CN108641026B - Application of benzyl imine pyridine iron complex in preparation of isoprene rubber - Google Patents
Application of benzyl imine pyridine iron complex in preparation of isoprene rubber Download PDFInfo
- Publication number
- CN108641026B CN108641026B CN201810399947.2A CN201810399947A CN108641026B CN 108641026 B CN108641026 B CN 108641026B CN 201810399947 A CN201810399947 A CN 201810399947A CN 108641026 B CN108641026 B CN 108641026B
- Authority
- CN
- China
- Prior art keywords
- isoprene
- polyisoprene
- molecular weight
- preparation
- imine pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920003049 isoprene rubber Polymers 0.000 title claims abstract description 16
- WHJXGGISJBFSJJ-UHFFFAOYSA-N iron;pyridine Chemical compound [Fe].C1=CC=NC=C1 WHJXGGISJBFSJJ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- AFDMODCXODAXLC-UHFFFAOYSA-N phenylmethanimine Chemical compound N=CC1=CC=CC=C1 AFDMODCXODAXLC-UHFFFAOYSA-N 0.000 title claims abstract description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 70
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 150000002466 imines Chemical class 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 15
- 150000004698 iron complex Chemical class 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000007787 solid Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012300 argon atmosphere Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000010791 quenching Methods 0.000 description 10
- 230000000171 quenching effect Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- DGSRAILDFBJNQI-UHFFFAOYSA-N (2,4,6-trimethylphenyl)methanamine Chemical compound CC1=CC(C)=C(CN)C(C)=C1 DGSRAILDFBJNQI-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- -1 pyridine alkyl imine Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 description 2
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
Images
Classifications
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/03—Sideramines; The corresponding desferri compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a benzyl imine pyridine iron complex, a preparation method thereof and application thereof in isoprene rubber preparation. The method comprises the following steps: adding a main catalyst, a solvent and a cocatalyst, and then adding an isoprene monomer for polymerization reaction to obtain polyisoprene. The microstructure of the obtained polyisoprene can be regulated and controlled by regulating the steric hindrance of the main catalyst, the trans-1,4 structure of the polyisoprene accounts for 30-62%, the cis-1,4 structure accounts for 21-30%, and the 3,4 structure accounts for 17-42%, and the polymer has high molecular weight and narrow molecular weight distribution. The preparation method of isoprene rubber provided by the invention can effectively improve the use efficiency and industrial application value of the iron catalyst.
Description
Technical Field
The present invention relates to the field of chemically synthesized macromolecules.
Background
The increasing demand in the rubber market and the insufficient productivity of natural rubber highlight the importance of synthetic rubber, which is rapidly developing as an integral part of petrochemicals. The isoprene rubber not only has certain similar characteristics to natural rubber and excellent comprehensive performance, but also has the characteristics of wide resources, good processability and the like, and is gradually developed into a pillar variety in the rubber industry. Since 1860 Williams separated isoprene from natural rubber decomposition products, more and more scientists have devoted themselves to the study of isoprene to synthesize natural rubber. There are four different microstructures for polyisoprene: cis-1, 4-polyisoprene; trans-1, 4-polyisoprene; 3, 4-polyisoprene and 1, 2-polyisoprene. Because of the differences in structural units and the manner in which the units are linked, there are large differences in performance between different polyisoprene species. In the process of synthesizing the isoprene rubber, different catalytic systems and synthesis processes are adopted to realize the structural adjustability of the polyisoprene so as to obtain the polyisoprene with different molecular weights, different structural units and different forms. It can be said that the catalyst is the core of the polyisoprene production process, and the technical progress of the isoprene rubber industry is mainly attributed to the progress of the catalyst.
In 1988, the Wangfang Poisson topic group adopted an iron-containing three-way catalytic system (Fe (acac)3/Al(i-Bu)3Nitrogen-containing electron donor) to obtain high molecular weight, high melting point and crystalline polyisoprene with 3,4 structure up to 70%. The experimental results show that Fe (acac)3/Al(i-Bu)3The binary catalytic system cannot cause isoprene polymerization, and the catalytic activity is remarkably improved when a small amount of nitrogen-containing donor is added. The disadvantage is that the system gives polyisoprene with a high gel content. In addition to using a nitrogen-containing electron donor as an additive, dialkyl phosphites may also be used as an electron donor to promote iron-catalyzed isoprene polymerization. The nitrogen or phosphorus containing electron donor is independently used as a third component to be added into a catalytic system, so that the active center of the catalyst can be stabilized, and the polymerization reaction can be promoted. With the gradual development of the ligand, the nitrogen-containing electron donor is improved to form a complex with iron element in a ligand mode to catalyze isoprene polymerization.
