CN114751943A - 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 80
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 150000002576 ketones Chemical class 0.000 title claims abstract description 40
- 150000002923 oximes Chemical class 0.000 title claims abstract description 40
- 150000001993 dienes Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 42
- 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
- 229940097267 cobaltous chloride Drugs 0.000 claims description 6
- 229920000642 polymer Polymers 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
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 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
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 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
- 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
- 239000008096 xylene Substances 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 45
- 230000000694 effects Effects 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- 239000007787 solid Substances 0.000 description 40
- MTFJSAGADRTKCI-VMPITWQZSA-N chembl77510 Chemical compound O\N=C\C1=CC=CC=N1 MTFJSAGADRTKCI-VMPITWQZSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000012300 argon atmosphere Substances 0.000 description 15
- OIKGFMHISSQNRL-UHFFFAOYSA-N N-[(6-methylpyridin-2-yl)methylidene]hydroxylamine Chemical compound CC1=CC=CC(C=NO)=N1 OIKGFMHISSQNRL-UHFFFAOYSA-N 0.000 description 6
- 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
- 229920001195 polyisoprene Polymers 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 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
- 238000000465 moulding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A pyridine-2-aldehyde (ketone) oxime/cobalt complex, a 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 the conjugated diene is not high. Under the anhydrous and oxygen-free conditions, dissolving a pyridine-2-aldehyde (ketone) oxime/cobalt complex by using an organic solvent, then sequentially adding a conjugated diene monomer and a cocatalyst, and carrying out polymerization reaction for 1 min-5 h at-30-70 ℃ to obtain the poly-conjugated diene. The pyridine-2-oxime-aldehyde (ketone) cobalt complex is simple to prepare, has good thermal stability and can still realize the effect at 70 DEG C>Conversion of 90% using pyridine-2-oxime-aldehyde (keto) cobalt complex/methylaluminoxane two-component catalystThe reaction activity of the system for catalyzing the polymerization of the conjugated diene can reach 1.9 multiplied by 106g/(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 rich raw materials, low price, easy processing and molding, and excellent comprehensive performance, and is widely applied to various aspects of our lives. Olefin polymerization catalysts are central to 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, including Ziegler-Natta catalysts, metallocene catalysts, non-metallocene catalysts, etc., have been developed. New non-metallocene transition metal olefin polymerization catalysts have attracted increasing attention from chemists. Compared with metallocene catalyst, non-metallocene transition metal catalyst has the advantages of simple synthetic route, easy preparation, low cost, strong compatibility to polar monomer functional group, etc.
In recent years, research on homogeneous catalysis of conjugated diene polymerization by cobalt complexes with clear structures has been rapidly developed, and the cobalt complexes have high catalytic polymerization selectivity but generally low catalytic activity. Therefore, the research of developing a novel cobalt catalyst with higher activity for olefin polymerization has important academic research significance and industrial application value.
Disclosure of Invention
The invention aims to solve the technical problem that the activity of the existing cobalt complex homogeneous catalyst for catalyzing the polymerization of the conjugated diene is not high, and provides a pyridine-2-aldehyde (ketone) oxime/cobalt complex, a preparation method thereof and application thereof in the polymerization of the conjugated diene.
The pyridine-2-aldehyde (ketone) oxime/cobalt complex has the structure as follows:
Further defined, the pyridine-2-carboxaldehyde (ketoxime)/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 an anhydrous solvent, mixing a pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride, stirring and reacting for 2-24 h at 0-50 ℃, filtering, washing, and draining to obtain the pyridine-2-aldehyde (ketone) oxime/cobalt complex.
Further defined, the pyridine-2-aldehyde (keto) oxime ligand is one of the following structures:
further defined, the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran and chloroform, and the molar ratio of the pyridine-2-aldehyde (ketone) oxime ligand to cobaltous chloride is 2: 1.
the application of the pyridine-2-aldehyde (ketone) oxime/cobalt complex in the polymerization of conjugated diene provided by the invention comprises the following specific processes:
under the anhydrous and oxygen-free conditions, dissolving a pyridine-2-aldehyde (ketone) oxime/cobalt complex by using an organic solvent, then sequentially adding a conjugated diene monomer and a cocatalyst, and carrying out polymerization reaction for 1 min-5 h at-30-70 ℃ to obtain the poly-conjugated diene.
