CN111233938B - Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same - Google Patents
Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same Download PDFInfo
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 34
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- -1 Pyrimidineacetylacetone Chemical compound 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 134
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 150000002466 imines Chemical class 0.000 claims abstract description 63
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims abstract description 42
- 238000009826 distribution Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000020335 dealkylation Effects 0.000 claims description 4
- 238000006900 dealkylation reaction Methods 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 39
- 239000003054 catalyst Substances 0.000 abstract description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 31
- 239000012300 argon atmosphere Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 9
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012380 dealkylating agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 3
- 239000000899 Gutta-Percha Substances 0.000 description 2
- 240000000342 Palaquium gutta Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229920000588 gutta-percha Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003203 stereoselective catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
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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
- C07F15/02—Iron compounds
-
- 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
- C08F136/06—Butadiene
-
- 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
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/06—Butadiene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/08—Isoprene
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A pyridine imine acetylacetone ferrous complex, a preparation method thereof and a method for catalyzing the polymerization of conjugated diene by using the pyridine imine acetylacetone ferrous complex. The invention belongs to the field of conjugated diene catalytic polymerization. The invention aims to solve the technical problems that the existing iron-based catalyst has poor solubility in a reaction system and the polymer catalyzed and polymerized by the iron-based catalyst has low molecular weight. The pyridine imine ferrous acetylacetonate complex is prepared by reacting a dichloromethane solution of pyridine imine with ferrous acetylacetonate, the pyridine imine ferrous acetylacetonate complex is used as a main catalyst in the polymerization of conjugated diene, the catalyst has good solubility in a reaction system and high activity, and the obtained polymer has high molecular weight and narrow molecular weight distribution.
Description
Technical Field
The invention belongs to the field of conjugated diene catalytic polymerization, and particularly relates to a pyridine imine ferrous acetylacetonate complex, a preparation method thereof and a method for catalyzing conjugated diene polymerization by using the pyridine imine ferrous acetylacetonate complex.
Background
Trans (trans) -1,4-polyisoprene (TPI for short) is a synthetic rubber mainly containing trans-1,4 structure, and the relative molecular mass is about 50000. Has the similar structure and performance of natural gutta percha and gutta percha. Because of low dynamic heat generation, small rolling resistance, excellent wear resistance and dynamic fatigue performance, trans-1,4-polyisoprene is one of raw materials for manufacturing high-performance green tires such as radial tires, air springs and other dynamic products. The trans-order of the material makes the material easy to crystallize at normal temperature, has certain hardness and tensile strength, and melts at 60 ℃ and has good plasticity, so that the material is widely applied to medical orthopedic materials, splints, golf balls and other materials.
The main polymerization system adopted in the artificial synthesis of trans-1,4-polyisoprene at present is bulk polymerization catalyzed by a load titanium system, and a solution polymerization method using a vanadium system catalyst and a rare earth system is adopted. However, vanadium metal has high toxicity and the purification process of the product is complex; the rare metal catalyst belongs to non-renewable energy sources due to high price and moderate activity, and the development of the rare metal catalyst is restricted. Therefore, the development of novel economic, environment-friendly, high-activity, high-regioselectivity and stereoselective catalysts will have important scientific research values and application research requirements. In recent years, iron-based catalysts have also attracted attention in isoprene polymerization because of their environmental friendliness, economy, biocompatibility, and good tolerance to polar monomers. However, the conventional iron-based catalyst technology has problems that the catalyst is poor in solubility in a reaction system, or the molecular weight of a polymer is low.
Disclosure of Invention
The invention provides a pyridine imine ferrous acetylacetonate complex, a preparation method thereof and a method for catalyzing polymerization of conjugated diene by using the pyridine imine ferrous acetylacetonate complex, aiming at solving the technical problems that the existing iron catalyst has poor solubility in a reaction system and a polymer catalyzed by the iron catalyst has low molecular weight.
The structural general formula of the pyridine imine acetylacetone ferrous complex is as follows:
wherein acac is acetylacetone-based negative ions; r is 1 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl, R 2 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl, R 3 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl, R 4 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl, R 5 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl, R 6 Selected from hydrogen, methyl, ethyl, phenyl or adamantyl.
Further limited, the specific structure of the pyridine imine ferrous acetylacetonate complex is as follows:
the preparation method of the pyridine imine acetylacetone ferrous complex comprises the following steps: under the anhydrous and oxygen-free conditions, pyridine imine ligand and ferrous acetylacetonate are added into an anhydrous solvent to react at the temperature of 0-60 ℃, and after the reaction is finished, post-treatment is carried out to obtain the pyridine imine ferrous acetylacetonate complex.
Further defined, the pyridimine ligand has the formula:
further limiting, the molar ratio of the pyridine imine ligand to the ferrous acetylacetonate salt is 1:1.
Further defined, the anhydrous solvent is toluene, tetrahydrofuran, or dichloromethane.
Further defined, the reaction temperature is 25 ℃.
Further limiting, the post-processing steps are sequentially: filtering, collecting filtrate, concentrating to solid, washing with anhydrous n-hexane at 0 deg.C, collecting solid, and vacuum drying.
The method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
under the anhydrous and anaerobic conditions, adding a solvent, a pyridine imine ferrous acetylacetonate complex, a cocatalyst and a conjugated diene monomer into a reactor in any order, carrying out polymerization reaction for 1-6 h at the temperature of 0-50 ℃, adding a quenching agent after the reaction is finished, and separating and purifying to obtain the poly-conjugated diene.
Further defined, the polymerization temperature is 25 ℃.
Further defined, the polymerization time was 2 hours.
Further limiting, the solvent is one or a mixture of several of toluene, petroleum ether, pentane and n-hexane in any ratio.
Further defined, the volume ratio of conjugated diene monomer to solvent is 1: (1-50).
Further defined, the conjugated diene monomer is one or a mixture of two of isoprene and butadiene according to any ratio.
Further defined, when the conjugated diene monomer is a mixture of isoprene and butadiene, the molar ratio of isoprene to butadiene is 1:1.
Further limiting, a chain transfer reagent is added into the polymerization reaction system, and the chain transfer reagent is allyl chloride, allyl bromide, diethylsilane, triphenylsilane, trimethylsilane, triethylaluminum or triisobutylaluminum.
Further defined, the molar ratio of the chain transfer reagent to the pyridine imine ferrous acetylacetonate complex is (1-100): 1.
further defined, the molar ratio of the chain transfer agent to the ferrous pyridinimide acetylacetonate complex is 20.
Further, the molar ratio of the conjugated diene monomer to the pyridinimine ferrous acetylacetonate complex is (1000 to 20000): 1.
Further defined, the molar ratio of the conjugated diene monomer to the ferrous pyridinium imine acetylacetonate complex is 2000.
Further defined, the cocatalyst is a single component system or a two component system; when the cocatalyst is a single component system, the cocatalyst is methylaluminoxane or modified methylaluminoxane; when the cocatalyst is a two-component system, the cocatalyst is a mixture of an aluminum alkyl and a dealkylating agent.
Further limiting, when the cocatalyst is a single-component system, the molar ratio of the cocatalyst to the pyridine imine acetylacetone ferrous complex is (1-1000)): 1.
Further defined, when the cocatalyst is a single component system, the molar ratio of the cocatalyst to the pyridine imine ferrous acetylacetonate complex is 500.
Further limiting, when the cocatalyst is a two-component system, the molar ratio of the alkyl aluminum to the pyridine imine acetylacetone ferrous complex is (1-100): 1.
Further limiting, when the cocatalyst is a two-component system, the molar ratio of the aluminum alkyl to the pyridine imine ferrous acetylacetonate complex is 20.
Further defined, when the cocatalyst is a two-component system, the molar ratio of the dealkylation reagent to the pyridine imine acetylacetone ferrous complex is (1-10): 1.
Further defined, when the cocatalyst is a two-component system, the molar ratio of the dealkylating agent to the ferrous pyridineimine acetylacetonate complex is 1:1.
Further defined, the aluminum alkyl is trimethylaluminum, triethylaluminum, or triisobutylaluminum.
Further defined, the dealkylating agent is B (C) 6 F 5 ) 3 ，[Ph 3 C][B(C 6 F 5 ) 4 ]Or [ PhNMe 2 H][B(C 6 F 5 ) 4 ]。
Further defined, the feeding sequence is any one of the following three types:
(1) Sequentially adding a cocatalyst, a solvent and a conjugated diene monomer in sequence, and then adding a pyridine imine ferrous acetylacetonate complex; (2) Sequentially adding a cocatalyst, a solvent and a pyridine imine acetylacetone ferrous complex in sequence, and then adding a conjugated diene monomer; (3) Sequentially adding the pyridine imine ferrous acetylacetonate complex, the solvent and the conjugated diene monomer in sequence, and then adding the cocatalyst.
Further defined, the quenching agent is a mixed solution of methanol and hydrochloric acid, wherein the volume ratio of methanol to hydrochloric acid is 50.
Further defined, the quencher to solvent volume ratio is 2:1.
Further, it is also possible to add an aging inhibitor, which is a 1% by mass ethanol solution of 2,6-di-tert-butyl-4-methylphenol, after the polymerization is completed.
Further defined, the volume ratio of the aging inhibitor to the solvent is 1:5.
Further limiting, the obtained poly-conjugated diene has the number average molecular weight of 2 to 20 ten thousand and the molecular weight distribution of 1.4 to 5.0; the cis-1,4 structure accounts for 0% -20%, the trans-1,4 structure accounts for 70% -90%, and the 3,4 (1,2-) structure accounts for 10% -20%.
Further defined, the poly-conjugated diene is primarily used in tire manufacture, especially in the manufacture of automobile tires.
Compared with the prior art, the invention has the following remarkable effects:
the invention provides a novel high-efficiency iron catalyst system by taking cheap iron as a metal center and pyridine imine as a main framework. The pyridine imine ferrous acetylacetonate complex catalyst system provided by the invention has the characteristics of definite molecular structure, high activity, excellent selectivity and the like, and obtains a polymer with relatively high molecular weight (the number average molecular weight is 2-20 ten thousand) and narrow molecular weight distribution (PDI = 1.4-5.0). The technical effects obtained are as follows:
1) The iron catalyst is a pyridine imine acetylacetone ferrous complex with a clear molecular structure, the solubility of the catalyst in a reaction solvent (such as toluene or normal hexane) is obviously improved compared with the existing iron halide complex with the same skeleton, the reaction system is a homogeneous catalysis system, the reaction efficiency is good, and the iron catalyst has an industrial application prospect.
2) The pyridine imine acetylacetone ferrous complex shows higher activity under a lower cocatalyst, and the obtained polymer has high molecular weight (2-20 ten thousand), narrow molecular weight distribution (1.4-5.0) and high structural content of trans-1,4 up to 70-90 percent; and the molecular weight of the polymer can be regulated by a chain transfer reagent.
Drawings
Fig. 1 is a crystal structure diagram of a ferrous pyridineimine acetylacetonate complex obtained in the first embodiment.
Detailed Description
The first embodiment is as follows: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, first, anhydrous Fe (acac) was added to a 25mL Schlenk tube 2 (566.3mg, 2.23mmol), and then the pyridine imine ligand L 1 (224.3mg, 2.23mmol) is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated, washed by normal hexane for 2 times and dried in vacuum for 12 hours, and a brown solid product, namely, the pyridine imine acetylacetone ferrous complex (marked as catalyst 1), 682mg and 63.7 percent of yield are obtained.
Mass spectrometry analysis: c 25 H 30 FeN 2 O 4 :[M+H] + : theoretical value: 479.1628; measured value: 479.1577.
elemental analysis: [ C ] 25 H 30 FeN 2 O 4 +0.5CH 2 Cl 2 ]Theoretical value: c,58.81; h,6.00; n,5.38, found C,59.36%; h,6.19%; n,4.40 percent.
The second embodiment is as follows: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, anhydrous Fe (acac) was first added to a 25mL Schlenk tube 2 (216.21mg, 0.85mmol), followed by the pyridine imine ligand L 2 (150mg, 0.85mmol) is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated, washed by n-hexane for 2 times, and dried in vacuum for 12 hours, so that a green solid product, namely the pyridine imine acetylacetone ferrous complex (marked as catalyst 2), is obtained, wherein the yield is 160mg and 43.7%.
Mass spectrometry analysis: c 21 H 30 FeN 2 O 4 :[M+H] + : theoretical value: 431.1628; measured value: 431.1573.
elemental analysis: c 21 H 30 FeN 2 O 4 : theoretical value: c,58.61%; h,7.03%; n,6.51%; found C,57.81%; h,6.97%; n,6.31 percent.
The third concrete implementation mode: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, anhydrous Fe (acac) was first added to a 25mL Schlenk tube 2 (254.06mg, 1mmol)), followed by the pyridine imine ligand L 3 (240mg, 1mmol) is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated, washed by n-hexane for 2 times and dried in vacuum for 12 hours, and a brown solid product, namely, a pyridine imine acetylacetone ferrous complex (marked as a catalyst 3), 345.8mg and 70 percent of yield, is obtained.
Mass spectrometry analysis: c 26 H 34 FeN 2 O 4 :[M+H] + : theoretical value: 495.1941; measured value: 495.1899.
elemental analysis: [ C ] 26 H 34 FeN 2 O 4 +0.5C 6 H 14 ]: theoretical value: c,64.80%; h,7.69%; n,5.21%; found C,65.21%; h,7.19%; and 6.09 percent of N.
The fourth concrete implementation mode: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, anhydrous Fe (acac) was first added to a 25mL Schlenk tube 2 (95.94mg, 0.378mmol), followed by the addition of a pyridinimine ligand L 4 (90mg, 0.378mmol) is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated and washed by n-hexane for 2 times, and the filtrate is dried for 12 hours in vacuum, so that a dark green solid product, namely the pyridine imine acetylacetone ferrous complex (marked as catalyst 4), is obtained, wherein the yield is 100mg and 54%.
Mass spectrometry analysis: c 26 H 32 FeN 2 O 4 :[M+H] + : theoretical values are as follows: 493.1784; measured value: 493.1785.
elemental analysis: c 26 H 32 FeN 2 O 4 : theoretical value: c,63.42%; h,6.55%; n,5.69%; found C,63.25%; h,7.02%; and N,6.01 percent.
The fifth concrete implementation mode: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, anhydrous Fe (acac) was first added to a 25mL Schlenk tube 2 (254.06mg, 1mmol), followed by the pyridine imine ligand L 5 (238.33mg, 1mmol) of ligand is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated, washed by n-hexane for 2 times, and dried in vacuum for 12 hours to obtain a brown solid product, namely, the pyridine imine ferrous acetylacetonate complex (marked as catalyst 5), 225mg and the yield is 45.7%.
Mass spectrometry analysis: c 26 H 32 FeN 2 O 4 :[M+H] + : theoretical values are as follows: 493.1784; measured value: 493.1740.
elemental analysis: c 26 H 32 FeN 2 O 4 : theoretical value: c,63.42%; h,6.55%; n,5.69%; found C,62.82%; h,6.47%; n,5.71 percent.
The sixth specific implementation mode: the structural formula of the pyridine imine acetylacetone ferrous complex of the embodiment is as follows:
the preparation method comprises the following steps: under argon atmosphere, anhydrous Fe (acac) was first added to a 25mL Schlenk tube 2 (213.20mg, 0.839mmol), and then adding a pyridine imine ligand L 6 (200mg, 0.839 mmol) is added into the system, 20mL of dichloromethane solvent is added, the mixture is stirred and reacted for 2 days at the temperature of 25 ℃, after the reaction is finished, the filtrate is collected by filtration, concentrated and washed by normal hexane for 2 times, and the vacuum drying is carried out for 12 hours, so as to obtain a green solid product, namely the pyridine imine acetylacetone ferrous complex (marked as catalyst 6), and the yield of 186mg is 45%.
Mass spectrometry analysis: c 26 H 32 FeN 2 O 4 :[M+H]+: theoretical value: 493.1784; measured value: 493.1788.
elemental analysis: c 26 H 32 FeN 2 O 4 : theoretical values are as follows: c,63.42%; h,6.55%; n,5.69%; found:%; h,%; n,%.
The seventh concrete implementation mode: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under argon atmosphere, catalyst 1 (4.78mg, 10. Mu. Mol) obtained in the first embodiment, anhydrous toluene (5 mL), isoprene (2.00mL, 20.0 mmol), MAO (5mmol, 500eq.), which was polymerized at 25 ℃ for 120min, was quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol having a mass concentration of 1% was added, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield: >99%, number average molecular weight (Mn): 3.7 ten thousand, molecular weight distribution (PDI): 1.7. the proportion of different structures: the trans-1,4-structure accounts for 82%, and the 3,4-structure accounts for 18%.
The specific implementation mode is eight: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
under argon atmosphere, catalyst 1 (4.78mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (5 mL), isoprene (2.00ml, 20.0 mmol), and MMAO (5mmol, 500eq.) were sequentially added to a 25mL Schlenk tube, polymerized at 25 ℃ for 120min, quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), added with 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol having a mass concentration of 1%, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield: 90%, number average molecular weight (Mn): 2.3 ten thousand, molecular weight distribution (PDI): 1.6. the proportion of different structures: the trans-1,4-structure accounts for 68%, the cis-1,4-structure accounts for 12%, and the 3,4-structure accounts for 20%.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: the solvent is 5mL of anhydrous petroleum ether, and other steps and parameters are the same as those of the eighth embodiment.
As a result: yield: >99%, number average molecular weight (Mn): 6.5 million, molecular weight distribution (PDI): 1.8. the proportion of different structures: the structure of trans-1,4-is 81%, and the structure of 3,4-is 19%.
The detailed implementation mode is ten: the eighth embodiment is different from the eighth embodiment in that: the solvent is 5mL of anhydrous n-hexane, and other steps and parameters are the same as those of the eighth embodiment.
As a result: yield: 87%, number average molecular weight (Mn): 4.5 ten thousand, molecular weight distribution (PDI): 1.5. the proportion of different structures: the structure of trans-1,4-accounts for 83%, and the structure of 3,4-accounts for 17%.
The concrete implementation mode eleven: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under argon atmosphere, catalyst 1 (4.78mg, 10. Mu. Mol) obtained in the first embodiment, anhydrous toluene (5 mL), isoprene (2.00mL, 20.0 mmol), MAO (2.5mmol, 250eq.), which was polymerized at 25 ℃ for 120min, was quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol having a mass concentration of 1% was added, and the mixture was washed twice with ethanol to obtain a white polymer.
As a result: yield: 85%, number average molecular weight (Mn): 3.8 ten thousand, molecular weight distribution (PDI): 3.4. the proportion of different structures: the trans-1,4-structure accounts for 77%, the cis-1,4-structure accounts for 7%, and the 3,4-structure accounts for 16%.
The specific implementation mode twelve: the present embodiment is different from the first embodiment in that: the amount of MAO used was 1mmol,100eq, and the other steps and parameters were the same as those in the first embodiment.
As a result: yield: 80%, number average molecular weight (Mn): 3.8 ten thousand, molecular weight distribution (PDI): 4.1. the proportion of different structures: the trans-1,4-structure accounts for 80%, and the 3,4-structure accounts for 20%.
The specific implementation mode is thirteen: the present embodiment is different from the first embodiment in that: the amount of MAO used was 0.5mmol,50eq., and other steps and parameters were the same as those in the first embodiment.
As a result: yield: 58%, number average molecular weight (Mn): 2.3 ten thousand, molecular weight distribution (PDI): 2.9. the proportion of different structures: the trans-1,4-structure accounts for 80%, and the 3,4-structure accounts for 20%.
The specific implementation mode is fourteen: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 1 (4.78mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (10 mL), isoprene (4.00ml, 40.0 mmol), MAO (5mmol, 500eq.) were sequentially added, polymerized at 25 ℃ for 240min, then quenched with 20mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), added 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass concentration of 1%, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield: 90%, number average molecular weight (Mn): 15.8 ten thousand, molecular weight distribution (PDI): 1.9. the proportion of different structures: the trans-1,4-structure accounts for 87%, and the 3,4-structure accounts for 13%.
The concrete implementation mode is fifteen: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 1 (4.78mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (5 mL), isoprene (8.00ml, 80.0 mmol), MAO (10mmol, 1000eq.) were sequentially added, polymerized at 25 ℃ for 360min, then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), added 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass concentration of 1%, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield: 65%, number average molecular weight (Mn): 19.8 ten thousand, molecular weight distribution (PDI): 1.8. the proportion of different structures: the trans-1,4-structure accounts for 85%, and the 3,4-structure accounts for 15%.
The specific implementation mode is sixteen: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under argon atmosphere, catalyst 2 (4.30mg, 10. Mu. Mol) obtained in accordance with EXAMPLE II, anhydrous toluene (5 mL), isoprene (2.00mL, 20.0 mmol), MAO (5mmol, 500eq.) (5 mL), was added in this order, and polymerization was carried out at 25 ℃ for 120min, followed by quenching with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), adding 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol having a mass concentration of 1%, and finally washing with ethanol twice to obtain a white polymer.
As a result: yield: 52%, number average molecular weight (Mn): 2.7 ten thousand, molecular weight distribution (PDI): 1.7. the proportion of different structures: the trans-1,4-structure accounts for 82%, the cis-1,4-structure accounts for 5%, and the 3,4-structure accounts for 13%.
Seventeenth embodiment: this embodiment is sixteen different from the specific embodiment: catalyst 3 (4.94mg, 10. Mu. Mol) obtained in EXAMPLE III, the other steps and parameters being identical to those of EXAMPLE sixteen.
As a result: yield: 52%, number average molecular weight (Mn): 1.9 ten thousand, molecular weight distribution (PDI): 1.9. the proportion of different structures: the trans-1,4-structure accounts for 82%, the cis-1,4-structure accounts for 5%, and the 3,4-structure accounts for 13%.
Eighteen specific embodiments: this embodiment is sixteen different from the specific embodiment: catalyst 4 (4.92mg, 10. Mu. Mol) obtained in accordance with embodiment four, and the other steps and parameters were the same as those in embodiment sixteen.
As a result: yield: 86%, number average molecular weight (Mn): 5.8 million, molecular weight distribution (PDI): 2.3. the proportion of different structures: the trans-1,4-structure accounts for 80%, and the 3,4-structure accounts for 20%.
The detailed embodiment is nineteen: this embodiment is sixteen different from the specific embodiments in that: catalyst 5 (4.92mg, 10. Mu. Mol) obtained in the fifth embodiment, and the other steps and parameters were the same as those in the sixteenth embodiment.
As a result: yield: 87%, number average molecular weight (Mn): ten thousand, molecular weight distribution (PDI): . The proportion of different structures: the structure of trans-1,4-is 82%, and the structure of 3,4-is 18%.
The specific implementation mode twenty: this embodiment is sixteen different from the specific embodiment: catalyst 6 (4.92mg, 10. Mu. Mol) obtained in the sixth embodiment, and the other steps and parameters were the same as those in the sixteenth embodiment.
As a result: yield: >99%, number average molecular weight (Mn): 3.3 ten thousand, molecular weight distribution (PDI): 2.0. the proportion of different structures: the trans-1,4-structure accounts for 73%, the cis-1,4-structure accounts for 8%, and the 3,4-structure accounts for 19%.
The specific implementation mode is twenty one: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 1 (4.78mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (5 mL), allyl chloride (200 μmol), isoprene (2.00ml, 20.0 mmol), MAO (5 mmol, 500eq.) were sequentially added, polymerized at 25 ℃ for 120min, then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), followed by addition of 1mL of a 1% by mass solution of 2,6-di-tert-butyl-4-methylphenol in ethanol, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield: >99%, number average molecular weight (Mn): 2.3, molecular weight distribution (PDI): 2.5. the proportion of different structures: the trans-1,4-structure accounts for 83%, and the 3,4-structure accounts for 17%.
Specific embodiment twenty-two: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under an argon atmosphere, catalyst 1 (4.78mg, 10 μmol) obtained in the first embodiment, anhydrous toluene (5 mL), butadiene (1.75ml, 20.0 mmol), MAO (5 mmol, 500eq.), was added in this order, polymerized at 25 ℃ for 120min, then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), added 1mL of an ethanol solution of 8978 zft 8978-di-t-butyl-4-methylphenol with a mass concentration of 1%, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield:>99% number average molecular weight (M) n ): 4.5 ten thousand, molecular weight distribution (PDI): 2.2. the proportion of different structures: the trans-1,4-structure accounts for 80%, and the 1,2-structure accounts for 20%.
Specific embodiment twenty-three: the method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex comprises the following steps:
to a 25mL Schlenk tube under argon atmosphere, catalyst 1 (9.56mg, 20. Mu. Mol) obtained in the first embodiment, anhydrous toluene (10 mL), a mixture of isoprene (2mL, 20.0 mmol) and butadiene (1.75mL, 20.0 mmol), MAO (10mmol, 1000eq.) were added in this order, polymerized at 25 ℃ for 120min, then quenched with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio = 50/1), followed by addition of 1mL of an ethanol solution of 2,6-di-tert-butyl-4-methylphenol having a mass concentration of 1%, and finally washed twice with ethanol to obtain a white polymer.
As a result: yield:>99% number average molecular weight (M) n ): 2.7 ten thousand, molecular weight distribution (PDI): 2.2. the proportion of different structures: isoprene: butadiene =1:1; isoprene segment: the trans-1,4-structure accounts for 82 percent, and the 3,4-structure accounts for 18 percent; butadiene segment: the trans-1,4-structure accounts for 80%, and the 1,2-structure accounts for 20%.
Claims (6)
1. A method for catalyzing conjugated diene polymerization by a pyridine imine ferrous acetylacetonate complex is characterized by comprising the following steps: under the anhydrous and anaerobic conditions, adding a solvent, a pyridine imine ferrous acetylacetonate complex, a cocatalyst and a conjugated diene monomer into a reactor in any order, carrying out polymerization reaction for 2 hours at 25 ℃, adding a quenching agent after the reaction is finished, and separating and purifying to obtain the poly-conjugated diene;
the specific structure of the pyridine imine ferrous acetylacetonate complex is as follows:
the number average molecular weight of the obtained poly-conjugated diene is 2-20 ten thousand, and the molecular weight distribution is 1.4-5.0; according to the mass fraction, 0-20% of the polymer is cis-1,4-structure, 70-90% is trans-1,4-structure, and 10-20% is 3,4-structure or 1,2-structure.
2. The method for catalyzing the polymerization of the conjugated diene by the pyridine imine ferrous acetylacetonate complex according to claim 1, wherein the preparation method of the pyridine imine ferrous acetylacetonate complex comprises the following steps: under the anhydrous and oxygen-free conditions, pyridine imine ligand and ferrous acetylacetonate are added into an anhydrous solvent to react at the temperature of 0-60 ℃, and after the reaction is finished, post-treatment is carried out to obtain the pyridine imine ferrous acetylacetonate complex.
3. The method for catalyzing polymerization of conjugated diene by using the pyridine imine ferrous acetylacetonate complex according to claim 1, wherein the solvent is one or a mixture of toluene, petroleum ether, pentane and n-hexane; the volume ratio of the conjugated diene monomer to the solvent is 1: (1-50).
4. The method for catalyzing polymerization of conjugated diene by using the ferrous pyridine imine acetylacetonate complex according to claim 1, wherein the conjugated diene monomer is one or a mixture of isoprene and butadiene; when the conjugated diene monomer is a mixture of isoprene and butadiene, the molar ratio of isoprene to butadiene is 1:1; the molar ratio of the conjugated diene monomer to the pyridine imine acetylacetone ferrous complex is (1000-20000): 1.
5. The method for catalyzing the polymerization of the conjugated diene by using the pyridine imine ferrous acetylacetonate complex according to claim 1, wherein a chain transfer reagent is further added into a polymerization reaction system, and the chain transfer reagent is allyl chloride, allyl bromide, diethylsilane, triphenylsilane, trimethylsilane, triethylaluminum or triisobutylaluminum; the molar ratio of the chain transfer reagent to the pyridine imine acetylacetone ferrous complex is (1-100): 1.
6. the method for catalyzing polymerization of conjugated diene through pyridine imine ferrous acetylacetonate complex according to claim 1, wherein said co-catalysis is performedThe agent is a single-component system or a two-component system; when the cocatalyst is a single component system, the cocatalyst is methylaluminoxane or modified methylaluminoxane; when the cocatalyst is a two-component system, the cocatalyst is a mixture of aluminum alkyl and dealkylation reagent; when the cocatalyst is a single-component system, the molar ratio of the cocatalyst to the pyridine imine acetylacetone ferrous complex is (1-1000): 1; when the cocatalyst is a two-component system, the molar ratio of the alkyl aluminum to the pyridine imine ferrous acetylacetonate complex is (1-100) to 1, and the molar ratio of the dealkylation reagent to the pyridine imine ferrous acetylacetonate complex is (1-10) to 1; the alkyl aluminum is trimethyl aluminum, triethyl aluminum or triisobutyl aluminum; the dealkylation reagent is B (C) 6 F 5 ) 3 ，[Ph 3 C][B(C 6 F 5 ) 4 ]Or [ PhNMe 2 H][B(C 6 F 5 ) 4 ]。
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| 过渡金属配合物催化异戊二烯配位聚合综合实验的设计;刘文静;《化学教育》;20180518;全文 * |
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