above-mentioned aminating reaction, a kind of preferred
In embodiment, the first solution of the ethylene-propylene copolymer being grafted containing acrylic compounds is heated to 80~120 DEG C, then
Aminated compounds is added dropwise under agitation, and reacts 2~4h under conditions of 0.1~0.2MPa of reaction pressure.
After above-mentioned steps S22, above-mentioned steps S2 can also include from the second solution separating-purifying viscosity index (VI) change
Into the step of agent；In order to improve the efficiency of above-mentioned separating-purifying, it is preferable that above-mentioned separating-purifying step includes: by the second solution
Falling film evaporation is carried out, to obtain viscosity index improver.
Other hand according to the present invention additionally provides a kind of viscosity index improver, which is
CH3-(CH2CH2)a-(CH2CH(CH3))b-CH2CRCOOR ', a are 500~1000, preferably 700~900；B is 500~1200,
Preferably 700~1000；A:b ratio 0.9~1.5, preferably 0.95~1.2；R is H or CH3；R ' is N, N ,-diisopropyl-
1,4- phenylenediamine and/or N- (1,3- dimethylbutyl)-N'- phenyl -1,4- phenylenediamine.
The low-temperature stability of above-mentioned ethylene-propylene copolymer viscosity index improver, high temperature thickening ability and shear stability are equal
It is horizontal that T615 viscosity index improver can be reached.
The preparation side of viscosity index improver provided by the invention is further illustrated below in conjunction with embodiment and comparative example
Method.
Following embodiments carry out in the 1.0L autoclave of laboratory, and reaction kettle uses Electric heating, and collet changes
Thermal medium is conduction oil, and second the third polymer hexane solution is taken from EP rubbers process units.
Embodiment 1
The initial temperature of the third polymer of second hexane solution is between 15~25 DEG C in the present embodiment, solid content 4.0%, second
The content of the corresponding molecule chain element of alkene is 48.5%, polymer Mooney viscosity (ML1+4 100DEG C) it is 6.0, the equal molecule of polymer number
Amount is 7.9 ten thousand, weight average molecular weight is 15.8 ten thousand, relative molecular mass distribution 2.00.
It takes above-mentioned polymer hexane solution 0.6L to be added in reaction kettle, benzoyl peroxide and acrylic acid, acrylic acid is added
Weight be the 1.0% of EP rubbers polymer weight, the weight of benzoyl peroxide is EP rubbers polymer weight
2.0%, agitation revolution 125r/min, reaction kettle internal temperature be 80 DEG C~82 DEG C, reactor pressure be 0.115MPa~
0.120MPa after reaction 4 hours, stops stirring, slowly opens gaseous phase outlet valve and carries out flashing operation, the gaseous phase materials of discharge are logical
It crosses condenser condensation and stops flashing operation and heating when recycling condensate liquid is close to 200mL.Restore normal pressure to reactor pressure.This
When, glue solid content is 5.9%, and temperature is 66 DEG C.
Above-mentioned polymer hexane solution 400mL is heated to 80 DEG C~82 DEG C, under agitation, is added dropwise using syringe
N, N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine is in above-mentioned hexane solution, N, N, and-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine weight is second third
The 0.10% of rubber polymer weight, agitation revolution 125r/min, under conditions of reaction pressure 0.115MPa~0.120MPa
4h is reacted, stirring is stopped, gaseous phase outlet valve is slowly opened and carries out flashing operation, the gaseous phase materials of discharge are condensed by condenser,
When recycling condensate liquid close to 50mL, stop flashing operation.Condenser rear vacuum valve is opened, vacuum desolvation agent operation is carried out,
Vacuum takes off low molecule 10 minutes no lime set again, closes vacuum valve and electric heating, restores reactor pressure and continue to pour nitrogen extremely
0.15MPa releases material when temperature of reaction kettle is reduced to 50 DEG C or less.
Embodiment 2
The present embodiment the difference from embodiment 1 is that:
The solid content of second the third polymer hexane solution is 8.1%, and the solid content of glue is 12.0% after flash distillation.
Embodiment 3
The present embodiment the difference from embodiment 1 is that:
The solid content of second the third polymer hexane solution is 14.4%, and the solid content of glue is 21.2% after flash distillation.
Embodiment 4
The present embodiment the difference from example 2 is that:
The content of the corresponding molecule chain element of ethylene is 55% in EP rubbers polymer, the Mooney of EP rubbers polymer
Viscosity is 58, and polymer number-average molecular weight is 7.2 ten thousand, weight average molecular weight is 14.0 ten thousand, relative molecular mass distribution 1.94.
Embodiment 5
The present embodiment the difference from example 2 is that:
The content of the corresponding molecule chain element of ethylene is 67% in EP rubbers polymer, the Mooney of EP rubbers polymer
Viscosity is 7.5, and polymer number-average molecular weight is 7.8 ten thousand, weight average molecular weight is 14.1 ten thousand, relative molecular mass distribution 1.81.
