CN114702519B - Titanium imine pyridine complex, preparation method thereof and application thereof in preparation of conjugated diene-ethylene copolymer - Google Patents
Titanium imine pyridine complex, preparation method thereof and application thereof in preparation of conjugated diene-ethylene copolymer Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 67
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 84
- 150000002466 imines Chemical class 0.000 title claims description 56
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 13
- 239000010936 titanium Substances 0.000 title claims description 9
- 229910052719 titanium Inorganic materials 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000005977 Ethylene Substances 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 48
- -1 Titanium iminopyridine Chemical compound 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 238000003780 insertion Methods 0.000 claims abstract description 25
- 230000037431 insertion Effects 0.000 claims abstract description 25
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- UAUWQDYZTPSTBL-UHFFFAOYSA-N pyridine;titanium Chemical compound [Ti].C1=CC=NC=C1 UAUWQDYZTPSTBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 7
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 125000000879 imine group Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 153
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 128
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 53
- 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 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- TYZDVIKVOSCQIG-UHFFFAOYSA-L pyridine-2-carboxylate titanium(2+) Chemical compound [Ti++].[O-]C(=O)c1ccccn1.[O-]C(=O)c1ccccn1 TYZDVIKVOSCQIG-UHFFFAOYSA-L 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920006247 high-performance elastomer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 58
- 239000000460 chlorine Substances 0.000 description 36
- 238000005259 measurement Methods 0.000 description 36
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 25
- 239000012300 argon atmosphere Substances 0.000 description 24
- 230000037048 polymerization activity Effects 0.000 description 24
- 239000007789 gas Substances 0.000 description 23
- 125000001309 chloro group Chemical group Cl* 0.000 description 20
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 18
- 238000000921 elemental analysis Methods 0.000 description 18
- 238000004949 mass spectrometry Methods 0.000 description 18
- 239000007858 starting material Substances 0.000 description 15
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 2
- OZIMPUNGBUYCSP-UHFFFAOYSA-N 3-fluoropyridine-2-carbaldehyde Chemical compound FC1=CC=CN=C1C=O OZIMPUNGBUYCSP-UHFFFAOYSA-N 0.000 description 2
- JDYVLWWFVYNMTN-UHFFFAOYSA-N 3-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=CN=C1C=O JDYVLWWFVYNMTN-UHFFFAOYSA-N 0.000 description 2
- UAKMHSRHDUBNJR-UHFFFAOYSA-N 4-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=NC(C=O)=C1 UAKMHSRHDUBNJR-UHFFFAOYSA-N 0.000 description 2
- IACCXWQKIQUVFQ-UHFFFAOYSA-N 5-fluoropyridine-2-carbaldehyde Chemical compound FC1=CC=C(C=O)N=C1 IACCXWQKIQUVFQ-UHFFFAOYSA-N 0.000 description 2
- SARODJOLCPBJHK-UHFFFAOYSA-N 5-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=C(C=O)N=C1 SARODJOLCPBJHK-UHFFFAOYSA-N 0.000 description 2
- YDNWTNODZDSPNZ-UHFFFAOYSA-N 6-methoxypyridine-2-carbaldehyde Chemical compound COC1=CC=CC(C=O)=N1 YDNWTNODZDSPNZ-UHFFFAOYSA-N 0.000 description 2
- AHISYUZBWDSPQL-UHFFFAOYSA-N 6-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=CC(C=O)=N1 AHISYUZBWDSPQL-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- 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
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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)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Pyridine Compounds (AREA)
Abstract
Titanium iminopyridine complex, preparation method thereof and application thereof in preparation of conjugated diene-ethylene copolymer. The present invention belongs to the field of polymer synthesis. The invention aims to solve the technical problem that the conventional catalyst for olefin homopolymerization has low polymerization efficiency on conjugated diene. Under the anhydrous and anaerobic condition, adding a main catalyst, a solvent, a cocatalyst, conjugated diene monomer and ethylene monomer into a reaction vessel, carrying out polymerization reaction, adding a quenching agent and an anti-aging agent after the reaction is finished, washing, and vacuum drying to obtain the conjugated diene-ethylene copolymer with a high cis-1,4 structure, wherein the main catalyst is an imine pyridine titanium complex, and the number average molecular weight of the obtained conjugated diene-ethylene copolymer with the high cis-1,4 structure is 1 multiplied by 10 5 g/mol～10×10 5 The g/mol, the molecular weight distribution is 3.0-7.0, the proportion of conjugated diene in the copolymer is 60-99%, the proportion of trans-1,4 structure is 1-15%, the proportion of cis-1,4 structure is 85-99%, and the insertion rate of ethylene monomer is 1-40%.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to an imine titanium pyridine complex, a preparation method thereof and application thereof in preparation of conjugated diene-ethylene copolymer.
Background
Plastics and rubber are the most widely used synthetic polymers, penetrating every corner of our lives, but are almost impossible to biodegrade due to their nature, known as "white" and "black" contaminations. In the foreseeable future, how to effectively combine plastics and rubber to produce high-performance materials, meeting the requirements of all aspects, simplifying the recycling process is a focus of constant attention. At the same time, the price is increased by 3 times due to the reduced yield of conjugated diene, and the combination of plastic and rubber is attractive and urgent at any time from the industrial point of view.
The study of the polymerization behavior of purely conjugated olefins has been increasingly limited, and in certain fields, more requirements are placed on the properties thereof, such as rigidity, tensile strength, toughness, etc. Copolymerization of ethylene with conjugated olefins is a hotspot and difficulty in the field of new rubber materials that have been studied. For example: ethylene is the most abundant monomer, while butadiene is a byproduct of ethylene refining, both of which are used to make the most common polyethylene plastics and polybutene rubbers. The hard polyethylene units are combined into a soft butadiene (isoprene) main chain, so that a molecular-grade hybrid material is hopeful to be obtained, and due to the difference of microstructures, new materials with different performances can be prepared by copolymerization of the materials, and the comprehensive performance of the polymer is greatly improved, and the use strength, impact resistance, wear resistance, chemical solvent resistance and the like are greatly improved. At the same time, it is possible to excellently overcome the drawbacks of polybutadiene (isoprene) rubber while imparting new special properties thereto. Therefore, the problem of high-efficiency controllable copolymerization of ethylene and conjugated olefin is solved, not only can bulk monomers such as ethylene, butadiene, isoprene and the like be effectively utilized to synthesize high-performance low-cost materials, but also functionalized polyolefin can be simply and efficiently obtained through double bond reaction. However, due to the inherent polymerization activity and mechanism of the two monomers, at the same time, conjugated dienes (butadiene, isoprene) often form stable allyl intermediates with the catalyst to poison the catalyst, occupying two coordination sites of the catalytic species to terminate the polymerization. Most catalysts used in olefin homo-polymerization are therefore very challenging processes for the polymerization of conjugated dienes where the copolymerization of mono-alpha-olefins (ethylene, propylene) with conjugated dienes (butadiene, isoprene) is inefficient.
Disclosure of Invention
The invention aims to solve the technical problem that the conventional catalyst for olefin homopolymerization reaction has low polymerization reaction efficiency on conjugated diene, and provides an imine titanium pyridine complex, a preparation method thereof and application thereof in preparation of conjugated diene-ethylene copolymer.
The imine pyridine titanium complex has a structure shown in a general formula I:
wherein R is 1 、R 2 、R 3 、R 4 Is one of methyl, ethyl, propyl, isopropyl, fluorine atom, chlorine atom, methoxy and quinoline; x is a sulfur atom or an oxygen atom.
Further defined, when X is a sulfur atom, the specific structure of the titanium iminopyridine complex is one of the following structural formulas:
further defined, when X is an oxygen atom, the specific structure of the titanium iminopyridine complex is one of the following structural formulas:
the preparation method of the imine pyridine titanium complex comprises the following steps:
mixing an imine pyridine ligand and titanium tetrachloride in an equimolar ratio in methylene dichloride at room temperature, reacting overnight, and filtering, washing and pumping to obtain an imine pyridine titanium complex, wherein the imine pyridine ligand has a structural general formula:
wherein R is 1 、R 2 、R 3 、R 4 Is one of methyl, ethyl, propyl, isopropyl, fluorine atom, chlorine atom, methoxy and quinoline; x is a sulfur atom or an oxygen atom.
Further defined, the specific structure of the imine pyridine ligand is one of the following structural formulas:
the preparation method of the conjugated diene-ethylene copolymer comprises the following steps:
in anhydrous and anaerobic stripsUnder the condition of the piece, adding a main catalyst, a solvent, a cocatalyst, conjugated diene monomer and ethylene monomer into a reaction vessel according to any sequence, carrying out polymerization reaction for 1-24 h at 0-100 ℃, adding a quenching agent and an anti-aging agent after the reaction is finished, washing and drying in vacuum to obtain the conjugated diene-ethylene copolymer with a high cis-1,4 structure, wherein the main catalyst is an imine pyridine titanium complex, and the number average molecular weight of the obtained conjugated diene-ethylene copolymer with the high cis-1,4 structure is 1 multiplied by 10 5 g/mol～10×10 5 The g/mol, the molecular weight distribution is 3.0-7.0, the proportion of conjugated diene in the copolymer is 60-99%, the proportion of trans-1,4 structure is 1-15%, the proportion of cis-1,4 structure is 85-99%, and the insertion rate of ethylene monomer is 1-40%.
