CN114751943B - Pyridine-2-aldehyde (ketone) oxime/cobalt complex, preparation method thereof and application thereof in conjugated diene polymerization - Google Patents
Pyridine-2-aldehyde (ketone) oxime/cobalt complex, preparation method thereof and application thereof in conjugated diene polymerization Download PDFInfo
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 84
- 150000002576 ketones Chemical class 0.000 title claims abstract description 53
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 150000002923 oximes Chemical class 0.000 title claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 45
- 150000001993 dienes Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- 238000009826 distribution Methods 0.000 claims description 19
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229940097267 cobaltous chloride Drugs 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 239000007787 solid Substances 0.000 description 38
- MTFJSAGADRTKCI-VMPITWQZSA-N chembl77510 Chemical compound O\N=C\C1=CC=CC=N1 MTFJSAGADRTKCI-VMPITWQZSA-N 0.000 description 18
- 239000012300 argon atmosphere Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 8
- OIKGFMHISSQNRL-UHFFFAOYSA-N N-[(6-methylpyridin-2-yl)methylidene]hydroxylamine Chemical compound CC1=CC=CC(C=NO)=N1 OIKGFMHISSQNRL-UHFFFAOYSA-N 0.000 description 7
- LNMJFGMGAAFXNW-UHFFFAOYSA-N n-pyridin-2-ylhydroxylamine Chemical compound ONC1=CC=CC=N1 LNMJFGMGAAFXNW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XEZORVGMRQRIMY-RMKNXTFCSA-N (NE)-N-(1-pyridin-2-ylethylidene)hydroxylamine Chemical compound C1=CN=C(C=C1)/C(=N/O)/C XEZORVGMRQRIMY-RMKNXTFCSA-N 0.000 description 1
- RSJDEVMJZLLAHS-WYMLVPIESA-N (NE)-N-[phenyl(pyridin-2-yl)methylidene]hydroxylamine Chemical compound C=1C=CC=NC=1C(=N/O)/C1=CC=CC=C1 RSJDEVMJZLLAHS-WYMLVPIESA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- -1 transition metal olefin Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Pyridine-2-aldehyde (ketone) oxime/cobalt complex, preparation method thereof and application thereof in conjugated diene polymerization. The invention belongs to the field of cobalt catalysts, and preparation and application thereof. The invention aims to solve the technical problem that the activity of the existing cobalt complex homogeneous catalyst for catalyzing the polymerization of conjugated diene is not high. Under the anhydrous and anaerobic condition, pyridine-2-aldehyde (ketone) oxime/cobalt complex is dissolved by an organic solvent, conjugated diene monomer and cocatalyst are sequentially added, and polymerization reaction is carried out for 1min to 5h at the temperature of minus 30 to 70 ℃ to obtain the poly conjugated diene. The pyridine-2-oxime-aldehyde (ketone) cobalt complex has simple preparation, better thermal stability and can be realized at 70 DEG C>The conversion rate is 90%, the two-component catalytic system of pyridine-2-oxime-aldehyde (ketone) cobalt complex and methylaluminoxane is used for catalyzing the polymerization of conjugated diene, and the reaction activity can reach 1.9x10 6 g/(mol·h)。
Description
Technical Field
The invention belongs to the field of cobalt catalysts and preparation and application thereof, and particularly relates to a pyridine-2-aldehyde (ketone) oxime/cobalt complex, a preparation method thereof and application thereof in conjugated diene polymerization.
Background
The polyolefin material has the advantages of abundant raw materials, low price, easy processing and forming, excellent comprehensive performance and very wide application in various aspects of our life. Olefin polymerization catalysts are the core in the development and industrial production of polyolefin materials, and the development of the synthetic rubber industry is mainly dependent on the development and application of olefin polymerization catalysts. Throughout the development of olefin polymerization catalysts, several key stages, such as Ziegler-Natta catalysts, metallocene catalysts, non-metallocene catalysts, etc., have been mainly experienced. New non-metallocene transition metal olefin polymerization catalysts have attracted increasing attention from chemists. Compared with metallocene catalyst, the non-metallocene transition metal catalyst has the advantages of simple synthetic route, easy preparation, low cost, strong compatibility to polar monomer functional groups, and the like.
In recent years, research on homogeneously catalyzed conjugated diene polymerization of cobalt complex with definite structure has been rapidly developed, and the catalytic polymerization selectivity is higher, but the catalytic activity is generally lower. Therefore, the development of a novel cobalt catalyst with higher activity for researching olefin polymerization has important academic research significance and industrial application value.
