CN107501489B - A kind of Miktoarm star polymer of carbazolyl-containing and its preparation method and application - Google Patents
A kind of Miktoarm star polymer of carbazolyl-containing and its preparation method and application Download PDFInfo
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- CN107501489B CN107501489B CN201710734426.3A CN201710734426A CN107501489B CN 107501489 B CN107501489 B CN 107501489B CN 201710734426 A CN201710734426 A CN 201710734426A CN 107501489 B CN107501489 B CN 107501489B
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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
- C08F301/00—Macromolecular compounds not provided for in groups C08F10/00 - C08F299/00
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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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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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
- C08F8/04—Reduction, e.g. hydrogenation
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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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
Abstract
The present invention provides a kind of Miktoarm star polymer and its preparation method and application of carbazolyl-containing, belongs to technical field of polymer materials.It solves existing pour depressant for lubricating oil and viscosity index improver performance is lower, the problem of compatibility difference.The general structure of the polymer is An‑C‑Bm, wherein A is that polyisoprene and/or polybutadiene are long-armed, and B is polycarbazole arm, and C is polydivinylbenezene core, and m and n are arm number, and the value range of m is 3-20, and the value range of n is 3-20.The present invention also provides a kind of preparation methods of the Miktoarm star polymer of carbazolyl-containing.Application the present invention also provides the Miktoarm star polymer of above-mentioned carbazolyl-containing as lubrication oil assistant.There is lubrication oil assistant of the invention lubricating oil viscosity to refer to the double action with pour point depression, realize that V100 reaches 12mm2/ s, CCS reach 400mPa.s, and pour point declines 20 DEG C of high-performance.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of Miktoarm star polymer of carbazolyl-containing and its
Preparation method and application.
Background technique
Lubricating oil is significant for the reliability and service life that improve mechanical movement.It is added in base oil different
Auxiliary agent can effectively improve the performance indicator of lubricating oil, therefore the performance of auxiliary agent has decisive role for lubricating oil, especially
The high perofmrnace lubricating oils applied under extreme harsh conditions, the requirement for auxiliary agent are stringenter.
In recent years, it is high and cold to be located at the Northeast for our province for the industries high speed development such as automobile, aviation, track train, national defence
The particular surroundings feature in area, the safe operation of equipment in winter is greatly affected, especially in high-speed rail and national defence.Wherein
One major reason is exactly that cryogenic property is impacted in winter for lubricating oil, and mobility is deteriorated, and influences stability under low-temperature and high-speed.
In order to improve lubricating oil viscosity index and cryogenic property, two kinds of important auxiliary agents are often added --- lubricating oil drop
Solidifying agent and lubricating oil viscosity index improver.The addition of pour depressant for lubricating oil can effectively reduce the characteristics of lubricating oil, improve
Low temperature flow；The effect of lubricating oil viscosity index improver is to adjust lubricating oil viscosity index, realizes high-temperature thickening, low
Temperature guarantees pump-conveying property.Due to difference of two kinds of auxiliary agents in the mechanism of action and composed structure, cause compatibility poor, mixing makes
Cryogenic property after further declines (CN102731739A, CN1291223A, CN1234823A).
For this purpose, develop a kind of high performance adjuvant for having both lubricating oil viscosity index improver and pour-point depressant have a vast market foreground and
Important strategy function.
Summary of the invention
The purpose of the present invention is to solve existing pour depressant for lubricating oil and viscosity index improver performance are lower, compatibility difference is asked
Topic, and a kind of Miktoarm star polymer and its preparation method and application of carbazolyl-containing is provided.
Present invention firstly provides a kind of Miktoarm star polymer of carbazolyl-containing, the general structure of the polymer is An-C-
Bm, wherein A is that polyisoprene and/or polybutadiene are long-armed, and B is polycarbazole arm, and C is polydivinylbenezene core, and m and n are arm
Number, the value range of m are 3-20, and the value range of n is 3-20.