In 2002, Porri topic group studied (Bipy)2FeEt2And isoprene is subjected to polymerization reaction catalyzed by MAO system to obtain the crystalline polyisoprene with 3,4 structure content as high as 85%. In 2012, the Ritter topic combines an iron/imine pyridine complex, combines an aluminum alkyl and a boron salt to form a ternary system to catalyze isoprene polymerization, and shows high activity and regioselectivity. The polyisoprene prepared by the complex containing alkyl substituent is mainly of trans-1,4 structure, while the polyisoprene prepared by the complex containing aryl substituent is mainly of cis-1,4 structure. On the basis, the Chengyngle task group designs and synthesizes a series of iron/pyridine alkyl imine and iron/pyridine aryl imine complexes. The influence of ligands containing different substituents on reactivity and stereoselectivity was investigated with MAO as a cocatalyst.
Although iron-catalyzed isoprene polymerization has been reported, the reactivity and selectivity of the existing iron-catalyzed systems are relatively low, and have a great gap from industrial application. Therefore, the development of more efficient catalysts that can control polymer properties, especially the development of new, highly active, highly selective, well-defined catalysts with good functional group compatibility, has been an important but challenging task.
Disclosure of Invention
In order to solve the problems of low reaction activity and selectivity of the iron catalytic system and the like, the invention provides an iron complex, a preparation method thereof and a method for preparing polyisoprene by using the iron complex catalyst. The method can adjust the microstructure of the polyisoprene under a mild condition by changing the steric hindrance of the iron complex, and meanwhile, the isoprene rubber has a large molecular weight and a narrow molecular weight distribution.
The invention is realized by the following technical scheme:
a benzyl imine pyridine iron complex, the structure is shown in formula I,
in the formula, R is one or more than two of bromo, methyl, ethyl, isopropyl, phenyl or methoxy; preferably R is methyl and the formula is III:
an iron-based catalyst system comprises a main catalyst and a cocatalyst,
the main catalyst is an iron complex, and the structural general formula of the main catalyst is as follows:
the cocatalyst is methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride and ethylaluminum dichloride, preferably methylaluminoxane, and the structural general formula isWherein n is a natural number of 4 to 40;
the molar ratio of the iron element in the main catalyst to the aluminum element in the cocatalyst is 1 (100-1000), preferably 1: 500;
the preparation method of the benzyl imine pyridine iron complex comprises the steps of mixing imine pyridine ligand and ferrous chloride in an equimolar ratio in dichloromethane at the temperature of 25 ℃, and carrying out aftertreatment to obtain the iron complex.
The structural general formula of the imine pyridine ligand is as follows:specifically, the structural formula is one or more than two of the following structural formulas:
the invention also provides an application of the benzyl imine pyridine iron complex in isoprene rubber preparation. The benzyl imine pyridine iron complex is used as a main catalyst, and the cocatalyst is one or more than two of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride and ethylaluminum dichloride; the general structural formula of the Methylaluminoxane (MAO) isWherein n is a natural number of 4 to 40; the molar ratio of the aluminum element in the cocatalyst to the iron element in the main catalyst is (100-1000): 1.
The method comprises the following steps: adding a main catalyst, a solvent and a cocatalyst, and then adding an isoprene monomer for polymerization reaction to obtain polyisoprene.
The polymerization solvent is toluene, p-xylene, n-hexane, cyclohexane, pentane, dichloromethane and tetrahydrofuran, and toluene is preferred; the amount of the solvent is as follows: the volume ratio of the solvent to the isoprene is (1-10): 1.