Disclosure of Invention
The invention aims to solve the technical problem that the existing cobalt complex homogeneous catalyst for catalyzing the polymerization of conjugated dienes is low in activity, and provides a pyridine-2-aldehyde (ketone) oxime/cobalt complex, a preparation method thereof and application thereof in the polymerization of conjugated dienes.
The pyridine-2-aldehyde (ketone) oxime/cobalt complex has the structure that:
Further defined, the pyridine-2-aldehyde (ketone) oxime/cobalt complex is one of the following structures:
the preparation method of the pyridine-2-aldehyde (ketone) oxime/cobalt complex comprises the following steps:
in anhydrous solvent, mixing pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride, stirring and reacting for 2-24 h at 0-50 ℃, filtering, washing and pumping to obtain pyridine-2-aldehyde (ketone) oxime/cobalt complex.
Further defined, the pyridine-2-aldehyde (ketone) oxime ligand is one of the following structures:
further defined, the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran, chloroform, and the molar ratio of the pyridine-2-aldehyde (ketone) oxime ligand to the cobalt chloride is 2:1.
the invention relates to application of a pyridine-2-aldehyde (ketone) oxime/cobalt complex in conjugated diene polymerization, which comprises the following specific processes:
under the anhydrous and anaerobic condition, pyridine-2-aldehyde (ketone) oxime/cobalt complex is dissolved by an organic solvent, conjugated diene monomer and cocatalyst are sequentially added, and polymerization reaction is carried out for 1min to 5h at the temperature of minus 30 to 70 ℃ to obtain the poly conjugated diene.
Further limited, the cocatalyst is one or more of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride and monoethylaluminum dichloride, the conjugated diene monomer is butadiene or isoprene, and the organic solvent is one of toluene, paraxylene, n-hexane, cyclohexane, pentane, methylene dichloride and tetrahydrofuran.
Further defined, the molar ratio of the conjugated diene monomer to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1000 to 10000): 1, the molar ratio of aluminum element in the cocatalyst to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1-1000): 1, wherein the volume ratio of the organic solvent to the conjugated diene monomer is (1-10): 1.
further defined, the polymerization is carried out at 25℃for 10min.
Further defined, the number average molecular weight of the resulting conjugated diene is 0.5X10 5 g/mol～3.0×10 5 The g/mol and the molecular weight distribution are 1.6-2.2, the proportion of cis-1,4 structure in the polymer is 50-80%, and the proportion of 3,4 structure is 20-50%.
Compared with the prior art, the invention has the remarkable effects that:
1) The pyridine-2-oxime-aldehyde (ketone) cobalt complex has simple preparation, better thermal stability and can be realized at 70 DEG C>The conversion rate is 90%, the two-component catalytic system of pyridine-2-oxime-aldehyde (ketone) cobalt complex and methylaluminoxane is used for catalyzing the polymerization of conjugated diene, and the reaction activity can reach 1.9x10 6 g/(mol·h)。
2) The cobalt catalyst of the application can realize the high number average molecular weight (0.5 multiplied by 10) 5 g/mol～3.0×10 5 g/mol), narrow molecular weight distribution (1.6-2.2).
3) The hydroxyl electron donating group is directly introduced to the imine, so that the electron cloud density of nitrogen atoms on the imine is increased, the coordination with a metal center is tighter, and the catalyst structure is more stable, thereby being possibly beneficial to the good reaction activity at high temperature.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of polyisoprene obtained in application example 5;
FIG. 2 is a nuclear magnetic resonance spectrum of polyisoprene obtained in application example 5;
FIG. 3 is a GPC chart of polyisoprene obtained in application example 5.
Detailed Description
The first embodiment is as follows: the structure of the pyridine-2-aldehyde (ketone) oxime/cobalt complex is shown as a formula I:
wherein R is 1 、R 2 Is one of hydrogen, methyl, ethyl, isopropyl and phenyl.
Further defined, the pyridine-2-aldehyde (ketone) oxime/cobalt complex is one of structures shown in formulas II-V:
the preparation method for preparing the pyridine-2-aldehyde (ketone) oxime/cobalt complex comprises the following steps:
in anhydrous solvent, mixing pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride, stirring and reacting for 2-24 h at 0-50 ℃, filtering, washing and pumping to obtain pyridine-2-aldehyde (ketone) oxime/cobalt complex.