The present invention also provides a kind of preparation methods of the Miktoarm star polymer of carbazolyl-containing, this method comprises:
Step 1: under organic solvent, using butyl lithium as initiator, cause isoprene and/or polymerizing butadiene, obtain
Living polymerization object A；
Step 2: under organic solvent, using sec-butyl lithium as initiator, cause vinyl carbazole polymerization, obtain living chain
Polymer B；
Step 3: the living polymerization object A that step 1 the obtains and living polymerization object B that step 2 obtains is mixed, so
Divinylbenzene is added afterwards and carries out coupling reaction, obtains the Miktoarm star polymer of carbazolyl-containing.
Preferably, the polymerization temperature of the step one is 0-60 DEG C, and the reaction time is 0.5-6 hours.
Preferably, in the step one, the molar ratio of isoprene and butadiene is (1-10): (1-10).
Preferably, the polymerization temperature of the step two is -70-0 DEG C, and the reaction time is 4-12 hours.
Preferably, in the step two, the molar ratio of initiator and vinyl carbazole is 1:(10-10000).
Preferably, the coupling temperature of the step three is -60-0 DEG C, and the reaction time is 8-24 hours.
Preferably, in the step three, the molar ratio of living polymerization object A and living polymerization object B are (1-10):
(1-10)。
Application the present invention also provides the Miktoarm star polymer of above-mentioned carbazolyl-containing as lubrication oil assistant.
Preferably, the application method are as follows: be catalyzed the Miktoarm star polymer of carbazolyl-containing obtained above
Hydrogenation reaction is carried out under the action of agent, obtains lubrication oil assistant.
Beneficial effects of the present invention
Present invention firstly provides a kind of Miktoarm star polymers of carbazolyl-containing, and the Miktoarm star polymer is by controlling not
The length of star structure together, star-shaped quantity and linking arm, and function monomer carbazole group is introduced, make the polymer
There is viscous finger performance and pour point depression performance simultaneously, thoroughly solving two kinds of auxiliary agents is used separately compatibility from the design of the structure of molecular level
Property difference problem, and improve a lot to the cryogenic property of lubricating oil.
The present invention also provides a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing, this method is poly- using anion
The means of conjunction prepare Miktoarm star polymer in a manner of " Graft onto ".The carbazolyl-containing that the preparation method is simple, obtains
Miktoarm star polymer have excellent properties.
Application the present invention also provides the Miktoarm star polymer of above-mentioned carbazolyl-containing as lubrication oil assistant.Of the invention
There is lubrication oil assistant lubricating oil viscosity to refer to the double action with pour point depression, realize that V100 reaches 12mm2/ s, CCS reach 400mPa.s,
Pour point declines 20 DEG C of high-performance.
Detailed description of the invention
Fig. 1 is the GPC figure for the product that the embodiment of the present invention 1 is prepared；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the product that the embodiment of the present invention 2 is prepared.
Specific embodiment
Present invention firstly provides a kind of Miktoarm star polymer of carbazolyl-containing, the general structure of the polymer is An-C-
Bm, wherein A is that polyisoprene and/or polybutadiene are long-armed, and range of number-average molecular weight 2000-90000g/mol, B are poly-
Carbazole arm, range of number-average molecular weight 1000-20000g/mol, C are polydivinylbenezene core, and m and n are arm number, the value of m
Range is 3-20, and the value range of n is 3-20.
The present invention also provides a kind of preparation methods of the Miktoarm star polymer of carbazolyl-containing, this method comprises:
Step 1: under organic solvent, using butyl lithium as initiator, cause isoprene and/or polymerizing butadiene, obtain
Living polymerization object A；
Step 2: under organic solvent, using sec-butyl lithium as initiator, cause vinyl carbazole polymerization, obtain living chain
Polymer B；
Step 3: the living polymerization object A that step 1 the obtains and living polymerization object B that step 2 obtains is mixed, so
Divinylbenzene is added afterwards and carries out coupling reaction, obtains the Miktoarm star polymer of carbazolyl-containing.