Further limited, the cocatalyst is one or more of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride and ethylaluminum 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.
Further limiting, the molar ratio of the conjugated diene monomer to the cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1000-10000): 1, the molar ratio of the aluminum element in the cocatalyst to the 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.
further defined, the polymerization was carried out at 25 ℃ for 10 min.
Further, the number average molecular weight of the obtained poly-conjugated diene is 0.5X 105g/mol～3.0×105g/mol, the molecular weight distribution is 1.6-2.2, the proportion of cis-1,4 structures in the polymer is 50-80%, and the proportion of 3,4 structures in the polymer is 20-50%.
Compared with the prior art, the invention has the following remarkable effects:
1) the pyridine-2-oxime-aldehyde (ketone) cobalt complex is simple to prepare, has good thermal stability and can still realize the effect at 70 DEG C>90 percent of conversion rate, the polymerization of the conjugated diene is catalyzed by a pyridine-2-oxime-aldehyde (ketone) cobalt complex/methylaluminoxane two-component catalyst system, and the reaction activity can reach as high as 1.9 multiplied by 106g/(mol·h)。
2) The cobalt catalyst can realize higher number average molecular weight (0.5 multiplied by 10) of polyisoprene5g/mol～3.0×105g/mol), narrow molecular weight distribution (1.6-2.2).
3) The hydroxyl electron-donating group is directly introduced into 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 beneficial to still showing better reaction activity at high temperature.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of polyisoprene obtained in application example 5;
FIG. 2 is a nuclear magnetic carbon 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 of the embodiment is shown as formula I:
wherein R is1、R2Is one of hydrogen, methyl, ethyl, isopropyl and phenyl.
Further limited, the pyridine-2-aldehyde (ketone) oxime/cobalt complex is one of structures shown in formulas II-V:
the preparation method of the pyridine-2-aldehyde (ketone) oxime/cobalt complex comprises the following steps:
mixing a pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride in an anhydrous solvent, stirring and reacting for 2-24 h at 0-50 ℃, and filtering, washing and draining to obtain the pyridine-2-aldehyde (ketone) oxime/cobalt complex.
Further defined, the pyridine-2-aldehyde (ketone) oxime ligand is one of the structures shown as A-D:
further defined, the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran and chloroform, and the molar ratio of the pyridine-2-aldehyde (ketone) oxime ligand to cobaltous chloride is 2: 1.
the second embodiment is as follows: the application of the pyridine-2-aldehyde (ketone) oxime/cobalt complex in the polymerization of conjugated diene according to the first embodiment comprises the following specific steps:
under the anhydrous and oxygen-free conditions, dissolving a pyridine-2-aldehyde (ketone) oxime/cobalt complex by using an organic solvent, then sequentially adding a conjugated diene monomer and a cocatalyst, and carrying out polymerization reaction for 1 min-5 h at-30-70 ℃ to obtain the poly-conjugated diene.
Further limited, the cocatalyst is one or more of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride and ethylaluminum 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.
Further limiting, the molar ratio of the conjugated diene monomer to the cobalt element in the pyridine-2-aldehyde (ketone) oxime/cobalt complex is (1000-10000): 1, the molar ratio of the aluminum element in the cocatalyst to the 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.
further defined, the polymerization was carried out at 25 ℃ for 10 min.
Further, the number average molecular weight of the obtained poly-conjugated diene is 0.5X 105g/mol～3.0×105g/mol, the molecular weight distribution is 1.6-2.2, the proportion of cis-1,4 structures in the polymer is 50-80%, and the proportion of 3,4 structures in the polymer is 20-50%.
Preparation of pyridine-2-aldehyde (ketone) oxime/cobalt complexes of formulae II to V
Example 1: the preparation method of the pyridine-2-aldoxime/cobalt complex shown in the formula II comprises the following steps:
10mL of redistilled dichloromethane and anhydrous CoCl were added to a 25mL dry reaction tube in sequence in a glove box2(150.0mg, 1.16mmol) and pyridine-2-oxime ligand A (285.0mg, 2.32mmol) are stirred at room temperature for 15h to obtain a light red suspension, after the reaction is finished, dichloromethane is pumped out in vacuum, the obtained solid is washed 3 times by 5mL dry n-hexane and pumped out in vacuum to constant weight, 359mg of pink solid, namely the pyridine-2-aldoxime/cobalt complex shown in the formula II is obtained (yield: 83%).