Embodiment 6
The present embodiment the difference from embodiment 1 is that:
The weight of acrylic acid is the 0.20% of EP rubbers polymer weight.
Embodiment 7
The present embodiment the difference from embodiment 1 is that:
The weight of acrylic acid is the 3.0% of EP rubbers polymer weight.
Embodiment 8
The present embodiment the difference from embodiment 1 is that:
The weight of graft initiator is the 0.01% of EP rubbers polymer weight.
Embodiment 9
The present embodiment the difference from embodiment 1 is that:
The weight of graft initiator is the 1.0% of EP rubbers polymer weight.
Embodiment 10
The present embodiment and the difference of embodiment 9 are:
Reaction kettle internal temperature is 100 DEG C~102 DEG C, and reactor pressure is 0.145MPa~0.150MPa, reacts 4h.
Embodiment 11
The present embodiment and the difference of embodiment 9 are:
Reaction kettle internal temperature is 118 DEG C~120 DEG C, and reactor pressure is 0.145MPa~0.150MPa, reacts 4h.
Embodiment 12
The present embodiment and the difference of embodiment 9 are:
N, N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine weight are the 0.05% of EP rubbers polymer weight.
Embodiment 13
The present embodiment and the difference of embodiment 9 are:
N, N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine weight are the 0.20% of EP rubbers polymer weight.
Embodiment 14
The present embodiment and the difference of embodiment 9 are:
2h is reacted under conditions of reaction pressure 0.145MPa~0.150MPa.
Embodiment 15
The present embodiment and the difference of embodiment 9 are:
4h is reacted under conditions of reaction pressure 0.195MPa~0.200MPa.
Viscosity index improver class criteria is as shown in table 1, using GB/T265-88 " oil product kinematic viscosity measuring method
With dynamic viscosity calculating method ", SH/T0566-93 " lubricating oil viscosity index improver thickening capabilities measuring method ", SH/T0103-
2007 " measurements (diesel injector method) of the stability containing polymeric shear " refer to the viscosity being prepared in above-described embodiment 1 to 15
Kinematic viscosity, thickening ability and the shear stability of number modifier are tested, and test result is as shown in table 2.
Table 1
| Project | T612 | T613 | T614 | T615 | |
| Kinematic viscosity (100 DEG C)/mm2·s-1 | It is not less than | 600 | 800 | 650 | 550 |
| Thickening ability/mm2·s-1 | It is not less than | 4.5 | 4.8 | 4.5 | 4.0 |
| The spray of shear stability (100 DEG C)/bavin | It is not more than | 50 | 35 | 27 | 20 |
Table 2
It is equal to can be seen that the viscosity index improver being prepared in the embodiment of the present application 1 to 15 from above-mentioned test result
It is horizontal that T-615 in viscosity index improver class criteria can be reached.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1, the ethylene-propylene copolymer viscosity index improver product that the present invention obtains, low-temperature stability, are cut high temperature thickening ability
T-615 level can be reached by cutting stability.
2, the present invention makes full use of polymer in hexane solution sufficiently to stretch using EP rubbers polymer hexane solution as raw material
Exhibition and the lower feature of system viscosity, can be reacted under lower reaction temperature and pressure, avoid high-temperature operation item
Part.
3, the preparation method of above-mentioned viscosity index improver of the invention can directly be changed on existing process units
It makes, increased graft reaction and aminating reaction equipment belong to common chemical industry equipment, and operating condition is not also harsh, eliminates original
Glue high temperature flashes concentrate, extruding and pelletizing process, enormously simplifies practical operation difficulty.
4, the preparation method of above-mentioned viscosity index improver of the invention is able to use bibasic ethylene propylene rubber grade transition mistake
The transition material generated in journey, can not only make full use of raw material resources, can also greatly promote the additional of this partial material
Value, significantly lifting device creates efficiency power.
5, it is according to the present invention grafting, aminating reaction technique can generate it is a certain amount of containing acrylic compounds, benzene
The useless hexane of diamines, can get rid of the organic impurities in hexane by the technique of acid-base neutralization, and recycling use can satisfy life
It produces and requires.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of viscosity index improver, which comprises the following steps:
Graft initiator, acrylic compounds, EP rubbers polymer and solvent are mixed and are carried out graft reaction, obtain by S1
To the first solution of the ethylene-propylene copolymer for including acrylic compounds grafting；
First solution is mixed with aminated compounds and is carried out aminating reaction, obtains the viscosity index improver by S2.
2. preparation method according to claim 1, which is characterized in that the dosage of the acrylic compounds is the second
The 0.2~3.0% of third rubber polymer dosage.
3. preparation method according to claim 1, which is characterized in that the acrylic compounds are selected from acrylic acid, first
Any one of base acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate are more
Kind.
