CN108456266A - Catalyst for compound stereoscopic regularity polyvinylpyridine and application - Google Patents
Catalyst for compound stereoscopic regularity polyvinylpyridine and application Download PDFInfo
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- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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Abstract
The present invention provides a kind of catalyst for compound stereoscopic regularity polyvinylpyridine and application, belongs to olefin polymerization catalysis technical field.The biomolecule expressions that the catalyst of the present invention has are as follows：LnR3(L1)(L2) catalyst institute of the present invention polymer vinylpyridine monomers biomolecule expressions it is as follows：The catalyst is for being catalyzed a kind of vinylpyridine monomers homopolymerization or the copolymerization of two or more vinylpyridine monomers.The catalyst activity of the present invention is high, and the stereoregularity of controllable polymer, can prepare the polymer with unsaturated carbon-carbon double bond, the block that a variety of vinylpyridine monomers can be achieved or random copolymerization at molecular weight.
Description
Technical field
The invention belongs to olefin polymerization catalysis technical field, more particularly to a kind of catalytic activation vinylpyridine synthesis is vertical
The rare-earth metal catalyst of structure regularity polyvinylpyridine.
Background technology
Vinylpyridine has as a kind of functional polarity monomer being easily modified compared to traditional nonpolar olefinic monomer
There are apparent superior surface property, such as good color adhesive force and hydrophily, is one kind to traditional nonpolar olefinic monomer
Modified, in recent years, along with the rapid development of macromolecule subject, people are to the polymerization of vinylpyridine and its polymer
Modified aspect all has made intensive studies.Contain pyridine groups in vinylpyridine molecule, can be made by acid and halogenated hydrocarbon
With and generate quaternary ammonium salt, can also with various metals ion occur complexing generate complex, these unique properties can quilt
Several functions high molecular material is prepared, such as polymeric membrane, polyelectrolyte, biodegradable material, polymer
Compatilizer, zymophore etc..In addition, polyvinylpyridine and its copolymer and trimer because of its self assembly and are easy to micella
The multi-functional property formed, has extensive prospect of the application in scopes such as electrochemistry, optics, nanometer membrane technologies.
The mode of synthesizing ethylene pyridine polymer is to make polar vinyl monomer that polymerisation occur.It is adoptable at present
Polymerization methods include：Coordination polymerization, free radical polymerization, anionic polymerisation, steric hindrance type Lewis Acids and Bases are to polymerization and group transfer
Polymerization.Free radical polymerization is to be used for the mode of vinylpyridine monomers polymerization earliest, and catalyst is mainly 2,2,6,6- tetra-
Methyl piperidine nitrogen oxides and azo-bis-isobutyl cyanide, however this polymerization methods institute suitable monomers have apparent limitation,
Main performance is as follows：1) polymer molecular weight cannot be controlled；2) three-dimensional regularity of polymer cannot be controlled；3) it is unable to region choosing
Selecting property polymerize more vinylpyridines.And in free radical polymerization (CN200710101637.X；CN201510957959.9) document
In few its stereoselectivity is reported.Thus this polymerization methods are above limited in application.Anionic polymerisation exists
There is highly important status in the research of polar vinyl monomer polymerization, the work of initiator can be reduced by the way that conditioning agent is added
Property, (- 78 DEG C) are caused with n-BuLi, trityl sodium, cumene potassium, cumene caesium, amido magnesium under cryogenic
Agent, may be implemented living polymerization (J.Polym.Sci.1961,51,487；Makromol.Chem.1960,37,160).However,
Catalyst is very sensitive to polar group, is easy poisoning and inactivates.Thus, this polymerization methods are difficult to make on a large scale in the industry
With in addition to this, reaction must carry out at very low temperature, extremely consume energy.Meanwhile this polymerization methods require it is very harsh
Polymerizing condition, such as stringent anhydrous, anaerobic.Thus, this polymerization methods are difficult large-scale use in the industry.Steric hindrance type Louis
This acid-base pair polymerization system is the polymerization of developed recently, and unique property is also shown to vinylpyridine monomers polymerization
Can, the polymer of high molecular weight can be obtained.But this polymerization methods efficiency of initiation is very low, cannot control polymer point
Son amount, to which its application value is not high.There are one shared in polymerising ethylene vinylpyridine monomers for these above-mentioned polymerization methods
Disadvantage cannot effectively control the stereoeffect of polymer, can not stereotactic polymer.