In the application, the feeding sequence can be as follows: sequentially adding a main catalyst/solvent/cocatalyst/isoprene and sequentially adding a cocatalyst/solvent, isoprene and a dichloromethane solution of the main catalyst, preferably sequentially adding the main catalyst/solvent/cocatalyst/isoprene to obtain polyisoprene, i.e. isoprene rubber;
in the application, the molar ratio of the isoprene monomer to the iron element in the main catalyst is preferably (2000) -5000: 1, and preferably 2000: 1;
the application is that the temperature of the polymerization reaction is-30-50 ℃, preferably 25 ℃;
the polymerization time is 10min-16h, preferably 2 h;
the polyisoprene, i.e. the isoprene rubber obtained by the application has the number average molecular weight of 5.2 multiplied by 104-5.7×105The molecular weight distribution is 1.8-4.6;
according to the application, the micro structure of polyisoprene, namely isoprene rubber, can be adjusted according to different structures of the added main catalyst, the proportion range of the obtained polyisoprene, namely isoprene rubber trans-1,4 structure is 0-84%, the proportion range of cis-1,4 structure is 10-53%, and the proportion of 3,4 structure is 6-47%.
Advantageous effects
(1) The iron complex/methylaluminoxane two-component catalytic system is used for catalyzing isoprene polymerization, and the boron salt price of the three components is lower than that of the three components in background introduction;
(2) the iron-based catalyst can realize high-activity controllable polymerization of isoprene to obtain high molecular weight (5.2 multiplied by 10)4-5.7×105) And iron-based isoprene rubber with narrow molecular weight distribution (1.8-4.6).
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum with R being a methyl ligand;
FIG. 2 is a nuclear magnetic hydrogen spectrum with R being a phenyl ligand;
FIG. 3 is a nuclear magnetic hydrogen spectrum of polyisoprene obtained in example 1;
FIG. 4 is a nuclear magnetic carbon spectrum of the polyisoprene obtained in example 1.
Detailed Description
Preparation example 1
This example prepares an iron imine pyridine complex of formula II:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (40mL), benzylamine (1.2g, 10.8mmol) and 6-bromopyridine-2-carbaldehyde (2.0g, 10.8mmol) were added in that order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtered, spin-dried, and vacuum-dried to give a yellow liquid (2.4g, yield: 82%) of the formula
25mL of dry reaction tube, and 15mL of redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2(100mg, 0.8mmol) and the above prepared imidazopyridine ligand (217mg, 0.8mmol) were stirred at room temperature for 15 h. After the reaction was completed, methylene chloride was vacuum-dried, and then 10mL of dry n-hexane was added and washed 3 times, and vacuum-dried to a constant weight, whereby 285mg of red color was obtained (yield: 90%).
Mass spectrometry analysis: c13H11BrClFeN2[M-Cl]+Theoretical value: 364.9144, respectively; measured value: 364.9173.
elemental analysis: c13H11BrCl2FeN2: theoretical value: c, 38.85%; h, 2.76%; n, 6.97%; measured value: c, 38.76%; h, 2.83%; n,6.91 percent.
Preparation example 2
This example prepares an iron imine pyridine complex of formula III:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (60mL), 2-methylbenzylamine (1.1g, 9.3mmol), and pyridine-2-carbaldehyde (1.0g, 9.3mmol) were added in this order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtered, spin-dried, and vacuum-dried to give a yellow liquid (2.2g, yield: 61%) of the formula
25mL dry reaction tube, successively added in a glove box15mL of redistilled dichloromethane, anhydrous FeCl of equimolar ratio2(100.0mg, 0.8mmol) and the imine pyridine ligand prepared above (165.9mg, 0.8mmol) were stirred at room temperature for 15 h. After the reaction was completed, methylene chloride was vacuum-dried, 10mL of dry n-hexane was added and washed 3 times, and vacuum-dried to a constant weight to obtain 155mg of brick red solid (yield: 58%).
Mass spectrometry analysis: c14H14Cl2FeN2[M-Cl]+Theoretical value: 301.0195, respectively; measured value: 301.0173.
elemental analysis: c14H14Cl2FeN2: theoretical value: c, 49.89%; h, 4.19%; n, 8.31%; measured value: c, 49.98%; h, 3.44%; and N, 8.15%.
Preparation example 3
This example prepares an iron imine pyridine complex of formula IV:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (60mL), 2-methylbenzylamine (1.9g, 14.0mmol), and pyridine-2-carbaldehyde (1.5g, 14.0mmol) were added in this order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtered, spin-dried, and vacuum-dried to give a yellow liquid (2.6g, yield: 84%) of the formula
25mL of dry reaction tube, and 15mL of redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2(100.0mg, 0.8mmol) and the imine pyridine ligand prepared above (177.0mg, 0.8mmol) were stirred at room temperature for 15 h. After the reaction was completed, methylene chloride was vacuum-dried, and then 10mL of dry n-hexane was added and washed 3 times, and vacuum-dried to a constant weight to obtain 244mg of a red solid (yield: 88%).