According to the present invention, under organic solvent, using butyl lithium as initiator, cause isoprene and/or polymerizing butadiene,
The polymerization temperature is preferably 0-60 DEG C, and more preferably 50 DEG C, the reaction time is preferably 0.5-6 hours, and more preferably 4 is small
When, obtain living polymerization object A；The solvent is preferably toluene, mole of the isoprene, butadiene and initiator
Than for (1-10): (1-10): (1/10-1/106), the volume ratio of more preferable isoprene and butadiene is 1:1.
According to the present invention, under organic solvent, using sec-butyl lithium as initiator, cause vinyl carbazole polymerization, it is described
Polymerization temperature is preferably -70-0 DEG C, and more preferably 0 DEG C, the reaction time is preferably 4-24 hours, more preferably 12 hours, is obtained
Living polymerization object B；The solvent is preferably toluene, and the molar ratio of initiator and vinyl carbazole is preferably 1:(10-
10000), it is furthermore preferred that the volume (mL) of the initiator: the quality (g) of vinyl carbazole is 0.2:(2-4).
According to the present invention, living polymerization object A and living polymerization object B is mixed, toluene solution dilution is added, then plus
Enter divinylbenzene and carry out coupling reaction, the coupling temperature is preferably -60-0 DEG C, and more preferably 0 DEG C, the reaction time is preferred
It is 8-24 hours, more preferably 12 hours, obtains the Miktoarm star polymer of carbazolyl-containing.The living polymerization object A and
Living polymerization object B molar ratio is preferably (1-10): (1-10), the volume (mL) of the divinylbenzene: vinyl carbazole
Quality (g) be 2:(2-4).
Application the present invention also provides the Miktoarm star polymer of above-mentioned carbazolyl-containing as lubrication oil assistant.
According to the present invention, the application method are as follows: urging the Miktoarm star polymer of carbazolyl-containing obtained above
Hydrogenation reaction is carried out under the action of agent, obtains lubrication oil assistant.The catalyst is preferably nickel naphthenate/alkyl aluminum, or
Nickel octoate/alkyl aluminum.The hydrogenation reaction temperature is preferably 50 DEG C, and the reaction time is preferably 3h.
The present invention will be further described in detail combined with specific embodiments below, and the raw material being related in embodiment is
It is commercially available.
Embodiment 1
The flask of 100mL under gas lamp heating condition, vacuumizes-leads to nitrogen displacement three times, the water oxygen etc. in removing system
Impurity finally keeps being cooled to room temperature under condition of nitrogen gas, and toluene 50mL obtained and distillation purification after sodium reflux purification is added
Isoprene 5mL, purified tetrahydrofuran 0.5mL, n-BuLi 1ml (0.2mol/L), 50 DEG C of reaction temperature, react 4 hours,
Obtain living polymerization object A；
It separately takes under 100mL flask gas lamp heating condition, vacuumizes-lead to nitrogen displacement three times, the water oxygen in removing system
Equal impurity finally keep being cooled to room temperature under condition of nitrogen gas, 4g vinyl carbazole are added, vacuumize and lead to nitrogen after twenty minutes, then
The dissolution of 40mL refined toluene is added, is added 0 DEG C of reaction temperature of s-butyl lithium 0.2mL (1.0mol/L), the reaction time 12 hours, obtains
To living polymerization object B；
By above-mentioned living polymerization object A and living polymerization object B solution, by threeway addition, through anhydrous and oxygen-free, treated
It is mixed in 250mL flask full of nitrogen, 2ml is added and refines divinylbenzene, 0 DEG C of reaction temperature, the reaction time 12 hours, obtains
To the Miktoarm star polymer of carbazolyl-containing.