Further defined, the pyridine-2-aldehyde (ketone) oxime ligand is one of the structures shown in A-D:
further defined, the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran, chloroform, and the molar ratio of the pyridine-2-aldehyde (ketone) oxime ligand to the cobalt chloride is 2:1.
the second embodiment is as follows: the application of the pyridine-2-aldehyde (ketone) oxime/cobalt complex in conjugated diene polymerization in the embodiment I comprises the following specific processes:
under the anhydrous and anaerobic condition, pyridine-2-aldehyde (ketone) oxime/cobalt complex is dissolved by an organic solvent, conjugated diene monomer and cocatalyst are sequentially added, and polymerization reaction is carried out for 1min to 5h at the temperature of minus 30 to 70 ℃ to obtain the poly conjugated diene.
Further limited, the cocatalyst is one or more of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride and monoethylaluminum dichloride, the conjugated diene monomer is butadiene or isoprene, and the organic solvent is one of toluene, paraxylene, n-hexane, cyclohexane, pentane, methylene dichloride and tetrahydrofuran.
Further defined, the molar ratio of the conjugated diene monomer to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1000 to 10000): 1, the molar ratio of aluminum element in the cocatalyst to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1-1000): 1, wherein the volume ratio of the organic solvent to the conjugated diene monomer is (1-10): 1.
further defined, the polymerization is carried out at 25℃for 10min.
Further defined, the number average molecular weight of the resulting conjugated diene is 0.5X10 5 g/mol～3.0×10 5 The g/mol and the molecular weight distribution are 1.6-2.2, the proportion of cis-1,4 structure in the polymer is 50-80%, and the proportion of 3,4 structure is 20-50%.
Preparation of pyridine-2-aldehyde (ketone) oxime/cobalt complexes represented by formulas II-V
Example 1: the preparation method of the pyridine-2-aldoxime/cobalt complex shown in the formula II comprises the following steps:
glove10mL of redistilled methylene chloride and anhydrous CoCl were added sequentially to a 25mL dry reaction tube in a tank 2 (150.0 mg,1.16 mmol) and pyridine-2-oxime ligand A (285.0 mg,2.32 mmol) were stirred at room temperature for 15h to give a pale red suspension, after the reaction was completed, dichloromethane was dried under vacuum to give a solid which was washed 3 times with 5mL of dry n-hexane and dried under vacuum to constant weight to give 359mg of a pink solid, namely pyridine-2-aldoxime/cobalt complex of formula II (yield: 83%).
Mass spectrometry: c (C) 18 H 16 CoN 6 O 3 Theoretical value: 423.0616; actual measurement value: 423.0604.
elemental analysis: c (C) 12 H 12 Cl 2 CoN 4 O 2 : theoretical value: c,38.85; h,3.26; n,15.10; actual measurement value: c,38.34; h,3.23; n,14.81.
Example 2: the preparation method of the pyridine-2-ketoxime/cobalt complex shown in the formula III comprises the following steps:
10mL of redistilled methylene chloride and anhydrous CoCl were added sequentially to 25mL of dry reaction tube in a glove box 2 (100.0 mg,0.77 mmol) and methyl-2-pyridylketoxime ligand B (211.8 mg,1.54 mmol) were stirred at room temperature for 15h to give a red suspension, after the reaction was completed, dichloromethane was dried under vacuum to give a solid which was washed 3 times with 5mL of dry n-hexane and dried under vacuum to a constant weight to give 276mg of a red solid, namely pyridin-2-ketoxime/cobalt complex of formula III (yield: 89%).
Mass spectrometry: c (C) 21 H 22 CoN 6 O 3 Theoretical value: 465.1085; actual measurement value: 465.1043.
elemental analysis: c (C) 14 H 16 Cl 2 CoN 4 O 2 : theoretical value: c,41.81; h,4.01; n,13.93; actual measurement value: c,42.33; h,3.99; n,14.13.
Example 3: the preparation method of the pyridine-2-ketoxime/cobalt complex shown in the formula IV comprises the following steps:
10mL of redistilled methylene chloride and anhydrous CoCl were added sequentially to 25mL of dry reaction tube in a glove box 2 (80.0 mg,0.62 mmol) and phenyl-2-pyridylketoxime ligand C (246.7 mg,1.24 mmol) were stirred at room temperature 1After the reaction was completed, methylene chloride was dried under vacuum for 5 hours to obtain a solid, which was washed 3 times with 5mL of dry n-hexane and dried under vacuum to constant weight to obtain 272mg of a pale pink solid, namely pyridin-2-one oxime/cobalt complex of formula IV (yield: 87%).