Mass spectrometry analysis: c14H14Cl2FeN2[M-Cl]+Theoretical value: 315.0351, respectively; measured value: 315.0342.
elemental analysis: c15H16Cl2FeN2: theoretical value: c, 51.32%; h, 4.59%; n, 7.98%(ii) a Measured value: c, 51.11%; h, 4.32%; n,8.14 percent.
Preparation example 4
This example prepares an iron imine pyridine complex of formula V:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (60mL), 2,4, 6-trimethylbenzylamine (1.4g, 9.4mmol) and pyridine-2-carbaldehyde (1.0g, 9.3mmol) were added in this order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtered, spin-dried, and vacuum-dried to give a yellow solid (1.2g, yield: 55%) of formula
25mL of dry reaction tube, and 15mL of redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2(100.0mg, 0.8mmol) and the imine pyridine ligand prepared above (188.0mg, 0.8mmol) were stirred at room temperature for 12 h. After the reaction was completed, a clear liquid was obtained, methylene chloride was vacuum-drained, 10mL of dry n-hexane was added and washed 3 times, and vacuum-drained to constant weight to obtain 178mg of brick-red flaky solid (yield: 62%).
Mass spectrometry analysis: c16H18ClFeN2[M-Cl]+Theoretical value: 329.0508, respectively; measured value: 329.0521.
elemental analysis: c16H18Cl2FeN2: theoretical value: c, 52.64%; h, 4.97%; n, 7.67%; measured value: c, 52.51%; h, 5.12%; and N, 7.89%.
Preparation example 5
This example prepares an iron imine pyridine complex of formula VI:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (60mL), 2,4, 6-trimethylbenzylamine (1.7g, 9.3mmol) and pyridine-2-carbaldehyde (1.0g, 9.3mmol) were added in this order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtration, spin-drying, and vacuum suction-drying gave a yellow solid (1.6g, yield: 63%) of formula
25mL of dry reaction tube, and 15mL of redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2(50.0mg, 0.4mmol) and the above prepared imidazopyridine ligand (107.4mg, 0.4mmol) were stirred at room temperature for 24 h. After the reaction was completed, a red suspension was obtained, methylene chloride was vacuum-drained, 10mL of dry n-hexane was added and washed 3 times, and vacuum-drained to a constant weight to obtain 98mg of a violet solid (yield: 62%).
Mass spectrometry analysis: c19H16ClFeN2[M-Cl]+Theoretical value: 363.0351, respectively; measured value: 363.0372.
elemental analysis: c19H16Cl2FeN2: theoretical value: c, 57.18%; h, 4.04%; n, 7.02%; measured value: c, 57.01%; h, 4.28%; and 6.89 percent of N.
Preparation example 6
This example prepares an iron imine pyridine complex of formula VII:
a100 mL dry reaction flask was charged with 4A molecular sieves and baked for 30 minutes. Under an argon atmosphere, dry dichloromethane (60mL), 2,4, 6-trimethylbenzylamine (1.3g, 9.4mmol) and pyridine-2-carbaldehyde (1.0g, 9.3mmol) were added in this order. The reaction was carried out overnight at room temperature and the aldehyde substrate was completely reacted as detected by TLC plate. Filtered, spin-dried, and vacuum-dried to give a yellow liquid (1.4g, yield: 66%) of the formula
25mL of dry reaction tube, and 15mL of redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2(100mg, 0.79mmol) and the imine pyridine ligand prepared above (178.5mg, 0.8mmol) were stirred at room temperature for 24 h. After the reaction was completed, methylene chloride was vacuum-dried, and then 10mL of dry n-hexane was added and washed 3 times, and vacuum-dried to a constant weight to obtain 134mg of a purple solid (yield: 48%).
Mass spectrometry analysis: c14H14ClFeN2O[M-Cl]+Theoretical value: 317.0144, respectively; measured in factThe value: 317.0166.
elemental analysis: c14H14Cl2FeN2O: theoretical value: c, 47.63%; h, 4.00%; n, 7.94%; measured value: c, 47.41%; h, 4.12%; and N,7.83 percent.