The Miktoarm star polymer of carbazolyl-containing obtained above is transferred to 200mL to add in hydrogen kettle, nickel naphthenate is added
And aluminum alkyl catalyst, al-ti ratio 4:1, Hydrogen Vapor Pressure 3.0MPa, the reaction time 3 hours, temperature 50 C after adding hydrogen, added
The nickel naphthenate for entering hydrogen peroxide oxidation remnants adds sebacic acid, and after precipitating is removed in centrifugation, methanol extraction is obtained by drying to profit
Lubricating oil auxiliary agent.
Lubrication oil assistant obtained above is tested for the property, Fig. 1 is the product that the embodiment of the present invention 1 is prepared
GPC figure；Curve A represents living polymerization object A in Fig. 1, and curve B represents living polymerization object B, and curve C represents carbazolyl-containing
Miktoarm star polymer, GPC test result, star polymer number-average molecular weight 680,000, polyisoprene arm number-average molecular weight 7.2
Ten thousand, average arm number about 7, polyvinyl carbazole activity arm number-average molecular weight 1.8 ten thousand, average arm number about 10.Degree of hydrogenation 97.3%.On
It states viscosity index improver to be dissolved in CNOOC 150SN base oil, adds dose quality score 1%, cryogenic property CCS is improved
400mPa.s, SSI 10.2%, V100 improves 8.9mm2/ s, -35 DEG C of condensation point.
Embodiment 2
The flask of 100mL under gas lamp heating condition, vacuumizes-leads to nitrogen displacement three times, the water oxygen etc. in removing system
Impurity finally keeps being cooled to room temperature under condition of nitrogen gas, and toluene 50mL obtained and distillation purification after sodium reflux purification is added
Butadiene 5mL, purified tetrahydrofuran 0.5mL, n-BuLi 0.8ml (0.2mol/L), 50 DEG C of reaction temperature, react 4 hours,
Living polymerization object A；
It separately takes under 100mL flask gas lamp heating condition, vacuumizes-lead to nitrogen displacement three times, the water oxygen in removing system
Equal impurity finally keep being cooled to room temperature under condition of nitrogen gas, 4g vinyl carbazole are added, vacuumize and lead to nitrogen after twenty minutes, then
The dissolution of 40mL refined toluene is added, is added 0 DEG C of reaction temperature of s-butyl lithium 0.2mL (1.0mol/L), the reaction time 12 hours, obtains
To living polymerization object B；
By above-mentioned living polymerization object A and living polymerization object B solution, by threeway addition, through anhydrous and oxygen-free, treated
It is mixed in 250mL flask full of nitrogen, 2ml is added and refines divinylbenzene, 0 DEG C of reaction temperature, the reaction time 12 hours, obtains
To the Miktoarm star polymer of carbazolyl-containing.
The Miktoarm star polymer of carbazolyl-containing obtained above is transferred to 200mL to add in hydrogen kettle, nickel naphthenate is added
And aluminum alkyl catalyst, al-ti ratio 4:1, Hydrogen Vapor Pressure 3.0MPa, the reaction time 3 hours, temperature 50 C after adding hydrogen, added
The nickel naphthenate for entering hydrogen peroxide oxidation remnants adds sebacic acid, and after precipitating is removed in centrifugation, methanol extraction is obtained by drying to profit
Lubricating oil auxiliary agent.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 2 adds the product being prepared after hydrogen, figure it is seen that this hair
It is bright successfully to prepare the Miktoarm star polymer for having synthesized carbazolyl-containing.Lubrication oil assistant progressive obtained above can be surveyed
Examination, GPC test result, star polymer number-average molecular weight 720,000, polybutadiene arm number-average molecular weight 90,000, average arm number about 7,
Polyvinyl carbazole activity arm number-average molecular weight 1.5 ten thousand, average arm number about 10.Degree of hydrogenation 97.9%.During above-mentioned viscosity index improver is dissolved in
In extra large oil 150SN base oil, add dose quality score 1%, CCS improves 420mPa.s, and SSI 9.2%, V100 is improved
9.1mm2/ s, -32 DEG C of condensation point.