Coordination polymerization is that catalyzed alkene monomer stereoselectivity polymerize to obtain stereotactic polymer most effective way,
It is widely used in industrial production, but the catalyst for vinylpyridine monomers polymerization or rare report, German B.Rieger
Four tooth amine phenol yttrium complex are reported to polymerize to obtain medium regularity (mm=0.61~0.87) polymerization for 2- vinylpyridines
Object (Polym.Chem.2015,6,6796；Macromolecules 2016, 49,6260；), Japanese K.Mashima is reported
Bidentate diamines yttrium complex polymerize to obtain high regularity oligomer that (mm=0.95, molecular weight are less than for 2- vinylpyridines
3000g/mol), our seminars realize the high stereoregulated polymerization of 2- vinylpyridines using four tooth phenolic ether yttrium catalyst,
The isotacticity mm values for obtaining polymer reach 0.96 (ACS Catal.2016,6,4907.).However, the system reported at present
It is required for, using the complicated assistant ligand of synthesis, being not easy to realize industrialized production.
Invention content
The present invention provides a kind of catalyst for compound stereoscopic regularity polyvinylpyridine.
Technical scheme of the present invention：
A kind of catalyst for compound stereoscopic regularity polyvinylpyridine, the molecular formula expression of the catalyst is such as
Under：
LnR3(L1)(L2)；
R is selected from the virtue of the silylation of 4~24 carbon atoms, the alkyl with 1~12 carbon atom, 6~24 carbon atoms
Base, 2~12 carbon atom chain alkenyls, 6~24 carbon atom benzyloxies and 6~24 carbon atom benzamido groups；
Ln is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium；
L1And L2Selected from tetrahydrofuran, monomethyl tetrahydrofuran, dimethyl-tetrahydrofuran, oxinane, 1,4- dioxies six
Ring, glycol dimethyl ether, thiophane, N, N- tetramethylethylenediamines, pyridine, 6-12 carbon atom alkyl substituted pyridines, 2-
Bromopyridine, 2- chloropyridines, 2- iodine pyridines, 3- bromopyridines, 3- chloropyridines, 3- iodine pyridines, 4-dimethylaminopyridine, 2,2 '-connection pyrroles
Pyridine, 4,4 '-bipyridyls, 1,4- diazabicylos [2.2.2] octane, 3~twelve carbon atom tertiary amine, 1,8- diazabicylos 11
Carbon -7- alkene, 7- methyl-1s, 5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene and diethylene glycol dimethyl ether, L1And L2It is identical or not
Together.
The catalyst structure formula is preferred, as follows：
R is the silylation of 4~24 carbon atoms；
L1And L2Selected from tetrahydrofuran, pyridine and 4-dimethylaminopyridine, L1And L2It is identical or different；
Central metal Ln is selected from yttrium, lutetium, holmium and dysprosium.
The catalyst structure formula is preferred, as follows：
R is trimethyl silicane methylene；
L1And L2Selected from tetrahydrofuran and pyridine, L1And L2It is identical or different；
Central metal Ln is lutetium.
The structural formula for the vinylpyridine monomers that catalyst is catalyzed is：
R1Selected from CH=CH2When, R2、R3、R4、R5Virtue selected from hydrogen, the alkyl of 1~12 carbon atom, 6~18 carbon atoms
The alkenyl of base, the benzyloxy of 6~18 carbon atoms and 1~12 carbon atom, R2、R3、 R4And R5It is identical or different；
R3Selected from CH=CH2When, R1、R2、R4、R5Alkyl selected from hydrogen, 1~12 carbon atom, the virtue of 6~18 carbon atoms
The alkenyl of base, the benzyloxy of 6~18 carbon atoms and 1~12 carbon atom, R1、 R2、R4And R5It is identical or different.
In the structural formula for the vinylpyridine monomers that catalyst is catalyzed, R1It preferably is selected from CH=CH2, R2、R3、 R4、R5For
Hydrogen.
In the structural formula for the vinylpyridine monomers being catalyzed, R3It preferably is selected from CH=CH2, R1、R2、R4、 R5For hydrogen.
In the structural formula for the vinylpyridine monomers being catalyzed, R1Selected from CH=CH2, R3It preferably is selected from CH=CH2, R2、R4、
R5For hydrogen.
Solvent in the catalysis vinylpyridine monomers polymerisation is selected from C6FmHn、C6ClmHn、 C6BrmHn、C6
(CH3)mHn, benzene, ethylbenzene, hexane, heptane, octane, tetrahydrofuran, ether, petroleum ether, chloroform, dichloromethane and N, N- dimethyl
Formamide, wherein m and n is selected from 1~6 and m+n=6；The molar ratio for being catalyzed reacting middle catalyst and vinylpyridine monomers is 1 ﹕
50~1:500000, reaction temperature is -78~220 DEG C, and the reaction time is 0.1~72 hour.
The catalyst and B (C6F5)3、Al(C6F5)3、Zn(C6F5)3、BPh3、BF3、AlR3、ZnX2、 MgX2Or
(MeAlO)yMixed catalyst system is formed, X is the alkyl of 1~12 carbon atom, and y is 10~1000.
The catalyst is total for being catalyzed a kind of vinylpyridine monomers homopolymerization or two or more vinylpyridine monomers
It is poly-.
The catalyst can be used to lower two methods and prepare：
First method includes the following steps：
In hydrocarbon solvent, the rare earth alkyl compound and the ethers that are coordinated using tetrahydrofuran, alkylene oxide hydro carbons, amine or
Pyridine compounds and their is 1 in molar ratio:1 or 1:Then 2 stirrings are added acquired solution being concentrated into solid precipitation, collect solid
Obtain rare-earth metal catalyst.
The solvent is the aromatic hydrocarbon of the alkane of 5~12 carbon, 6~18 carbon, preferably hexane, toluene or dimethylbenzene.Reaction
Temperature is -80~150 DEG C, preferably -20~100 DEG C；Reaction time is 0.5~72 hour, preferably 2~24 hours.React organic
Solvent dosage should be 20~100 times of reaction raw materials summation.
Second method includes the following steps：
The rare earth alkyl compound that tetrahydrofuran is coordinated is dissolved in ethers, alkylene oxide hydro carbons, amine or pyridines chemical combination
It in object, is then added and acquired solution is concentrated into solid precipitation, collect solid and obtain rare-earth metal catalyst.Solution temperature be-
80~150 DEG C, preferably -20~100 DEG C；Reaction time is 0.5~72 hour, preferably 2~24 hours.
The rare earth catalyst of the present invention polymerize for vinylpyridine monomers.Method for olefinic polymerization includes above-mentioned
Any one rare-earth metal catalyst is in contact at least one polar vinyl monomer；With rare earth catalyst itself as catalysis
Agent or rare earth catalyst and co-catalyst, such as B (C6F5)3、Al(C6F5)3、Zn(C6F5)3、 BPh3、BF3、AlR3、ZnR2、MgR2Or
(MeAlO)xForm mixed catalyst system；The molar ratio of co-catalyst and metal in major catalyst is 1~20000：1.Most preferably
Co-catalyst be boron alkyl (such as：B(C6F5)3Deng) composition co-catalyst system.The amount of co-catalyst can be in very wide model
Enclose interior variation.The molar ratio of wherein boron and rare-earth metal catalyst is preferably 1~1000:1, more preferably 1~150:1.Polymerization
Reaction can carry out in the liquid solution having no adverse effect to catalyst system.Such solvent includes pentane, hexane, and heptane is pungent
Alkane, hexamethylene, hexahydrotoluene, toluene, dimethylbenzene or mixed alkanes etc..Polymeric reaction temperature can become in a wide range
Change, typical temperature range is -20 DEG C~200 DEG C, more preferably ranging from 20 DEG C~160 DEG C.