Example 1
A 25mL dry reaction tube is transferred to a glove box, 4.0mg (10 mu mol) of a weighed main catalyst shown in formula II is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the reaction is carried out for 10min at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for stopping the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and the vacuum pumping is carried out at room temperature until the weight is constant, wherein the yield is 52 percent, the number average molecular weight is 325567, the molecular weight distribution is 2.0, the proportion of trans-1,4 structures is 52 percent, the proportion range of cis-1,4 structures is 22 percent, and the proportion of 3,4 structures is.
Example 2
A 25mL dry reaction tube is transferred to a glove box, 3.4mg (10 mu mol) of the weighed catalyst in the formula III is added, the mixture is transferred to the outside of the glove box, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the mixture reacts for 10min at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for stopping the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and is vacuumized to constant weight at room temperature, the yield is 75%, the number average molecular weight is 573947, the molecular weight distribution is 1.8, the proportion of trans-1,4 structures is 80%, the proportion range of cis-1,4 structures is 13%, and the proportion of 3,4 structures is 7%.
Example 3
A 25mL dry reaction tube is transferred to a glove box, 3.5mg (10 mu mol) of the weighed catalyst in the formula IV is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the reaction is carried out for 10min at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for terminating the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and is vacuumized to constant weight at room temperature, the yield is 60%, the number average molecular weight is 332142, the molecular weight distribution is 2.0, the proportion of trans-1,4 structures is 49%, the proportion range of cis-1,4 structures is 23%, and the proportion of 3,4 structures is 28%.
Example 4
A 25mL dry reaction tube is transferred to a glove box, 3.7mg (10 mu mol) of the weighed catalyst in the formula V is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the reaction is carried out for 10min at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for terminating the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and is vacuumized to constant weight at room temperature, the yield is 35%, the number average molecular weight is 219952, the molecular weight distribution is 2.1, the proportion of trans-1,4 structures is 38%, the proportion range of cis-1,4 structures is 21%, and the proportion of 3,4 structures is 41%.
Example 5
A 25mL dry reaction tube is transferred to a glove box, 4.0mg (10 mu mol) of the weighed catalyst in the formula VI is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the reaction is carried out for 16h at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for terminating the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and the solid is vacuumized to constant weight at room temperature, wherein the yield is 81%, the number average molecular weight is 198655, the molecular weight distribution is 2.4, the proportion of trans-1,4 structures is 0%, the proportion range of cis-1,4 structures is 50%, and the proportion of 3,4 structures is 50%.
Example 6
A 25mL dry reaction tube is transferred to a glove box, 3.5mg (10 mu mol) of the weighed catalyst in the formula VII is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 3.33mL (1.5M) of methylaluminoxane are added under the argon atmosphere, 2mL (20mmol) of isoprene monomer is added, the reaction is carried out for 10min at room temperature, methanol dilute hydrochloric acid solution (1:50, V/V) is used for terminating the reaction, a large amount of white solid is separated out and filtered, the solid is washed by a large amount of ethanol, and is vacuumized to constant weight at room temperature, the yield is 35%, the number average molecular weight is 219952, the molecular weight distribution is 2.1, the proportion of trans-1,4 structures is 38%, the proportion range of cis-1,4 structures is 32%, and the proportion of 3,4 structures is 30%.
Example 7
The method of example 2 was used to polymerize isoprene, except that the reaction time was extended to 2h, a large amount of white solid precipitated after quenching, the yield was 100%, the number average molecular weight was 513369, the molecular weight distribution was 1.8, the proportion of trans-1,4 structure was 81%, the proportion of cis-1,4 structure was 12%, and the proportion of 3,4 structure was 7%.
Example 8
Isoprene polymerization was carried out by the method of example 7, except that methylaluminoxane (0.67 mL, 1.5M) was quenched to precipitate a large amount of white solid, the yield was 78%, the number average molecular weight was 336528, the molecular weight distribution was 2.0, the proportion of trans-1,4 structure was 80%, the proportion of cis-1,4 structure was 12%, and the proportion of 3,4 structure was 8%.
Example 9
Isoprene polymerization was carried out by the method of example 7, except that 6.7mL (1.5M) of methylaluminoxane was quenched to precipitate a large amount of white solid with a yield of 100%, a number average molecular weight of 502179, a molecular weight distribution of 2.0, a proportion of trans-1,4 structure of 80%, a proportion of cis-1,4 structure of 12%, and a proportion of 3,4 structure of 8%.