Embodiment 3
The flask of 100mL under gas lamp heating condition, vacuumizes-leads to nitrogen displacement three times, the water oxygen etc. in removing system
Impurity finally keeps being cooled to room temperature under condition of nitrogen gas, and toluene 50mL obtained and distillation purification after sodium reflux purification is added
Butadiene 5mL, purified tetrahydrofuran 0.5mL, n-BuLi 1ml (0.2mol/L), 50 DEG C of reaction temperature, react 4 hours, it is living
Property chain polymerization object A；
It separately takes under 100mL flask gas lamp heating condition, vacuumizes-lead to nitrogen displacement three times, the water oxygen in removing system
Equal impurity finally keep being cooled to room temperature under condition of nitrogen gas, 4g vinyl carbazole are added, vacuumize and lead to nitrogen after twenty minutes, then
The dissolution of 40mL refined toluene is added, is added 0 DEG C of reaction temperature of s-butyl lithium 0.2mL (1.0mol/L), the reaction time 12 hours, obtains
To living polymerization object B；
By above-mentioned living polymerization object A and living polymerization object B solution, by threeway addition, through anhydrous and oxygen-free, treated
It is mixed in 250mL flask full of nitrogen, 2ml is added and refines divinylbenzene, 0 DEG C of reaction temperature, the reaction time 12 hours, obtains
To the Miktoarm star polymer of carbazolyl-containing.Reaction route is as follows:
The Miktoarm star polymer of carbazolyl-containing obtained above is transferred to 200mL to add in hydrogen kettle, nickel naphthenate is added
And aluminum alkyl catalyst, al-ti ratio 4:1, Hydrogen Vapor Pressure 4.0MPa, the reaction time 3 hours, temperature 50 C after adding hydrogen, added
The nickel naphthenate for entering hydrogen peroxide oxidation remnants adds sebacic acid, and after precipitating is removed in centrifugation, methanol extraction is obtained by drying to profit
Lubricating oil auxiliary agent.
Lubrication oil assistant obtained above is tested for the property, GPC test result, star polymer number-average molecular weight 60
Ten thousand, polybutadiene arm number-average molecular weight 6.8 ten thousand, averagely arm number about 8, polyvinyl carbazole activity arm number-average molecular weight 1.0 ten thousand are put down
Equal arm number about 10.Degree of hydrogenation 98.9%.Above-mentioned viscosity index improver is dissolved in CNOOC 150SN base oil, adds dose quality score 1%,
Its CCS improves 400mPa.s, and SSI 11.4%, V100 improves 9.2mm2/ s, -36 DEG C of condensation point.
Embodiment 4
The flask of 100mL under gas lamp heating condition, vacuumizes-leads to nitrogen displacement three times, the water oxygen etc. in removing system
Impurity finally keeps being cooled to room temperature under condition of nitrogen gas, and toluene 50mL obtained and distillation purification after sodium reflux purification is added
Isoprene 3mL, butadiene 3mL, purified tetrahydrofuran 0.5mL, n-BuLi 1ml (0.2mol/L), 50 DEG C of reaction temperature,
Reaction 4 hours, living polymerization object A；
It separately takes under 100mL flask gas lamp heating condition, vacuumizes-lead to nitrogen displacement three times, the water oxygen in removing system
Equal impurity finally keep being cooled to room temperature under condition of nitrogen gas, 2g vinyl carbazole are added, vacuumize and lead to nitrogen after twenty minutes, then
The dissolution of 40mL refined toluene is added, is added 0 DEG C of reaction temperature of s-butyl lithium 0.2mL (1.0mol/L), the reaction time 12 hours, obtains
To living polymerization object B；
By above-mentioned living polymerization object A and living polymerization object B solution, by threeway addition, through anhydrous and oxygen-free, treated
It is mixed in 250mL flask full of nitrogen, 2ml is added and refines divinylbenzene, 0 DEG C of reaction temperature, the reaction time 12 hours, obtains
To the Miktoarm star polymer of carbazolyl-containing.