Catalyst structure variation of the present invention is various, can significantly be regulated and controled to urge by changing the substituent group on central metal
The performance of agent, thus can be widely applied to the polymerization of catalysis vinylpyridine monomers.The stability of catalyst of the present invention is good, urges
Change activity height, is particularly suitable for the stereoselectivity polymerization of catalysis vinylpyridine monomers.
Description of the drawings
Fig. 1 is isotactic poly 2 vinyl pyridine carbon spectrogram.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but the present invention is not limited thereto.
Embodiment 1 [two (trimethyl silicane methylene)] lutetium [two (pyridine)]
This compound can be prepared by following two methods.
Method one：
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, removes solvent, and the pyridine and 10 milliliters of toluene of two equivalents is added, and removes solvent,
Crude product is recrystallized with hexane, obtains 1.93 grams of net product, yield 91.0%.
Method two：
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, removes solvent, and 10 milliliters of pyridines are added, and removes solvent, and crude product is tied again with hexane
Crystalline substance obtains 1.93 grams of net product, yield 91.0%.
Elemental analysis result：C,44.67；H,7.33；N,4.73..
By the method in embodiment 1, we have synthesized a series of compound, and both the above method changes each
It is all feasible to close object, only yield is different.The highest method of the preferred yield of each compound in following embodiment.
Embodiment 2 [two (trimethyl silicane methylene)] lutetium (pyridine) (tetrahydrofuran)
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, removes solvent, and the pyridine and 10 milliliters of toluene of monovalent is added, and removes solvent,
Crude product is recrystallized with hexane, obtains 1.89 grams of net product, yield 90.1%.Elemental analysis result：C,42.95；H,7.92；N,
2.36。
Embodiment 3 [two (trimethyl silicane methylene)] lutetium [two (4-dimethylaminopyridine)]
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, removes solvent, the 4-dimethylaminopyridine and 10 milliliters of toluene of monovalent is added,
Solvent is removed, crude product is recrystallized with hexane, obtains 2.23 grams of net product, yield 92.3%.
Elemental analysis result：C,45.91；H,7.88；N,8.25.
Embodiment 4 [two (trimethyl silicane methylene)] lutetium [two (1,4- diazabicylos [2.2.2] octane)]
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, remove solvent, be added monovalent Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane and
10 milliliters of toluene remove solvent, and crude product is recrystallized with hexane, obtains 2.21 grams of net product, yield 94.3%.
Elemental analysis result：C,43.67；H,8.62；N,8.43.
Embodiment 5 [two (trimethyl silicane methylene)] lutetium [two (11 carbon -7- alkene of 1,8- diazabicylos)]
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, remove solvent, be added monovalent 1,8- diazabicylos, 11 carbon -7- alkene and
10 milliliters of toluene remove solvent, and crude product is recrystallized with hexane, obtains 2.50 grams of net product, yield 95.3%.
Elemental analysis result：C,48.62；H,8.84；N,7.56.
Embodiment 6 [two (trimethyl silicane methylene)] yttrium [two (pyridine)]
Under a nitrogen, by trimethyl silicane methylene lithium 1.0 grams be dissolved in 10 milliliters of anhydrous tetrahydro furans, and with equivalent
Anhydrous tri-chlorination lutetium is stirred at room temperature 8 hours, removes solvent, and 10 milliliters of pyridines are added, and removes solvent, and crude product is tied again with hexane
Crystalline substance obtains 1.67 grams of net product, yield 92.4%.
Elemental analysis result：C,51.94；H,8.52；N,5.51.
Embodiment 7 [two (trimethyl silicane methylene)] yttrium (pyridine) (tetrahydrofuran)
Under a nitrogen, by N, N '-di-t-butyls -1.0 grams of benzenecarboximidamide is dissolved in 30 milliliters of dry toluenes, and with equivalent
The double trimethyl silicane methylene compounds of cyclopentadiene yttrium are stirred at room temperature 8 hours, remove solvent, and crude product is recrystallized with hexane,
Obtain 1.67 grams of net product, yield 94.1%.