Example 10
Isoprene polymerization was carried out by the method of example 7, except that 5.0mL (1.0M) of trimethylaluminum was used as the cocatalyst, and no solid was precipitated after quenching, with a yield of 0%.
Example 11
Isoprene was polymerized by the method of example 7, except that the cocatalyst was changed to triethylaluminum (5.0 mL) (1.0M), no solid was precipitated after quenching, and the yield was 0%.
Example 12
Isoprene was polymerized by the method of example 7, except that 5.0mL (1.0M) of triisobutylaluminum was used as the cocatalyst, and no solid was precipitated after quenching, resulting in a yield of 0%.
Example 13
Isoprene was polymerized by the method of example 7, except that the cocatalyst was changed to 5.0mL (1.0M) of diethylaluminum chloride, and no solid was precipitated after quenching, and the yield was 0%.
Example 14
Isoprene was polymerized by the method of example 7, except that the order of addition was changed: a25 mL dry reaction tube was transferred to a glove box, and 3.4mg (10. mu. mol) of the weighed main catalyst represented by formula III was added thereto, and then transferred to the outside of the glove box, and 5mL of anhydrous toluene and 2mL (20mmol) of isoprene were added thereto under an argon atmosphere, and 3.33mL (1.5M) of methylaluminoxane was further added thereto. After quenching, a large amount of white solid is separated out, the yield is 100%, the number average molecular weight is 236994, the molecular weight distribution is 2.0, the proportion of trans-1,4 structures is 73%, the proportion range of cis-1,4 structures is 12%, and the proportion of 3,4 structures is 15%.
Example 15
Isoprene was polymerized by the method of example 11, except that the order of addition was changed: a25 mL dry reaction tube was charged with 5mL of dry toluene, 2mL (20mmol) of isoprene, 3.33mL (1.5M) of methylaluminoxane under an argon atmosphere and finally a solution of 3.4mg (10. mu. mol) of catalyst (R is 4-methyl) in dichloromethane (1mL) was added. After quenching, a large amount of white solid is precipitated, the yield is 33%, the number average molecular weight is 765, the molecular weight distribution is 4.6, the proportion of trans-1,4 structures is 62%, the proportion of cis-1,4 structures is 21%, and the proportion of 3,4 structures is 17%.
Example 16
The method of example 7 was used to polymerize isoprene, except that the polymerization reaction was carried out at-30 ℃, a large amount of white solid was precipitated after quenching, the yield was 78%, the number average molecular weight was 52061, the molecular weight distribution was 1.8, the proportion of trans-1,4 structure was 10%, the proportion of cis-1,4 structure was 48%, and the proportion of 3,4 structure was 42%.
Example 17
Isoprene was polymerized by the method of example 7, except that the polymerization was carried out at-78 ℃ and no solid precipitated after 16h of quenching, the yield being 0%.
Example 18
Isoprene was polymerized by the method of example 7, except that the polymerization was carried out at 50 ℃, and after quenching, a large amount of white solid was precipitated, with a yield of 13%, a number average molecular weight of 113280, a molecular weight distribution of 3.8, a proportion of trans-1,4 structure of 23%, a proportion of cis-1,4 structure of 35%, and a proportion of 3,4 structure of 42%.
Claims (4)
1. The application of the benzyl imine pyridine iron complex in the preparation of isoprene rubber is characterized in that the benzyl imine pyridine iron complex is used as a main catalyst, a cocatalyst is methylaluminoxane, and the structural general formula of Methylaluminoxane (MAO) is shown in the specificationWherein n is a natural number of 4 to 40; the molar ratio of the aluminum element in the cocatalyst to the iron element in the main catalyst is (100-;
the preparation steps of the isoprene rubber are as follows: adding a main catalyst, a solvent and a cocatalyst, adding an isoprene monomer, and carrying out polymerization reaction at room temperature to obtain polyisoprene;
the structure of the benzyl imine pyridine iron complex is shown as a formula I,
in the formula, R is methyl;
the preparation method of the benzyl imine pyridine iron complex comprises the steps of mixing imine pyridine ligand and ferrous chloride in an equimolar ratio in dichloromethane at the temperature of 25 ℃, and carrying out aftertreatment to obtain the iron complex; the structural formula of the imine pyridine ligand is as follows:
2. the use according to claim 1, wherein the solvent is one or more of toluene, p-xylene, n-hexane, cyclohexane, pentane, dichloromethane and tetrahydrofuran; the molar ratio of the isoprene monomer to the iron element in the main catalyst is (2000) -5000) 1.