The Miktoarm star polymer of carbazolyl-containing obtained above is transferred to 200mL to add in hydrogen kettle, nickel naphthenate is added
And aluminum alkyl catalyst, al-ti ratio 4:1, Hydrogen Vapor Pressure 3.0MPa, the reaction time 3 hours, temperature 50 C after adding hydrogen, added
The nickel naphthenate for entering hydrogen peroxide oxidation remnants adds sebacic acid, and after precipitating is removed in centrifugation, methanol extraction is obtained by drying to profit
Lubricating oil auxiliary agent.
Lubrication oil assistant obtained above is tested for the property, GPC test result, star polymer number-average molecular weight 68
Ten thousand, polybutadiene-isoprene arm number-average molecular weight 6.5 ten thousand, average arm number about 8, the equal molecule of polyvinyl carbazole activity arm number
1.0 ten thousand are measured, average arm number about 15.Degree of hydrogenation 97.2%.Above-mentioned viscosity index improver is dissolved in CNOOC 150SN base oil, adds dosage matter
Score 1% is measured, CCS improves 400mPa.s, and SSI 10.2%, V100 improves 8.9mm2/ s, -35 DEG C of condensation point.
Claims (10)
1. a kind of Miktoarm star polymer of carbazolyl-containing, which is characterized in that the general structure of the polymer is An-C-Bm, wherein
A is that polyisoprene and/or polybutadiene are long-armed, and B is polycarbazole arm, and C is polydivinylbenezene core, and m and n are arm number, and m's takes
Value range is 3-20, and the value range of n is 3-20.
2. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 1, which is characterized in that should
Method includes:
Step 1: under organic solvent, using butyl lithium as initiator, cause isoprene and/or polymerizing butadiene, obtain activity
Chain polymerization object A；
Step 2: under organic solvent, using sec-butyl lithium as initiator, cause vinyl carbazole polymerization, obtain living polymerization
Object B；
Step 3: living polymerization object A that step 1 obtains and living polymerization object B that step 2 obtains are mixed, then plus
Enter divinylbenzene and carry out coupling reaction, obtains the Miktoarm star polymer of carbazolyl-containing.
3. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
The polymerization temperature of the step of stating one is 0-60 DEG C, and the reaction time is 0.5-6 hours.
4. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
In the step of stating one, the molar ratio of isoprene and butadiene is (1-10): (1-10).
5. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
The polymerization temperature of the step of stating two is -70-0 DEG C, and the reaction time is 4-12 hours.
6. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
In the step of stating two, the molar ratio of initiator and vinyl carbazole is 1:(10-10000).
7. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
The coupling temperature of the step of stating three is -60-0 DEG C, and the reaction time is 8-24 hours.
8. a kind of preparation method of the Miktoarm star polymer of carbazolyl-containing according to claim 2, which is characterized in that institute
In the step of stating three, the molar ratio of living polymerization object A and living polymerization object B are (1-10): (1-10).
9. application of the Miktoarm star polymer of carbazolyl-containing described in claim 1 as lubrication oil assistant.
10. application of the Miktoarm star polymer of carbazolyl-containing according to claim 9 as lubrication oil assistant, feature
Be, the application method are as follows: by the Miktoarm star polymer of carbazolyl-containing obtained above under the effect of the catalyst into
Row hydrogenation reaction obtains lubrication oil assistant.
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| US7501479B2 (en) * | 2007-05-07 | 2009-03-10 | Pittsburg State University | Cationic polymerization of biological oils with superacid catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102341342A (en) * | 2008-12-31 | 2012-02-01 | 株式会社普利司通 | Core-first nanoparticle formation process, nanoparticle, and composition |
| CN102731739A (en) * | 2012-07-05 | 2012-10-17 | 富阳经略化工技术有限公司 | Star polymer used as lubricating oil viscosity index improver, preparation method and application thereof |
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| CN107501489A (en) | 2017-12-22 |
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