Elemental analysis result：C,50.27；H,9.24；N,2.79.
The polymerization of 8 polar vinyl monomer of embodiment
At 20 milliliters in the reaction bulb with stirrer, 10 μm of ol rare earth catalysts, 10 milliliters of toluene are sequentially added, then
The vinylpyridine monomers polymerization that requirement is added starts.Reaction carries out at 20 DEG C, until complete monomer conversion is polymer.
After reaction, 1 methanol solution of the drop containing 10% hydrochloric acid is added and terminates reaction.By polymer pour into containing 200 milliliters just oneself
In alkane, stir 1 hour.Polymer is collected by filtration, 20 milliliters of n-hexane washings every time are used in combination three times, then in 50 DEG C of vacuum drying ovens
It dries to constant weight.Other application example is shown in Table 1~4, wherein by the difference of ligand, is respectively in by different experiment conditions each only
In vertical table.Polymerization process monitors polymerized monomer by nuclear-magnetism and obtains conversion ratio, until polymerized monomer is totally converted stopping reaction,
Resulting polymers measure its molecular weight and molecualr weight distribution by gel chromatography.
Table 1：Ligand molecule is the catalyst Ln (CH of tetrahydrofuran (THF) molecule2SiMe3)(THF)2
*Note, catalyst：10μmol；Solvent：10mL；Temperature：20℃
Table 2:The application example of different solvents
*Note, catalyst：Lu(CH2SiMe3)(THF)210μmol；Monomer：2mmol, solvent：10mL；Temperature： 20℃
The application example of 3 different temperatures of table
*Note, catalyst：Lu(CH2SiMe3)(THF)210μmol；Monomer：2mmol, solvent：10mL
Table 4：Ligand molecule is the catalyst Ln (CH of pyridine (Py) molecule2SiMe3)(Py)2
*Note, catalyst：10μmol；Monomer:10mmol, solvent：10mL
Table 5：Ligand molecule is the catalyst Ln (CH of pyridine (Py) molecule2SiMe3)(Py)2With urging for boron compound composition
Change system
*Note, catalyst：10μmol；Monomer：2mmol, solvent：10mL.
Claims (10)
1. a kind of catalyst for compound stereoscopic regularity polyvinylpyridine, which is characterized in that point of the catalyst
Minor is expressed as follows：
LnR3(L1)(L2)；
R is selected from the silylation of 4~24 carbon atoms, the alkyl with 1~12 carbon atom, the aryl of 6~24 carbon atoms, 2
~12 carbon atom chain alkenyls, 6~24 carbon atom benzyloxies and 6~24 carbon atom benzamido groups；
Ln is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium；
L1And L2Selected from tetrahydrofuran, monomethyl tetrahydrofuran, dimethyl-tetrahydrofuran, oxinane, 1,4- dioxane, second
Glycol dimethyl ether, thiophane, N, N- tetramethylethylenediamines, pyridine, 6-12 carbon atom alkyl substituted pyridines, 2- bromine pyrroles
Pyridine, 2- chloropyridines, 2- iodine pyridines, 3- bromopyridines, 3- chloropyridines, 3- iodine pyridines, 4-dimethylaminopyridine, 2,2 '-bipyridyls, 4,
4 '-bipyridyls, 1,4- diazabicylos [2.2.2] octane, 3~twelve carbon atom tertiary amine, 11 carbon -7- of 1,8- diazabicylos
Alkene, 7- methyl-1s, 5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene and diethylene glycol dimethyl ether, L1And L2It is identical or different.
2. catalyst according to claim 1, which is characterized in that in the catalyst structure formula：
R is the silylation of 4~24 carbon atoms；
L1And L2Selected from tetrahydrofuran, pyridine and 4-dimethylaminopyridine, L1And L2It is identical or different；
Central metal Ln is selected from yttrium, lutetium, holmium and dysprosium.
3. catalyst according to claim 1, which is characterized in that in the catalyst structure formula：
R is trimethyl silicane methylene；
L1And L2Selected from tetrahydrofuran and pyridine, L1And L2It is identical or different；
Central metal Ln is lutetium.
4. catalyst according to claim 1,2 or 3, which is characterized in that the structure for the vinylpyridine monomers being catalyzed
Formula is：
R1Selected from CH=CH2When, R2、R3、R4、R5Selected from hydrogen, the alkyl of 1~12 carbon atom, the aryl of 6~18 carbon atoms, 6
The alkenyl of the benzyloxy of~18 carbon atoms and 1~12 carbon atom, R2、R3、R4And R5It is identical or different；
R3Selected from CH=CH2When, R1、R2、R4、R5Alkyl selected from hydrogen, 1~12 carbon atom, the aryl of 6~18 carbon atoms, 6
The alkenyl of the benzyloxy of~18 carbon atoms and 1~12 carbon atom, R1、R2、R4And R5It is identical or different.
5. catalyst according to claim 4, which is characterized in that in the structural formula for the vinylpyridine monomers being catalyzed, R1
Selected from CH=CH2, R2、R3、R4、R5For hydrogen.
6. rare-earth metal catalyst according to claim 4, which is characterized in that the knot for the vinylpyridine monomers being catalyzed
In structure formula, R3Selected from CH=CH2, R1、R2、R4、R5For hydrogen.
7. rare-earth metal catalyst according to claim 4, which is characterized in that the knot for the vinylpyridine monomers being catalyzed
In structure formula, R1Selected from CH=CH2, R3Selected from CH=CH2, R2、R4、R5For hydrogen.
8. according to the catalyst described in claim 1,2,3,5,6 or 7, which is characterized in that the catalysis vinylpyridine list
Solvent in body polymerisation is selected from C6FmHn、C6ClmHn、C6BrmHn、C6(CH3)mHn, benzene, ethylbenzene, hexane, heptane, octane, four
Hydrogen furans, ether, petroleum ether, chloroform, dichloromethane and n,N-Dimethylformamide, wherein m and n is selected from 1~6 and m+n=6；
The molar ratio for being catalyzed reacting middle catalyst and vinylpyridine monomers is 1 ﹕ 50~1:500000, reaction temperature is -78~220
DEG C, the reaction time is 0.1~72 hour.
9. catalyst according to claim 8, which is characterized in that the catalyst and B (C6F5)3、Al(C6F5)3、Zn
(C6F5)3、BPh3、BF3、AlR3、ZnX2、MgX2Or (MeAlO)yMixed catalyst system is formed, X is the alkane of 1~12 carbon atom
Base, y are 10~1000.
10. according to the catalyst described in claim 1,2,3,5,6,7 or 9, which is characterized in that the catalyst is for being catalyzed
A kind of vinylpyridine monomers homopolymerization or the copolymerization of two or more vinylpyridine monomers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112940163A (en) * | 2021-02-08 | 2021-06-11 | 安徽师范大学 | Rare earth metal complex catalyst containing pyridine imine ligand, preparation method and application in 2-vinylpyridine polymerization reaction |
| CN116589500A (en) * | 2023-05-17 | 2023-08-15 | 吉林大学 | Biguanidine base and preparation method thereof, LPP catalyst and application thereof, 4-vinyl pyridine polymer and derivative and preparation method thereof |
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| CN112940163A (en) * | 2021-02-08 | 2021-06-11 | 安徽师范大学 | Rare earth metal complex catalyst containing pyridine imine ligand, preparation method and application in 2-vinylpyridine polymerization reaction |
| CN112940163B (en) * | 2021-02-08 | 2022-04-12 | 安徽师范大学 | Rare earth metal complex catalyst containing pyridine imine ligand, preparation method and application in 2-vinylpyridine polymerization reaction |
| CN116589500A (en) * | 2023-05-17 | 2023-08-15 | 吉林大学 | Biguanidine base and preparation method thereof, LPP catalyst and application thereof, 4-vinyl pyridine polymer and derivative and preparation method thereof |
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