Mass spectrometry: c (C) 36 H 28 CoN 6 O 3 Theoretical value: 651.1555; actual measurement value: 651.1542.
elemental analysis: c (C) 24 H 20 C l2 CoN 4 O 2 : theoretical value: c,54.77; h,3.83; n,10.65; actual measurement value: c,54.21; h,4.02; n,10.39.
Example 4: the preparation method of the 6-methylpyridine-2-aldoxime/cobalt complex shown in the formula V comprises the following steps:
10mL of redistilled methylene chloride and anhydrous CoCl were added sequentially to 25mL dry reaction tube in a glove box 2 (100.0 mg,0.77 mmol) and 6-methylpyridine-2-aldoxime ligand D (211.8 mg,1.56 mmol) were stirred at room temperature for 15 hours, after the completion of the reaction, a pale red suspension was obtained, dichloromethane was dried under vacuum, and the obtained solid was washed 3 times with 5mL of dry n-hexane and dried under vacuum until the weight was constant, to obtain 253mg of a pink solid, namely, 6-methylpyridine-2-aldoxime/cobalt complex represented by formula V (yield: 82%).
Mass spectrometry: c (C) 21 H 22 CoN 6 O 3 Theoretical value: 465.1085; actual measurement value: 465.1082.
elemental analysis: c (C) 14 H 16 Cl 2 CoN 4 O 2 : theoretical value: c,41.81; h,4.01; n,13.93; actual measurement value: c,41.96; h,4.02; n,13.92.
Application of pyridine-2-aldehyde (ketone) oxime/cobalt complex shown in formulas II-V in conjugated diene polymerization
Application example 1: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL (1.0M, 500 equivalent) of diethylaluminum chloride were added under argon atmosphere, 2mL (20 mmol,2000 equivalent) of isoprene monomer was added, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) at 25℃for 10 minutes, a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 50℃to constant weight.
The yield is>99%, activity was 8.2X10 5 g/(mol.h), number average molecular weight of 1.2X10 5 g/mol, molecular weight distribution of 1.6, cis-1,4 structure accounting for 69% and 3,4 structure accounting for 31%.
Application example 2: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL (1.0M, 500 equivalent) of diethylaluminum chloride were added under argon atmosphere, 2mL (20 mmol,2000 equivalent) of isoprene monomer was added, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) at 70℃for 10 minutes, a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 50℃to constant weight.
Yield 93% and activity 7.6X10) 5 g/(mol.h), number average molecular weight of 1.8X10 5 g/mol, molecular weight distribution of 2.0, cis-1,4 structure accounting for 64% and 3,4 structure accounting for 36%.
Application example 3: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 1.0mL (1.0M, 100 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 10min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
The yield is>99%, activity was 8.2X10 5 g/(mol.h), number average molecular weight of 1.6X10 5 g/mol, molecular weight distribution of 1.6, cis-1,4 structure accounting for 67% and 3,4 structure accounting for 33%.
Application example 4: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.5mL (1.0M, 50 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 10min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
The yield is>99%, activity was 8.2X10 5 g/(mol.h), number average molecular weight of 1.6X10 5 g/mol, molecular weight distribution of 1.7, cis-1,4 structure accounting for 66% and 3,4 structure accounting for 34%.
Application example 5: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 10min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
The yield is>99%, activity was 8.2X10 5 g/(mol.h), number average molecular weight of 1.8X10 5 g/mol, molecular weight distribution of 1.9, cis-1,4 structure accounting for 64% and 3,4 structure accounting for 36%.
Application example 6: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.5mL (1.0M, 50 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 5min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
Yield 71% and activity 1.1X10) 6 g/(mol.h), number average molecular weight of 1.3X10 5 g/mol, molecular weight distribution of 1.9, cis-1,4 structure accounting for 66% and 3,4 structure accounting for 34%.
Application example 7: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL (1.0M, 500 equivalent) of triethylaluminum were added under argon atmosphere, 2mL (20 mmol,2000 equivalent) of isoprene monomer was added, the reaction was terminated with a methanol diluted hydrochloric acid solution (1:50, V/V) at 25℃for 10min, a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 50℃to constant weight.
Yield 73%, activity 6.0X10) 5 g/(mol.h), number average molecular weight of 1.4X10 5 g/mol, molecular weight distribution of 1.8, cis-1,4 structure accounting for 67% and 3,4 structure accounting for 33%.
Application example 8: the application of the pyridine-2-aldoxime/cobalt complex shown in the formula II in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 3.7mg (10. Mu. Mol,1 equivalent) of pyridine-2-aldoxime/cobalt complex of formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 5min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
Yield was 83% and activity was 1.4X10) 6 g/(mol.h). Number average molecular weight of 1.0X10 5 g/mol, molecular weight distribution of 2.1, cis-1,4 structure accounting for 64% and 3,4 structure accounting for 36%.
Application example 9: the application of the pyridine-2-ketoxime/cobalt complex shown in the formula III in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 4.1mg (10. Mu. Mol,1 equivalent) of the pyridin-2-one oxime/cobalt complex of formula III was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride and 2mL (20 mmol,2000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 10min, quenched with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, and the solid was washed with methanol and dried under vacuum at 50℃to constant weight.
Yield rate>99%, activity was 8.2X10 5 g/(mol.h), number average molecular weight of 1.5X10 5 g/mol, molecular weight distribution of 1.9, cis-1,4 structure accounting for 65% and 3,4 structure accounting for 35%.
Application example 10: the application of the pyridine-2-ketoxime/cobalt complex shown in the formula III in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 4.1mg (10. Mu. Mol,1 equivalent) of the pyridin-2-one oxime/cobalt complex of formula III was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride and 5mL (50 mmol,5000 equivalent) of isoprene monomer were added under an argon atmosphere, reacted at 25℃for 10min, the reaction was terminated with a methanol-diluted hydrochloric acid solution (1:50, V/V) and a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 50℃to constant weight.
Yield 93%, activity 1.9X10) 6 g/(mol.h), number average molecular weight of 2.1X10 5 g/mol, molecular weight distribution of 1.7, cis-1,4 structure accounting for 66% and 3,4 structure accounting for 34%.
Application example 11: the application of the pyridine-2-ketoxime/cobalt complex shown in the formula IV in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 5.3mg (10. Mu. Mol,1 equivalent) of the weighed pyridin-2-one oxime/cobalt complex of formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene was added under an argon atmosphere, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride was added, 2mL (20 mmol,2000 equivalent) of isoprene monomer was added, the reaction was stopped at 25℃for 10min with a methanol-diluted hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 5℃to constant weight.
Yield rate>99%, activity was 8.2X10 5 g/(mol.h). Number average molecular weight of 1.8X10 5 g/mol, molecular weight distribution of 2.0, cis-1,4 structure accounting for 64% and 3,4 structure accounting for 36%.
Application example 12: the application of the pyridine-2-ketoxime/cobalt complex shown in the formula IV in isoprene polymerization is carried out according to the following steps:
25mL of a dry reaction tube was transferred to a glove box, 5.3mg (10. Mu. Mol,1 equivalent) of a weighed amount of pyridin-2-one oxime/cobalt complex of formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene was added under an argon atmosphere, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride was added, 2mL (20 mmol,2000 equivalent) of isoprene monomer was added, the reaction was stopped at-30℃for 10min with a methanol diluted hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated and filtered, the solid was washed with methanol, and vacuum-dried at 5℃to constant weight.
Yield 92% and activity 7.5X10) 5 g/(mol.h), number average molecular weight of 1.7X10 5 g/mol, molecular weight distribution of 2.0, cis-1,4 structure accounting for 67% and 3,4 structure accounting for 33%.
Application example 13: the application of the pyridine-2-ketoxime/cobalt complex shown in the formula IV in isoprene polymerization is carried out according to the following steps:
25mL of the dry reaction tube was transferred to a glove box, 5.3mg (10. Mu. Mol,1 equivalent) of the weighed pyridin-2-one oxime/cobalt complex of formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene was added under an argon atmosphere, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride was added, 1.7mL (20 mmol,2000 equivalent) of butadiene was added, the reaction was stopped at 25℃for 10min with a methanol diluted hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 5℃to constant weight.
The yield is>99%, activity was 6.5X10 5 g/(mol.h), number average molecular weight of 2.1X10 5 g/mol, molecular weight distribution of 1.9, cis-1,4 structure accounting for 69% and 3,4 structure accounting for 31%.
Application example 14: the application of the 6-methylpyridine-2-aldoxime/cobalt complex shown in the formula V in isoprene polymerization is carried out according to the following steps:
25mL of a dry reaction tube was transferred to a glove box, 4.1mg (10. Mu. Mol,1 equivalent) of a 6-methylpyridine-2-aldoxime/cobalt complex represented by formula V was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene was added under an argon atmosphere, 0.1mL (1.0M, 10 equivalent) of diethylaluminum chloride was added, 2mL (20 mmol,2000 equivalent) of isoprene monomer was further added, the reaction was stopped with a methanol diluted hydrochloric acid solution (1:50, V/V) at 25℃for 10 minutes, a large amount of white solid was precipitated and filtered, the solid was washed with methanol, and vacuum-dried at 50℃to a constant weight.
Yield rate>99%, activity was 8.2X10 5 g/(mol.h). Number average molecular weight of 2.2X10 5 g/mol, molecular weight distribution of 1.7, cis-1,4 structure accounting for 64% and 3,4 structure accounting for 36%.
Application example 15: the application of the 6-methylpyridine-2-aldoxime/cobalt complex shown in the formula V in isoprene polymerization is carried out according to the following steps:
25mL of a dry reaction tube was transferred to a glove box, 4.1mg (10. Mu. Mol,1 equivalent) of a 6-methylpyridine-2-aldoxime/cobalt complex represented by formula V was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene was added under an argon atmosphere, 0.5mL (1.0M, 50 equivalent) of diethylaluminum chloride was added, 2mL (20 mmol,2000 equivalent) of isoprene monomer was further added, the reaction was stopped with a methanol diluted hydrochloric acid solution (1:50, V/V) at 25℃for 10 minutes, a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-dried at 50℃to a constant weight.
The yield is>99%, activity was 8.2X10 5 g/(mol.h). Number average molecular weight of 1.7X10 5 g/mol, molecular weight distribution of 1.8, cis-1,4 structure accounting for 66% and 3,4 structure accounting for 34%.
Claims (9)
1. The application of pyridine-2-aldehyde (ketone) oxime/cobalt complex in conjugated diene polymerization is characterized in that under anhydrous and anaerobic conditions, the pyridine-2-aldehyde (ketone) oxime/cobalt complex is dissolved by an organic solvent, conjugated diene monomer and cocatalyst are sequentially added, and polymerization reaction is carried out for 1min to 5h at the temperature of minus 30 ℃ to 70 ℃ to obtain the poly conjugated diene, wherein the pyridine-2-aldehyde (ketone) oxime/cobalt complex has the structure that:
2. Use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 1 in the polymerization of conjugated dienes, wherein the pyridine-2-aldehyde (ketone) oxime/cobalt complex is one of the following structures:
3. use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 1 or 2 in the polymerization of conjugated dienes, characterized in that the preparation of said pyridine-2-aldehyde (ketone) oxime/cobalt complex is carried out according to the following steps:
in anhydrous solvent, mixing pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride, stirring and reacting for 2-24 h at 0-50 ℃, filtering, washing and pumping to obtain pyridine-2-aldehyde (ketone) oxime/cobalt complex.
4. Use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 3 in the polymerization of conjugated dienes, wherein the pyridine-2-aldehyde (ketone) oxime ligand is one of the following structures:
5. use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 3 in the polymerization of conjugated dienes, characterized in that the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran, chloroform, the molar ratio of pyridine-2-aldehyde (ketone) oxime ligand to cobaltous chloride is 2:1.
6. the application of pyridine-2-aldehyde (ketone) oxime/cobalt complex in conjugated diene polymerization according to claim 1, wherein the cocatalyst is one or more of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride and diethylaluminum dichloride, the conjugated diene monomer is butadiene or isoprene, and the organic solvent is one of toluene, p-xylene, n-hexane, cyclohexane, pentane, dichloromethane and tetrahydrofuran.
7. The use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 1 in the polymerization of conjugated dienes, wherein the molar ratio of conjugated diene monomer to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1000-10000): 1, the molar ratio of aluminum element in the cocatalyst to cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1-1000): 1, the volume ratio of the organic solvent to the conjugated diene monomer is (1-10): 1.
8. use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 1 in the polymerization of conjugated dienes, characterized in that it is polymerized for 10min at 25 ℃.
9. Use of a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 1 in the polymerization of conjugated dienes, characterized in that the number average molecular weight of the resulting poly conjugated dienes is 0.5 x 10 5 g/mol～3.0×10 5 The g/mol and the molecular weight distribution are 1.6-2.2, the proportion of cis-1,4 structure in the polymer is 50-80%, and the proportion of 3,4 structure is 20-50%.
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