Further defined, the cocatalyst is one of Methylaluminoxane (MAO), modified aluminoxane (MMAO), and dried aluminoxane (DMAO); the structural general formula of the Methylaluminoxane (MAO) is
Wherein n is a natural number of 4-40, the solvent is one or a mixture of several of toluene, paraxylene, normal hexane, cyclohexane, petroleum ether, pentane, methylene dichloride, tetrahydrofuran and hydrogenated gasoline according to any ratio, the conjugated diene monomer is butadiene or isoprene, when the conjugated diene monomer is butadiene, the butadiene exists in the form of toluene solution of butadiene, the concentration of the butadiene in the toluene solution of butadiene is 0.2 g/mL-0.3 g/mL, and the volume ratio of the solvent to the conjugated diene monomer is (1-10): 1, wherein the molar ratio of the conjugated diene monomer to the titanium element in the titanium imine pyridine complex is (2000-10000): 1, the molar ratio of the aluminum element in the cocatalyst to the titanium element in the titanium picoline imine complex is (100-2000): 1, wherein the amount of the ethylene monomer is 1atm to 50atm based on the pressure of the ethylene monomer in a reaction vessel, the anti-aging agent is an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol, the mass fraction of the 2, 6-di-tert-butyl-4-methylphenol is 1%, the volume ratio of the anti-aging agent to the solvent is 1:5, the quenching agent is a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1), and the quenching agent comprises the following components The volume ratio of the agent to the solvent was 1:2.
Further defined, the polymerization is carried out at 25 to 75℃for 1 to 4 hours.
Further defined, the molar ratio of conjugated diene monomer to titanium element in the titanium iminopyridine complex is 2000:1, the molar ratio of aluminum element in the cocatalyst to titanium element in the main catalyst is 1000:1, polymerization at 25℃for 2h.
Further defined, the resulting high cis-1,4 structure conjugated diene-ethylene copolymer is used to prepare high performance rubber.
Compared with the prior art, the invention has the remarkable effects that:
(1) The microstructure of the conjugated diene and ethylene copolymer prepared by the invention can be regulated and controlled by changing the steric hindrance and the electronic effect of the main catalyst.
(2) The copolymer of conjugated diene and ethylene prepared by the invention has flexible polybutadiene sequence and harder polyethylene sequence, and has great potential in the field of rubber products with ageing resistance and low temperature resistance.
(3) The invention uses a titanium complex/methylaluminoxane two-component catalytic system to successfully catalyze the copolymerization of ethylene and butadiene (isoprene), and compared with noble metals used in the background introduction, the invention has lower price and is environment-friendly.
Drawings
FIG. 1 is a hydrogen spectrum of a polymer obtained in example 19;
FIG. 2 is a carbon spectrum of the polymer obtained in example 19;
FIG. 3 is a GPC chart of a polymer obtained in example 19.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Preparation of titanium iminopyridine complexes of the formulae II to X and II' to X
Example 1: the preparation method of the imine pyridine titanium complex shown in the formula II comprises the following steps:
preparing an iminopyridine ligand shown in a formula II: adding a 4A molecular sieve into a 100mL dry reaction bottle, baking for 15 minutes, sequentially adding redistilled methylene chloride (40 mL), 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and pyridine-2-formaldehyde (0.8 g,8.2mmol,1 equiv.) under an argon atmosphere, reacting for 10 hours at room temperature, detecting that the reaction of a reaction aldehyde substrate is complete by a TLC plate, namely, indicating that the reaction is finished, and then filtering, concentrating under reduced pressure and vacuumizing the reaction system to obtain yellow solid (1.6 g, yield: 85%) which is an imine pyridine ligand of the formula II;
Preparing an imine titanium pyridine complex shown in a formula II: a100 mL dry reaction flask was prepared, potassium hydride (93.5 mg,2.3mmol,1 equiv.) and 10mL redistilled tetrahydrofuran were sequentially added in a glove box, a solution of the iminopyridine ligand of formula II (500 mg,2.3mmol,1 equiv.) was slowly added at-78deg.C, then reacted for 4 hours at room temperature, the tetrahydrofuran was evacuated, and then 30mL dichloromethane and anhydrous TiCl at an equimolar ratio to the iminopyridine ligand of formula II were continuously added to the above reaction flask in the glove box 4 (442 mg,2.3mmol,1 equiv.) stirring overnight at room temperature, after completion of the reaction, the dichloromethane was dried under vacuum, washed 3 times with 60mL of dry n-hexane, and dried under vacuum to constant weight to give 754mg of a green solid, i.e., the titanium iminopyridine complex of formula II (yield: 90%).
Mass spectrometry: c (C) 12 H 9 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 367.53; actual measurement value: 367.50.
elemental analysis: c (C) 12 H 9 Cl 3 N 2 OTi: theoretical value: c,39.22%; h,2.47%; n,7.62%; actual measurement value: c,39.20%; h,2.50%; n,7.67%.
Example 2: the preparation method of the imine pyridine titanium complex shown in the formula III is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula III, and the starting materials for the preparation of the imine pyridine ligand of formula III were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 3-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 381.52; actual measurement value: 381.50.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,40.93%; h,2.91%; n,7.34%; actual measurement value: c,40.95%; h,2.93%; n,7.30%.
Example 3: the preparation method of the imine pyridine titanium complex shown in the formula IV is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula IV, and starting materials for the preparation of the imine pyridine ligand of formula IV were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 4-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 381.52; actual measurement value: 381.49.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,40.93%; h,2.91%; n,7.34%; actual measurement value: c,40.97%; h,2.90%; n,7.36%.
Example 4: the preparation method of the imine pyridine titanium complex shown in the formula V is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula V, and the starting materials for the preparation of the imine pyridine ligand of formula V were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 5-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 381.52; actual measurement value: 381.42.
Elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,40.93%;h,2.91%; n,7.34%; actual measurement value: c,40.91%; h,2.95%; n,7.33%.
Example 5: the preparation method of the titanium picolinate complex shown in the formula VI is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula VI, and starting materials for the preparation of the imine pyridine ligand of formula VI were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 6-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 381.52; actual measurement value: 381.44.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,40.93%; h,2.91%; n,7.34%; actual measurement value: c,40.95%; h,2.93%; n,7.30%.
Example 6: the preparation method of the titanium picolinate complex shown in the formula VII is the same as that of example 1, except that: the ligand used was an imine pyridine ligand of formula VII, and starting materials for the preparation of the imine pyridine ligand of formula VII were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 3-fluoropyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 12 H 8 Cl 3 FN 2 OTi[M-Cl] + Theoretical value: 385.49; actual measurement value: 385.45.
elemental analysis: c (C) 12 H 8 Cl 3 FN 2 OTi: theoretical value: c,37.39%; h,2.09%; n,7.27%; actual measurement value: c,37.42%; h,2.11%; n,7.30%.
Example 7: the preparation method of the imine titanium pyridine complex shown in the formula VIII is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula VIII, and starting materials for the preparation of the imine pyridine ligand of formula VIII were 2-aminothiophenol (1.0 g,8.2mmol,1 equiv.) and 5-fluoropyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 12 H 8 Cl 3 FN 2 OTi[M-Cl] + Theoretical value: 385.49; actual measurement value: 385.43.
elemental analysis: c (C) 12 H 8 Cl 3 FN 2 OTi: theoretical value: c,37.39%; h,2.09%; n,7.27%; actual measurement value: c,37.41%; h,2.07%; n,7.31%.
Example 8: the preparation method of the titanium picolinate complex shown in the formula IX is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula IX, and starting materials for the preparation of the imine pyridine ligand of formula IX were 2-aminothiophenol (0.9 g,7.3mmol,1 equiv.) and 6-methoxypyridine-2-carbaldehyde (1.0 g,7.3mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 O 2 Ti[M-Cl] + Theoretical value: 397.52; actual measurement value: 397.50.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 O 2 Ti: theoretical value: c,39.38%; h,2.79%; n,7.05%; actual measurement value: c,39.40%; h,2.80%; n,7.07%.
Example 9: the preparation method of the titanium picolinate complex represented by formula X is the same as in example 1, except that: the ligand used was an imine pyridine ligand of formula X, and the starting materials for the preparation of the imine pyridine ligand of formula X were 2-aminothiophenol (0.8 g,6.4mmol,1 equiv.) and quinoline pyridine-2-carbaldehyde (1.0 g,6.4mmol,1 equiv.).
Mass spectrometry: c (C) 16 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 417.56; actual measurement value: 417.55.
elemental analysis: c (C) 16 H 11 Cl 3 N 2 OTi: theoretical value: c,46.02%; h,2.66%; n,6.71%; actual measurement value: c,46.00%; h,2.64%; n,6.69%.
Example 10: the preparation method of the titanium picolinate complex shown in the formula II' is the same as that of the example 1, except that: the ligand used was an imine pyridine ligand of formula II 'and starting materials for the preparation of the imine pyridine ligand of formula II' were 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and pyridine-2-carbaldehyde (0.8 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 12 H 9 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 351.43; actual measurement value: 351.40.
elemental analysis: c (C) 12 H 9 Cl 3 N 2 OTi: theoretical value: c,41.01%; h,2.58%; n,7.97%; actual measurement value: c,39.98%; h,2.55%; n,7.91%.
Example 11: the preparation method of the titanium picolinate complex shown in the formula III' is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula III 'and starting materials for the preparation of the imine pyridine ligand of formula III' were 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 3-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 365.46; actual measurement value: 365.44.
Elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,42.72%; h,3.03%; n,7.67%; actual measurement value: c,42.70%; h,3.00%; n,7.64%.
Example 12: the preparation method of the titanium picolinate complex shown in the formula IV' is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula IV 'and starting materials for the preparation of the imine pyridine ligand of formula IV' were 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 4-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 365.46; actual measurement value: 365.43.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,42.72%; h,3.03%; n,7.67%; actual measurement value: c,42.69%; h,2.99%; n,7.63%.
Example 13: the preparation method of the titanium picolinate complex represented by formula V' is the same as in example 1, except that: the ligand used was an imine pyridine ligand of formula V 'and starting materials for the preparation of the imine pyridine ligand of formula V' were 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 5-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 365.46; actual measurement value: 365.42.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,42.72%; h,3.03%; n,7.67%; actual measurement value: c,42.68%; h,2.98%; n,7.62%.
Example 14: the preparation method of the titanium picolinate complex shown in the formula VI' is the same as that of the example 1, and the only difference is that: the ligand used was an imine pyridine ligand of formula VI 'starting from 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 6-methylpyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.) in the preparation of the imine pyridine ligand of formula VI'.
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 365.46; actual measurement value: 365.41.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 OTi: theoretical value: c,42.72%; h,3.03%; n,7.67%; actual measurement value: c,42.72%; h,2.97%; n,7.65%.
Example 15: the preparation method of the titanium picolinate complex represented by formula VII' is the same as in example 1, except that: the ligand used was an imine pyridine ligand of the formula VII 'starting from 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 3-fluoropyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.) in the preparation of the imine pyridine ligand of the formula VII'.
Mass spectrometry: c (C) 12 H 8 Cl 3 FN 2 OTi[M-Cl] + Theoretical value: 369.42; actual measurement value: 369.40.
elemental analysis: c (C) 12 H 8 Cl 3 FN 2 OTi: theoretical value: c,39.02%; h,2.18%; n,7.58%; actual measurement value: c,38.99%; h,2.16%; n,7.55%.
Example 16: the preparation method of the imine titanium pyridine complex shown in the formula VIII' is the same as that of the example 1, and only the difference is that: the ligand used was an imine pyridine ligand of formula VIII 'and starting materials for the preparation of the imine pyridine ligand of formula VIII' were 2-aminophenol (0.9 g,8.2mmol,1 equiv.) and 5-fluoropyridine-2-carbaldehyde (1.0 g,8.2mmol,1 equiv.).
Mass spectrometry: c (C) 12 H 8 Cl 3 FN 2 OTi[M-Cl] + Theoretical value: 369.42; actual measurement value: 369.42.
elemental analysis: c (C) 12 H 8 Cl 3 FN 2 OTi: theoretical value: c,39.02%; h,2.18%; n,7.58%; actual measurement value: c,39.01%; h,2.17%; n,7.56%.
Example 17: the preparation method of the titanium picolinate complex represented by formula IX' is the same as in example 1, except that: the ligand used was an imine pyridine ligand of the formula IX ', and starting materials for the preparation of the imine pyridine ligand of the formula IX' were 2-aminophenol (0.8 g,7.3mmol,1 equiv.) and 6-methoxypyridine-2-carbaldehyde (1.0 g,7.3mmol,1 equiv.).
Mass spectrometry: c (C) 13 H 11 Cl 3 N 2 O 2 Ti[M-Cl] + Theoretical value: 381.46; actual measurement value: 381.45.
elemental analysis: c (C) 13 H 11 Cl 3 N 2 O 2 Ti: theoretical value: c,40.93%; h,2.91%; n,7.34%; actual measurement value: c,40.92%; h,2.89%; n,7.30%.
Example 18: the preparation method of the titanium picolinate complex represented by formula X' is the same as in example 1, except that: the ligand used was an imine pyridine ligand of formula X 'and starting materials for the preparation of the imine pyridine ligand of formula X' were 2-aminophenol (0.7 g,6.4mmol,1 equiv.) and quinoline pyridine-2-carbaldehyde (1.0 g,6.4mmol,1 equiv.).
Mass spectrometry: c (C) 16 H 11 Cl 3 N 2 OTi[M-Cl] + Theoretical value: 401.49; actual measurement value: 401.48.
Elemental analysis: c (C) 16 H 11 Cl 3 N 2 OTi: theoretical value: c,47.87%; h2.76%; n,6.98%; actual measurement value: c,47.86%; h,2.74%; n,6.97%.
Preparation of conjugated diene-ethylene copolymer with high cis-1,4 structure
Example 19: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 1 (formula II), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.16X10 4 g/mol.h, number average molecular weight (M n )：5.3×10 5 Molecular weight distribution (PDI): 3.5, 9% of the trans-1,4 structure of butadiene, 91% of the cis-1,4 structure of butadiene in the copolymer, and ethylene monomer insertion rate: 16%.
Example 20: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.8mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 2 (formula III), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.11X10.times.10 4 g/mol.h. Number average molecular weight (M) n )：7.8×10 5 Molecular weight distribution (PDI): 4.5, the trans-1,4 structure of butadiene in the copolymer accounts for 8%, the cis-1,4 structure accounts for 92%, and the ethylene monomer insertion rate is as follows: 20%.
Example 21: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.8mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 3 (formula IV), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (5 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.05X10 4 g/mol.h. Number average molecular weight (M) n )：8.7×10 5 Molecular weight distribution (PDI): 4.4, 11% trans-1,4 structure of butadiene, 89% cis-1,4 structure of butadiene in the copolymer, ethylene monomer insertion rate: 23%.
Example 22: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.8mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 4 (formula V), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, and the reaction was carried out at 25℃for 2 hours, and 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.94×10 4 g/mol.h. Number average molecular weight (M) n )：8.3×10 5 Molecular weight distribution (PDI): 5.5. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomer insertion rate is as follows: 22%.
Example 23: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.8mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 5 (formula VI), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.21×10 4 g/mol.h. Number average molecular weight (M) n )：5.5×10 5 Molecular weight distribution (PDI): 5.6. the trans-1,4 structure of butadiene in the copolymer accounts for 7%, the cis-1,4 structure accounts for 93%, and the ethylene monomer insertion rate is as follows: 19%.
Example 24: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.9mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 6 (formula VII), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.73X10 4 g/mol.h. Number average molecular weight (M) n )：6.7×10 5 Molecular weight distribution (PDI): 4.7. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomer insertion rate is as follows: 10%.
Example 25: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.9mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 7 (formula VIII), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (20 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.84×10 4 g/mol.h. Number average molecular weight (M) n )：5.8×10 5 Molecular weight distribution (PDI): 6.0. the trans-1,4 structure of butadiene in the copolymer accounts for 6%, the cis-1,4 structure accounts for 94%, and the ethylene monomer insertion rate is as follows: 25%.
Example 26: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 4.0mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 8 (formula IX), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.89×10 4 g/mol.h. Number average molecular weight (M) n )：5.9×10 5 Molecular weight distribution (PDI): 4.5. the trans-1,4 structure of butadiene in the copolymer accounts for 12%, the cis-1,4 structure accounts for 88%, and the ethylene monomer insertion rate is as follows: 25%.
Example 27: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 4.2mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 9 (formula X), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.94×10 4 g/mol.h. Number average molecular weight (M) n )：7.2×10 5 Molecular weight distribution (PDI): 3.9. the trans-1,4 structure of butadiene in the copolymer accounts for 8%, the cis-1,4 structure accounts for 92%, and the ethylene monomer insertion rate is as follows: 30%.
Example 28: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.5mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 10 (formula II'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 3.84×10 4 g/mol.h. Number average molecular weight (M) n )：7.3×10 5 Molecular weight distribution (PDI): 6.7. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomer insertion rate is as follows: 20%.
Example 29: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 11 (formula III'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.00×10 4 g/mol.h. Number average molecular weight (M) n )：6.1×10 5 Molecular weight distribution (PDI): 5.5. trans-1,4 structure of butadiene in copolymer6%, 94% cis-1,4 structure, ethylene monomer insertion rate: 15%.
Example 30: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 12 (formula IV') was sequentially added to a 50mL dry reaction flask with 10mL of dry toluene (1000 eq, 10000. Mu. Mol), the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, and the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature to obtain a conjugated diene-ethylene copolymer having a high cis-1,4 structure.
Polymerization activity: 4.38X10 4 g/mol.h. Number average molecular weight (M) n )：5.9×10 5 Molecular weight distribution (PDI): 6.5. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomer insertion rate is as follows: 28%.
Example 31: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 13 (formula V'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, and the reaction was carried out at 25℃for 2 hours, and 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, and the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature to obtain a conjugated diene-ethylene copolymer having a high cis-1,4 structure.
Polymerization activity: 4.32X10 4 g/mol.h. Number average molecular weight (M) n )：5.1×10 5 Molecular weight distribution (PDI): 4.2. the trans-1,4 structure of butadiene in the copolymer accounts for 8%, the cis-1,4 structure accounts for 92%, and the ethylene monomer insertion rate is as follows: 22%.
Example 32: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 14 (formula VI') was quenched with dry methylaluminoxane 580mg (1000 eq, 10000. Mu. Mol), 10mL of dry toluene was sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (30 atm) was introduced, and the reaction was carried out at 25℃for 2 hours, and 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.27×10 4 g/mol.h. Number average molecular weight (M) n )：6.6×10 5 Molecular weight distribution (PDI): 4.8. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomer insertion rate is as follows: 19%.
Example 33: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 15 (formula VII'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.21×10 4 g/mol.h. Number average molecular weight (M) n )：7.7×10 5 Molecular weight distribution (PDI): 5.3. the trans-1,4 structure of butadiene in the copolymer accounts for 7%, the cis-1,4 structure accounts for 93%, and the ethylene monomer insertion rate is as follows: 12%.
Example 34: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 16 (formula VIII'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.43×10 4 g/mol.h. Number average molecular weight (M) n )：6.7×10 5 Molecular weight distribution (PDI): 4.1. the trans-1,4 structure of butadiene in the copolymer accounts for 6%, the cis-1,4 structure accounts for 94%, and the ethylene monomer insertion rate is as follows: 14%.
Example 35: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 4.0mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 17 (formula IX'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, and the reaction was carried out at 25℃for 2 hours, and 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, and the obtained solid was washed 3 times with ethanol and vacuum-dried at room temperature to constant weight, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.27×10 4 g/mol.h. Number average molecular weight (M) n )：7.7×10 5 Molecular weight distribution (PDI): 3.9. the trans-1,4 structure of butadiene in the copolymer accounts for 8%, the cis-1,4 structure accounts for 92%, and the ethylene monomer insertion rate is as follows: 18%.
Example 36: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 4.2mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 18 (formula X'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added to a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced, the reaction was carried out at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.21×10 4 g/mol.h. Number average molecular weight (M) n )：7.3×10 5 Molecular weight distribution (PDI): 4.4. the trans-1,4 structure of butadiene in the copolymer accounts for 10%, the cis-1,4 structure accounts for 90%, and the ethylene monomer insertion rate is as follows: 17%.
Example 37: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 16 (formula VIII'), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, at a concentration of 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 1 hour, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol, and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.21×10 4 g/mol.h. Number average molecular weight (M) n )：6.2×10 5 Molecular weight distribution (PDI): 4.2. the trans-1,4 structure of butadiene in the copolymer accounts for 8%, the cis-1,4 structure accounts for 92%, and the ethylene monomer insertion rate is as follows: 15%.
Example 38: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 1 (formula II), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 8mL (4000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.86×10 4 g/mol.h. Activity: x 10 4 g/mol.h, number average molecular weight (M n )：6.3×10 5 Molecular weight distribution (PDI): 3.9, the trans-1,4 structure of butadiene in the copolymer accounts for 7%, the cis-1,4 structure accounts for 93%, and the ethylene monomer insertion rate: 18%.
Example 39: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 1 (formula II), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane, 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 2mL (2000 eq, 20000. Mu. Mol) of isoprene was added under argon atmosphere, ethylene gas (2 atm) was introduced, and the reaction was carried out at 25℃for 2 hours, and 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction to quench, the obtained solid was washed 3 times with ethanol, and vacuum-dried at room temperature to constant weight, to obtain a conjugated diene-ethylene copolymer having a high cis-1,4 structure.
Polymerization activity: 4.00×10 4 g/mol.h, number average molecular weight (M n )：6.0×10 5 Molecular weight distribution (PDI): 3.9, 11% of the trans-1,4 structure of isoprene in the copolymer, 89% of the cis-1,4 structure, ethylene monomer insertion rate: 13%.
Example 40: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
in a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 12 (formula IV') was sequentially added to a 50mL dry reaction flask with 10mL of dry toluene and 290mg (500 eq, 5000. Mu. Mol) of dry methylaluminoxane, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 25℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.10X10 4 g/mol.h. Number average molecular weight (M) n )：6.4×10 5 Molecular weight distribution (PDI): 5.7. the trans-1,4 structure of butadiene in the copolymer accounts for 9%, the cis-1,4 structure accounts for 91%, and the ethylene monomerInsertion rate: 25%.
Example 41: the preparation method of the conjugated diene-ethylene copolymer of this example is carried out according to the following steps:
In a glove box, 3.7mg (1 eq, 10. Mu. Mol) of the titanium iminopyridine complex shown in example 1 (formula II), 580mg (1000 eq, 10000. Mu. Mol) of dry methylaluminoxane and 10mL of dry toluene were sequentially added into a 50mL dry reaction flask, the reaction vessel was transferred to the outside of the glove box, 4mL (2000 eq, 0.27 g/mL) of a toluene solution of butadiene was added under an argon atmosphere, ethylene gas (2 atm) was introduced and reacted at 50℃for 2 hours, 5mL of a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1) and 2mL of an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methylphenol: 1 wt%) were added at the end of the reaction, the obtained solid was washed 3 times with ethanol and vacuum-dried to constant weight at room temperature, to obtain a conjugated diene-ethylene copolymer of high cis-1,4 structure.
Polymerization activity: 4.67×10 4 g/mol.h, number average molecular weight (M n )：5.7×10 5 Molecular weight distribution (PDI): 3.4, the trans-1,4 structure of butadiene in the copolymer accounts for 6%, the cis-1,4 structure accounts for 94%, and the ethylene monomer insertion rate is as follows: 19%.
Claims (5)
1. The application of the imine pyridine titanium complex in preparing conjugated diene-ethylene copolymer is characterized by comprising the following specific steps:
under the anhydrous and anaerobic condition, adding a main catalyst, a solvent, a cocatalyst, conjugated diene monomer and ethylene monomer into a reaction vessel according to any sequence, carrying out polymerization reaction for 1-24 h at 0-100 ℃, adding a quenching agent and an anti-aging agent after the reaction is finished, washing and drying in vacuum to obtain the conjugated diene-ethylene copolymer with a high cis-1,4 structure, wherein the main catalyst is an imine pyridine titanium complex, and the number average molecular weight of the conjugated diene-ethylene copolymer with the high cis-1,4 structure is 1 multiplied by 10 5 g/mol~10×10 5 g/mol, molecular weight distribution of 3.0-7.0, proportion of conjugated diene in copolymer of 60-99%, proportion of trans-1,4 structure of 1-15%, proportion of cis-1,4 structure of 85-99%, and insertion rate of ethylene monomer of1% -40%, wherein the specific structure of the titanium picolinate complex is one of the following structures:
2. the use of a titanium iminopyridine complex according to claim 1 for the preparation of a conjugated diene-ethylene copolymer, wherein said cocatalyst is one of MAO, MMAO, DMAO; the structural general formula of the MAO is
Wherein n is a natural number of 4-40, the solvent is one or a mixture of more of toluene, paraxylene, normal hexane, cyclohexane, petroleum ether, pentane, methylene dichloride, tetrahydrofuran and hydrogenated gasoline, the conjugated diene monomer is butadiene or isoprene, when the conjugated diene monomer is butadiene, the butadiene exists in the form of toluene solution of butadiene, the concentration of butadiene in the toluene solution of butadiene is 0.2 g/mL-0.3 g/mL, and the volume ratio of the solvent to the conjugated diene monomer is (1-10): 1, wherein the molar ratio of the conjugated diene monomer to titanium element in the titanium imine pyridine complex is (2000-10000): 1, the molar ratio of the aluminum element in the cocatalyst to the titanium element in the titanium picolinate complex is (100-2000): the amount of the ethylene monomer is 1 atm to 50 atm based on the pressure of the ethylene monomer in a reaction vessel, the anti-aging agent is an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol, the mass fraction of the 2, 6-di-tert-butyl-4-methylphenol is 1%, the volume ratio of the anti-aging agent to the solvent is 1:5, the quenching agent is a mixed solution of methanol and concentrated hydrochloric acid (v/v=50:1), and the volume ratio of the quenching agent to the solvent is 1:2.
3. The use of an imine titanium pyridine complex according to claim 1 in the preparation of conjugated diene-ethylene copolymer, characterized in that the polymerization is carried out for 1 to 4 hours at 25 to 75 ℃.
4. Use of a titanium iminopyridine complex according to claim 2 or 3 for the preparation of a conjugated diene-ethylene copolymer, characterized in that the molar ratio of conjugated diene monomer to titanium element in the titanium iminopyridine complex is 2000:1, the molar ratio of aluminum element in the cocatalyst to titanium element in the main catalyst is 1000:1, polymerization 2 h at 25 ℃.
5. The use of a titanium iminopyridine complex according to claim 1 for the preparation of conjugated diene-ethylene copolymers, characterized in that the resulting high cis-1,4 structure conjugated diene-ethylene copolymers are used for the preparation of high performance rubbers.
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