4. preparation method according to any one of claim 1 to 3, which is characterized in that the EP rubbers polymer is
Ethylene, propylene copolymer, wherein the content of the corresponding molecule chain element of the ethylene is 48~70%, the preferably described EP rubbers
The Mooney viscosity of polymer is 5~60, the weight of the preferably described EP rubbers polymer is the EP rubbers polymer and institute
State the 4~20% of solvent total weight.
5. the preparation method according to claim 4, which is characterized in that the graft initiator is peroxide, preferably institute
Stating graft initiator includes benzoyl peroxide and/or cumyl peroxide, and the dosage of the preferably described graft initiator is institute
State the 0.01~2.0% of EP rubbers polymer weight.
6. preparation method according to claim 1, which is characterized in that the solvent includes aromatic hydrocarbons, cycloalkane and straight
Paraffinic is any one or more of, and the linear paraffin class includes that hexane, heptane and octane are any one or more of, excellent
Selecting the solvent is hexane.
7. preparation method according to any one of claim 1 to 6, which is characterized in that in the step S1, described to connect
The reaction temperature of branch reaction is 80~120 DEG C, and reaction pressure is 0.1~0.2MPa, and the reaction time is 1.0~4.0h.
8. preparation method according to claim 7, which is characterized in that the solid content of first solution is 5~40%.
9. preparation method according to claim 1, which is characterized in that the aminated compounds be N, N,-diisopropyl -1,
4- phenylenediamine and/or N- (1,3- dimethylbutyl)-N'- phenyl-Isosorbide-5-Nitrae-phenylenediamine, the dosage of the preferably described aminated compounds are
The 0.05~0.2% of the EP rubbers polymer weight.
10. according to claim 1 or preparation method described in 9, which is characterized in that the step S2 includes following procedure:
First solution is heated to the first temperature by S21, and preferably described first temperature is 80~120 DEG C；
The aminated compounds is added dropwise into first solution after heating under agitation, so that described first is molten in S22
Liquid mixes with the aminated compounds and carries out aminating reaction, obtain include the viscosity index improver the second solution, it is excellent
The reaction pressure for selecting the aminating reaction is 0.1~0.2MPa, and the reaction time is 2~4h.
11. preparation method according to claim 10, which is characterized in that after the process S22, the step S2 is also
Include the steps that the viscosity index improver described in separating-purifying from second solution；It is preferred that the separating-purifying step packet
It includes:
Second solution is subjected to falling film evaporation, to obtain the viscosity index improver.
12. a kind of viscosity index improver, which is characterized in that the viscosity index improver is CH3-(CH2CH2)a-(CH2CH
(CH3))b-CH2It is 500~1200, a:b is 0.9~1.5:1 that CRCOOR ', a, which are 500~1000, b, and R is H or CH3, R ' is N,
N ,-diisopropyl-Isosorbide-5-Nitrae-phenylenediamine and/or N- (1,3- dimethylbutyl)-N'- phenyl-Isosorbide-5-Nitrae-phenylenediamine.
13. viscosity index improver according to claim 12, which is characterized in that a is 700~900；It is preferred that b be 700~
1000；It is preferred that a:b is 0.95~1.2:1.
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| CN201810432404.6A CN110452335A (en) | 2018-05-08 | 2018-05-08 | Viscosity index improver and preparation method thereof |
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| CN201810432404.6A CN110452335A (en) | 2018-05-08 | 2018-05-08 | Viscosity index improver and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232614A (en) * | 1989-02-23 | 1993-08-03 | Exxon Chemical Patents Inc. | Lubricating oil compositions and additives for use therein |
| US5384371A (en) * | 1990-02-23 | 1995-01-24 | Dsm Copolymer, Inc. | Continuous process for producing adducted EPM or EPDM oil solution |
| CN1214345A (en) * | 1997-10-15 | 1999-04-21 | 乙基公司 | Functionalized olefin copolymer additives |
| CN104560233A (en) * | 2015-01-19 | 2015-04-29 | 广汉市天舟航空发动机燃料科技有限公司 | Low-lead aviation gasoline and preparation method thereof |
-
2018
- 2018-05-08 CN CN201810432404.6A patent/CN110452335A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232614A (en) * | 1989-02-23 | 1993-08-03 | Exxon Chemical Patents Inc. | Lubricating oil compositions and additives for use therein |
| US5384371A (en) * | 1990-02-23 | 1995-01-24 | Dsm Copolymer, Inc. | Continuous process for producing adducted EPM or EPDM oil solution |
| CN1214345A (en) * | 1997-10-15 | 1999-04-21 | 乙基公司 | Functionalized olefin copolymer additives |
| CN104560233A (en) * | 2015-01-19 | 2015-04-29 | 广汉市天舟航空发动机燃料科技有限公司 | Low-lead aviation gasoline and preparation method thereof |
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Application publication date: 20191115 |