Mass spectrometry analysis: c18H16CoN6O3Theoretical value: 423.0616, respectively; measured value: 423.0604.
elemental analysis: c12H12Cl2CoN4O2: theoretical value: c, 38.85; h, 3.26; n, 15.10; measured 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:
in a glove box, 10mL of redistilled dichloromethane and anhydrous CoCl are added into a 25mL dry reaction tube in sequence2(1000mg, 0.77mmol) and methyl-2-pyridylketoxime ligand B (211.8mg, 1.54mmol) are stirred at room temperature for 15h to obtain a red suspension, after the reaction is finished, dichloromethane is pumped out in vacuum, the obtained solid is washed 3 times with 5mL of dry n-hexane and pumped out in vacuum to constant weight to obtain 276mg of red solid, namely pyridine-2-ketoxime/cobalt complex shown in formula iii (yield: 89%).
Mass spectrometry analysis: c21H22CoN6O3Theoretical value: 465.1085, respectively; measured value: 465.1043.
elemental analysis: c14H16Cl2CoN4O2: theoretical value: c, 41.81; h, 4.01; n, 13.93; measured 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 dichloromethane and anhydrous CoCl were added to a 25mL dry reaction tube in sequence in a glove box2(80.0mg, 0.62mmol) and phenyl-2-pyridylketoxime ligand C (246.7mg, 1.24mmol), stirring at room temperature for 15h to obtain a pink suspension, after the reaction is finished, vacuum-drying dichloromethane to obtain a solid, washing the solid with 5mL dry n-hexane for 3 times, and vacuum-drying to constant weight to obtain 272mg of light pink solid, namely the pyridine-2-ketoxime/cobalt complex shown in the formula IV (yield: 87%).
Mass spectrometry analysis: c36H28CoN6O3Theoretical value: 651.1555; measured value: 651.1542.
elemental analysis: c24H20Cl2CoN4O2: theoretical value: c, 54.77; h, 3.83; n, 10.65; measured 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 dichloromethane and anhydrous CoCl were added to a 25mL dry reaction tube in sequence in a glove box2(100.0mg, 0.77mmol) and 6-methylpyridine-2-carboxaldoxime ligand D (211.8mg, 1.56mmol) were stirred at room temperature for 15h to obtain a light red suspension after the reaction was completed, and the dichloromethane was vacuum-driedAlkane, the resulting solid was washed 3 times with 5mL of dry n-hexane and vacuum-dried to constant weight to give 253mg of a pink solid, i.e., the 6-methylpyridine-2-aldoxime/cobalt complex represented by formula V (yield: 82%).
Mass spectrometry analysis: c21H22CoN6O3Theoretical values are as follows: 465.1085, respectively; measured value: 465.1082.
elemental analysis: c14H16Cl2CoN4O2: theoretical value: c, 41.81; h, 4.01; n, 13.93; measured value: c, 41.96; h, 4.02; n, 13.92.
Application of pyridine-2-aldehyde (ketone) oxime/cobalt complex shown in formulas II to 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equiv.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL (1.0M, 500 equiv.) of diethylaluminum chloride were added under an argon atmosphere, 2mL (20mmol, 2000 equiv.) of isoprene monomer was added, the mixture was reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield is>99% and an activity of 8.2X 105g/(mol. h), number average molecular weight 1.2X 105g/mol, the molecular weight distribution is 1.6, the proportion range of cis-1,4 structure is 69%, and the proportion of 3,4 structure is 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equivalent.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL of diethylaluminum monochloride (1.0M, 500 equivalent.) and 2mL of isoprene monomer (20mmol, 2000 equivalent.) were added under an argon atmosphere, reacted at 70 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield was 93%, the activity was 7.6X 105g/(mol. h), number average molecular weight 1.8X 105g/mol, the molecular weight distribution is 2.0, the proportion range of cis-1,4 structure is 64%, and the proportion of 3,4 structure is 36%.
Application example 3: the application of the pyridine-2-aldoxime/cobalt complex shown as the formula II in isoprene polymerization comprises the following steps:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equivalent.) of pyridine-2-aldoxime/cobalt complex represented by 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 (20mmol, 2000 equivalent.) of isoprene monomer were added under an argon atmosphere, reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield is>99% and an activity of 8.2X 105g/(mol. h), number average molecular weight 1.6X 105g/mol, the molecular weight distribution is 1.6, the proportion range of cis-1,4 structure is 67%, and the proportion of 3,4 structure is 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equivalent.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.5mL of diethylaluminum monochloride (1.0M, 50 equivalent.) and 2mL of isoprene monomer (20mmol, 2000 equivalent.) were added under an argon atmosphere, reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield is>99% and an activity of 8.2X 105g/(mol. h), number average molecular weight 1.6X 105g/mol, molecular weight distribution of 1.7,the proportion of cis-1,4 structure is 66%, and the proportion of 3,4 structure is 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equivalent.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL of diethylaluminum monochloride (1.0M, 10 equivalent.) and 2mL of isoprene monomer (20mmol, 2000 equivalent.) were added under an argon atmosphere, reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield is>99% and an activity of 8.2X 105g/(mol. h), number average molecular weight of 1.8X 105g/mol, the molecular weight distribution is 1.9, the proportion range of cis-1,4 structure is 64%, and the proportion of 3,4 structure is 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10. mu. mol, 1 equiv.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.5mL of diethylaluminum monochloride (1.0M, 50 equiv.) and 2mL of isoprene monomer (20mmol, 2000 equiv.) were added under argon atmosphere, the mixture was reacted for 5min at 25 ℃, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield was 71%, the activity was 1.1X 106g/(mol. h), number average molecular weight 1.3X 105g/mol, the molecular weight distribution is 1.9, the proportion range of cis-1,4 structure is 66%, and the proportion of 3,4 structure is 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:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1equive.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 5.0mL of triethylaluminum (1.0M, 500equive.) and 2mL of isoprene monomer (20mmol, 2000equive.) were added under an argon atmosphere, reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield was 73% and the activity was 6.0X 105g/(mol. h), number average molecular weight 1.4X 105g/mol, the molecular weight distribution is 1.8, the proportion range of cis-1,4 structure is 67%, and the proportion of 3,4 structure is 33%.
Application example 8: the application of the pyridine-2-aldoxime/cobalt complex shown as the formula II in isoprene polymerization comprises the following steps:
a 25mL dry reaction tube was transferred to a glove box, 3.7mg (10 μmol, 1 equivalent.) of pyridine-2-aldoxime/cobalt complex represented by formula II was added, transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL of diethylaluminum monochloride (1.0M, 10 equivalent.) and 2mL of isoprene monomer (20mmol, 2000 equivalent.) were added under an argon atmosphere, reacted at 25 ℃ for 5min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield was 83%, the activity was 1.4X 106g/(mol. h). Number average molecular weight of 1.0X 105g/mol, the molecular weight distribution is 2.1, the proportion range of cis-1,4 structure is 64 percent, and the proportion of 3,4 structure is 36 percent.
Application example 9: the application of the pyridine-2-ketoxime/cobalt complex shown as the formula III in isoprene polymerization is carried out according to the following steps:
a25 mL dry reaction tube is transferred to a glove box, 4.1mg (10 mu mol, 1 equivalent.) of pyridine-2-ketoxime/cobalt complex shown in formula III is added, the glove box is transferred to the outside, 5mL of anhydrous toluene and 0.1mL (1.0M, 10 equivalent.) of diethylaluminum chloride are added under the argon atmosphere, 2mL (20mmol, 2000 equivalent.) of isoprene monomer are added, the reaction is carried out for 10min at 25 ℃, a 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 methanol, and the mixture is dried in vacuum at 50 ℃ to constant weight.
Yield of the product>99% and an activity of 8.2X 105g/(mol. h), number average molecular weight 1.5X 105g/mol, the molecular weight distribution is 1.9, the proportion range of cis-1,4 structure is 65%, and the proportion of 3,4 structure is 35%.
Application example 10: the application of the pyridine-2-ketoxime/cobalt complex shown as the formula III in isoprene polymerization is carried out according to the following steps:
a 25mL dry reaction tube was transferred to a glove box, 4.1mg (10. mu. mol, 1equive.) of pyridine-2-ketoxime/cobalt complex represented by formula III was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene, 0.1mL of diethylaluminum monochloride (1.0M, 10equive.) and 5mL of isoprene monomer (50mmol, 5000equive.) were added under argon atmosphere, the reaction was carried out at 25 ℃ for 10min, the reaction was terminated with a methanol dilute 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 50 ℃ to constant weight.
The yield was 93%, the activity was 1.9X 106g/(mol. h), number average molecular weight 2.1X 105g/mol, the molecular weight distribution is 1.7, the proportion range of cis-1,4 structure is 66%, and the proportion of 3,4 structure is 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:
a25 mL dry reaction tube was transferred to a glove box, 5.3mg (10. mu. mol, 1equive.) of a weighed pyridine-2-ketoxime/cobalt complex represented by formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene and 0.1mL (1.0M, 10equive.) of diethylaluminum chloride were added under an argon atmosphere, 2mL (20mmol, 2000equive.) of isoprene monomer was added, the mixture was reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-pumped at 5 ℃ to constant weight.
Yield of>99% and an activity of 8.2X 105g/(mol. h). Number average molecular weight of 1.8X 105g/mol, molecular weight distribution 2.The proportion range of the 0, cis-1,4 structure is 64 percent, and the proportion of the 3,4 structure is 36 percent.
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:
a 25mL dry reaction tube was transferred to a glove box, 5.3mg (10. mu. mol, 1equive.) of a weighed pyridine-2-ketoxime/cobalt complex represented by formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene and 0.1mL (1.0M, 10equive.) of diethylaluminum chloride were added under an argon atmosphere, 2mL (20mmol, 2000equive.) of isoprene monomer was added, the mixture was reacted at-30 ℃ for 10min, the reaction was terminated with a methanol dilute hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-pumped at 5 ℃ to constant weight.
The yield was 92% and the activity was 7.5X 105g/(mol. h), number average molecular weight 1.7X 105g/mol, the molecular weight distribution is 2.0, the proportion range of cis-1,4 structure is 67%, and the proportion of 3,4 structure is 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:
a25 mL dry reaction tube was transferred to a glove box, 5.3mg (10. mu. mol, 1equive.) of a weighed pyridine-2-ketoxime/cobalt complex represented by formula IV was added, the mixture was transferred to the outside of the glove box, 5mL of anhydrous toluene and 0.1mL (1.0M, 10equive.) of diethylaluminum chloride were added under an argon atmosphere, 1.7mL (20mmol, 2000equive.) of butadiene were added, the mixture was reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-pumped at 5 ℃ to constant weight.
The yield is>99% and an activity of 6.5X 105g/(mol. h), number average molecular weight 2.1X 105g/mol, the molecular weight distribution is 1.9, the proportion range of cis-1,4 structure is 69%, and the proportion of 3,4 structure is 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:
a25 mL dry reaction tube was transferred to a glove box, 4.1mg (10. mu. mol, 1equive.) of 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 and 0.1mL (1.0M, 10equive.) of diethylaluminum chloride were added under an argon atmosphere, 2mL (20mmol, 2000equive.) of isoprene monomer was added, the mixture was reacted at 25 ℃ for 10min, the reaction was terminated with a methanol dilute hydrochloric acid solution (1:50, V/V), a large amount of white solid was precipitated, filtered, the solid was washed with methanol, and vacuum-pumped at 50 ℃ to constant weight.
Yield of>99% and an activity of 8.2X 105g/(mol. h). Number average molecular weight of 2.2X 105g/mol, the molecular weight distribution is 1.7, the proportion range of cis-1,4 structure is 64%, and the proportion of 3,4 structure is 36%.
Application example 15: the application of the 6-methylpyridine-2-aldoxime/cobalt complex shown in the formula V in isoprene polymerization comprises the following steps:
a25 mL dry reaction tube is transferred to a glove box, 4.1mg (10 mu mol, 1 equivalent.) of 6-methylpyridine-2-aldoxime/cobalt complex shown in formula V is added, the mixture is transferred to the outside of the glove box, 5mL of anhydrous toluene and 0.5mL (1.0M, 50 equivalent.) of diethylaluminum chloride are added under the argon atmosphere, 2mL (20mmol, 2000 equivalent.) of isoprene monomer are added, the mixture is reacted at 25 ℃ for 10min, the reaction is stopped by methanol dilute hydrochloric acid solution (1:50, V/V), a large amount of white solid is separated out, the solid is filtered, the solid is washed by methanol, and the mixture is dried in vacuum at 50 ℃ until the constant weight is reached.
The yield is>99% and an activity of 8.2X 105g/(mol. h). Number average molecular weight of 1.7X 105g/mol, the molecular weight distribution is 1.8, the proportion range of cis-1,4 structure is 66%, and the proportion of 3,4 structure is 34%.
Claims (10)
1. A pyridine-2-aldehyde (ketone) oxime/cobalt complex, wherein the complex has the structure:
2. A pyridine-2-carboxaldehyde (ketoxime)/cobalt complex as claimed in claim 1 wherein the pyridine-2-carboxaldehyde (ketoxime)/cobalt complex is of one of the following structures:
3. a process for the preparation of a pyridine-2-carboxaldehyde (ketoxime)/cobalt complex as claimed in claim 1 or 2, which comprises the steps of:
mixing a pyridine-2-aldehyde (ketone) oxime ligand with cobaltous chloride in an anhydrous solvent, stirring and reacting for 2-24 h at 0-50 ℃, and filtering, washing and draining to obtain the pyridine-2-aldehyde (ketone) oxime/cobalt complex.
4. The process of claim 3, wherein the pyridine-2-aldehyde (ketone) oxime ligand is one of the following structures:
5. the method for preparing a pyridine-2-aldehyde (ketone) oxime/cobalt complex according to claim 3, wherein the anhydrous solvent is one of anhydrous dichloromethane, toluene, xylene, tetrahydrofuran and chloroform, and the molar ratio of the pyridine-2-aldehyde (ketone) oxime ligand to cobaltous chloride is 2: 1.
6. the application of the pyridine-2-aldehyde (ketone) oxime/cobalt complex in the polymerization of conjugated diene as claimed in claim 1 or 2, wherein the pyridine-2-aldehyde (ketone) oxime/cobalt complex is dissolved in an organic solvent under anhydrous and oxygen-free conditions, and then a conjugated diene monomer and a cocatalyst are sequentially added for polymerization reaction at-30-70 ℃ for 1 min-5 h to obtain the poly-conjugated diene.
7. The use of a pyridine-2-carboxaldehyde (one) oxime/cobalt complex as defined in claim 6 in the polymerization of conjugated diene, wherein the cocatalyst is one or more selected from methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride and ethylaluminum dichloride, the conjugated diene monomer is butadiene or isoprene, and the organic solvent is one selected from toluene, p-xylene, n-hexane, cyclohexane, pentane, dichloromethane and tetrahydrofuran.
8. The use of a pyridine-2-carboxaldehyde (ketoxime)/cobalt complex in the polymerization of a conjugated diene according to claim 6, wherein the molar ratio of the conjugated diene monomer to the cobalt element in the pyridine-2-carboxaldehyde (ketoxime)/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.
9. the use of a pyridine-2-carboxaldehyde (ketoxime)/cobalt complex as claimed in claim 6 for the polymerization of conjugated dienes, wherein the polymerization is carried out at 25 ℃ for 10 min.
10. Use of a pyridine-2-carboxaldehyde (keto) oxime/cobalt complex as defined in claim 6 in the polymerization of conjugated dienes, wherein the resulting poly-conjugated diene has a number average molecular weight of 0.5 x 105g/mol～3.0×105g/mol, the molecular weight distribution is 1.6-2.2, the proportion of cis-1,4 structures in the polymer is 50-80%, and the proportion of 3,4 structures in the polymer is 20-50%.
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