3. Use according to claim 1, wherein the polymerization time is from 10min to 16 h.
4. Use according to claim 1, characterized in that the polyisoprene obtained has a number-average molecular weight of 5.2X 104-5.7×105The molecular weight distribution is 1.8-4.6; the obtained polyisoprene trans-1,4 structure accounts for 0-84%, the cis-1,4 structure accounts for 10-53%, and the 3,4 structure accounts for 6-47%.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810399947.2A CN108641026B (en) | 2018-04-28 | 2018-04-28 | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber |
PCT/CN2018/096292 WO2019205309A1 (en) | 2018-04-28 | 2018-07-19 | Pyridine imine iron or cobalt metal complex catalyst, preparation method therefor, and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810399947.2A CN108641026B (en) | 2018-04-28 | 2018-04-28 | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108641026A CN108641026A (en) | 2018-10-12 |
CN108641026B true CN108641026B (en) | 2020-03-06 |
Family
ID=63748576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810399947.2A Active CN108641026B (en) | 2018-04-28 | 2018-04-28 | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108641026B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111233938B (en) * | 2020-03-27 | 2023-02-17 | 中国科学院青岛生物能源与过程研究所 | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
CN112175123B (en) * | 2020-09-27 | 2022-09-27 | 中国科学院青岛生物能源与过程研究所 | Poly-conjugated diene liquid rubber and preparation method and application thereof |
CN112442092B (en) * | 2020-11-24 | 2022-10-28 | 中国科学院青岛生物能源与过程研究所 | 6-methoxypyridine iron imine complex, preparation method thereof and application thereof in preparation of high-cis-poly conjugated diene |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9290591B2 (en) * | 2011-02-08 | 2016-03-22 | President And Fellows Of Harvard College | Iron complexes and methods for polymerization |
CN106632764B (en) * | 2016-10-17 | 2018-10-26 | 曲阜师范大学 | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization |
-
2018
- 2018-04-28 CN CN201810399947.2A patent/CN108641026B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN108641026A (en) | 2018-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
CN106632764B (en) | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization | |
Edelmann | Lanthanide metallocenes in homogeneous catalysis | |
EP1379562B1 (en) | Supported olefin polymerization catalysts | |
CN109851700B (en) | Tridentate pyridinimine iron-based catalyst and preparation method and application thereof | |
CN110452272B (en) | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization | |
CN108586641B (en) | High-efficiency iron-based catalyst for catalyzing isoprene polymerization and preparation method and application thereof | |
CN109053937B (en) | Alkyl substituted pyridylamine iron-based catalyst and preparation method and application thereof | |
CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
Jie et al. | Highly active and stereospecific polymerization of 1, 3-butadiene catalyzed by dinuclear cobalt (II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes | |
CN109134730B (en) | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof | |
CN109912732B (en) | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof | |
CN112442092B (en) | 6-methoxypyridine iron imine complex, preparation method thereof and application thereof in preparation of high-cis-poly conjugated diene | |
EP3808753B1 (en) | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene | |
CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
CN108659055B (en) | Iron complex based on flexible framework, preparation method thereof and application thereof in isoprene polymerization | |
CN110283264A (en) | A kind of bipyridyl iron complex and the preparation method and application thereof | |
Zhu et al. | Ligand-regulated polymerization of conjugated dienes catalyzed by confined iminopyridine iron complexes with high activity and thermal stability | |
Kempe | Rare earth polymerization catalysts supported by bulky aminopyridinato ligands | |
CN108484809B (en) | Olefin polymerization catalyst | |
CN112707937B (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method thereof and application thereof in catalysis of polymerization of conjugated diene | |
CN110305168A (en) | A kind of substitution bipyridyl ferrous coordination compound and the preparation method and application thereof | |
KR100440480B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefins | |
CN108341903B (en) | Olefin polymerization catalyst | |
CN114751943B (en) | Pyridine-2-aldehyde (ketone) oxime/cobalt complex, preparation method thereof and application thereof in conjugated diene polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |