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WO2019205309A1 - Complexe métallique catalytique de pyridine-imine de fer ou de cobalt, son procédé de préparation et son application - Google Patents

Complexe métallique catalytique de pyridine-imine de fer ou de cobalt, son procédé de préparation et son application Download PDF

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Publication number
WO2019205309A1
WO2019205309A1 PCT/CN2018/096292 CN2018096292W WO2019205309A1 WO 2019205309 A1 WO2019205309 A1 WO 2019205309A1 CN 2018096292 W CN2018096292 W CN 2018096292W WO 2019205309 A1 WO2019205309 A1 WO 2019205309A1
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Prior art keywords
metal complex
cobalt metal
iron
complex catalyst
mmol
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English (en)
Chinese (zh)
Inventor
王庆刚
王晓武
王亮
赵梦梦
咸漠
张献辉
朱广乾
荆楚杨
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Priority claimed from CN201810399964.6A external-priority patent/CN108658850A/zh
Priority claimed from CN201810399947.2A external-priority patent/CN108641026B/zh
Priority claimed from CN201810400881.4A external-priority patent/CN108586641B/zh
Priority claimed from CN201810400838.8A external-priority patent/CN108530571B/zh
Priority claimed from CN201810400796.8A external-priority patent/CN108659055B/zh
Application filed by Qingdao Institute of Bioenergy and Bioprocess Technology of CAS filed Critical Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
Publication of WO2019205309A1 publication Critical patent/WO2019205309A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • 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
    • C08F136/08—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof

Definitions

  • the invention relates to the field of chemical synthesis, in particular to a pyridinium-based iron or cobalt metal complex catalyst and a preparation method and application thereof.
  • olefin polymerization catalysts are of great importance for the development of the polyolefin industry.
  • Conjugated diolefins (butadiene, isoprene, 1,3-pentadiene, etc.) are another important type of olefin monomer different from alpha-olefins and styrene, which have two conjugated double bonds. It can be 1,4-addition polymerization to give cis-1,4- or vice versa.
  • the polymer can also be obtained by a 1,2- or 3,4-addition reaction through a 1,2- or 3,4-structure.
  • the microscopic chain structure of polyisoprene is as follows:
  • Isoprene rubber is one of the most important polyconjugated dienes obtained from isoprene monomers under polymerization conditions. Due to its identical molecular structure (high cis-1,4 content) and physical properties to natural rubber, it is commonly referred to as synthetic natural rubber. Synthetic natural rubber has good raw rubber strength, basic viscosity, anti-aging properties and resilience. It can replace natural rubber in automotive tires, hoses, sponges, adhesives, conveyor belts, medical adhesives and other materials.
  • Titanium catalysts catalyze the conjugated diene system mainly in titanium catalysts formed by mono-, di- and a few post-ligand ligands.
  • the titanium catalyst has the characteristics of high activity and wide molecular weight distribution.
  • the rare earth catalyst has the characteristics of high activity, narrow molecular weight distribution and good selectivity to conjugated diene.
  • titanium and rare earth metal catalysts are poorly resistant to polar monomers and do not catalyze the copolymerization of conjugated dienes with polar monomers.
  • titanium and rare earth catalysts have poor tolerance to polar monomers and do not favor the copolymerization of conjugated dienes and polar monomers.
  • the present invention provides a pyridinium-based iron or cobalt metal complex catalyst, and a preparation method and application thereof.
  • the pyridinium-based iron or cobalt metal complex catalyst according to the present invention has a structural formula of any one of the following:
  • M represents a Fe element or a Co element
  • R 1 represents H, CH 3 , a phenyl group, a substituted phenyl group, a biphenyl group or a heterocyclic ring
  • R 2 represents H, CH 3 , an ethyl group or a phenyl group or a cycloalkane
  • R 3 represents H, alkyl, aryl or halogen
  • R 4 represents H, alkyl, alkoxy, aryl, substituted aryl, biphenyl or halogen
  • F is 2-fluoro, 4-fluoro, 4 - any of trifluoromethyl, 2,6-difluoro, 2,4,6-trifluoro.
  • R 2 represents H
  • R 3 is one of H, methyl (Me), isopropyl (ipr), phenyl (Ph), and methoxy (OMe).
  • the structural formula of the pyridinium-based iron or cobalt metal complex catalyst is any one of the following:
  • the invention also provides a preparation method of the above pyridinium-based iron or cobalt metal complex catalyst, which is prepared as follows: the pyridinium ligand and the metal catalyst are dissolved in dichloromethane or tetrahydrofuran, and the reaction is 12- After 48 hours, after purification, a pyridinium-based iron or cobalt metal complex catalyst is obtained, which is FeCl 2 , Fe(OAc) 2 , Fe(acac) 2 , FeCl 3 , CoCl 2 , Co(OAc) 2 Or Co(acac) 2 .
  • the molar ratio of the pyridazolium ligand to the metal catalyst is 1:1.
  • the structural formula of the pyridazolium ligand is any one of the following:
  • the present invention also provides the use of the above pyridinium-based iron or cobalt metal complex catalyst for preparing a conjugated olefin, which is polyisoprene, polybutadiene or isoprene-butyl Diene copolymer.
  • the polyisoprene is prepared by using a pyridinium-based iron or cobalt metal complex catalyst
  • the cocatalyst, the pyridinium-based iron or cobalt metal complex catalyst and the isoprene monomer are dissolved in a solvent.
  • the polymerization reaction is carried out by stirring under an argon atmosphere, and the product polyisoprene is obtained after separation and purification.
  • the reaction system is a two-component reaction system.
  • the molar ratio of the cocatalyst to the pyridinium iron or cobalt metal complex is (5-1000): 1; the monomer isoprene and the pyridinium iron or cobalt metal
  • the molar ratio of the catalyst is (1250-20000): 1; the concentration of the cocatalyst in the solvent is 0.05-2 mol/L.
  • the solvent is one or a mixture of two or more of toluene, hexane, petroleum ether, tetrahydrofuran, dichloromethane, and hydrogenated gasoline.
  • each solvent is Mix in any ratio.
  • the cocatalyst is trialkyl aluminum AlR 3 , methyl aluminoxane MAO, MMAO (modified MAO), Cl 2 AlEt, ClAlEt 2 , sesquiethyl aluminum SEAC, diethylaluminum chloride And one or a mixture of two or more of AlMe 3 , AlEt 3 , and AliBu 3 , and when the catalyst is a mixture of two or more kinds, the catalysts are mixed in an arbitrary ratio, and the MAO structure is Where n is a natural number from 4 to 40.
  • the above-mentioned reaction system for preparing polyisoprene by using a pyridinium-based iron or cobalt metal complex catalyst includes a dealkylating agent, which constitutes a three-component reaction system, and the dealkylation
  • the reagent is one or more of an aluminate or a borate.
  • the borate is [Ph 3 C] + [B(C 6 F 5 ) 4 ] - , [NH 2 Ph 2 ] + [B(C 6 F 5 ) 4 ] - or [NH 2 Me 2 ] + [B(C 6 F 5 ) 4 ] - .
  • the molar ratio of the cocatalyst to the pyridinium iron or cobalt metal complex is (5-1000): 1; the monomer isoprene and the pyridinium iron or cobalt metal
  • the molar ratio of the catalyst is (1250-2500):1, the concentration of the cocatalyst in the solvent is 0.05-2 mol/L; the dealkylating reagent reagent is complexed with pyridinium iron or cobalt metal
  • the molar ratio of the substance is (1-5): 1.
  • the temperature of the polymerization reaction is -40 ° C to 50 ° C, and the reaction time is 1 to 240 minutes.
  • the polymerization temperature is from 0 to 30 °C.
  • the polyisoprene has a molecular weight of 1000-500,000 and a molecular weight distribution of 1.5-8 by using a pyridinium-based iron or cobalt metal complex catalyst; the cis-1,4 structural ratio is 55%-95%, trans- The ratio of 1,4 structure is 90%-98%, and the ratio of 3,4-unit is 5%-45%.
  • the isoprene polymerization catalyst system of the present invention the catalyst used for the preparation of the pyridinium-based iron or cobalt metal complex is simple and easy to obtain, and the cost is low; the isoprene polymerization reaction can be used in the cocatalyst It is also carried out in two components of commercial methyl aluminoxane (MAO) or the like, and may also be carried out in three components containing a dealkylating agent.
  • the overall catalytic isoprene polymerization system has a high reactivity: 3 ⁇ 10 6 - 5 ⁇ 10 8 g. (mol Fe) -1 .h -1 ).
  • the polyisoprene synthesized by catalytic polymerization of the isoprene monomer with the pyridazolium iron or cobalt metal complex of the present invention has a molecular weight of 1000-500000 and a molecular weight distribution of 1.5-8.
  • the cis-1,4 structure ratio is 55%-95%
  • the trans-1,4 structure ratio is 90%-98%
  • the 3,4-unit ratio is 5%-45%.
  • the pyridazolium iron or cobalt metal complex catalyst of the invention has low selectivity and activity to temperature, and high tolerance to industrial isoprene and reagent pure isoprene.
  • the two-component system does not use expensive dealkylation reagents, has lower cost and has good industrial value.
  • the anti-aging agent used in the isoprene polymerization reaction example is 2,6-di-tert-butyl-p-cresol.
  • the structural formula of the catalyst 2 is:
  • the structural formula of the catalyst 76 is:
  • the structural formula of the catalyst 72 is:
  • the structural formula of the catalyst 73 is:
  • the structural formula of the catalyst 74 is:
  • the structural formula of the catalyst 18 is:
  • the structural formula of the catalyst 1 is:
  • the structural formula of the catalyst 42 is:
  • reaction tube 25 mL reaction tube was placed in a glove box, anhydrous FeCl 2 (100.0 mg, 0.80 mmol) was dissolved in 5 mL of dichloromethane, and a solution of the ligand L23 (183.0 mg, 0.80 mmol) in dichloromethane (5 mL) was added dropwise at room temperature. After stirring for 48 h, a large amount of precipitate was precipitated. It was filtered under an argon atmosphere, and the solid was washed with n-hexane (10 mL ⁇ 2), and dried purple complex 42 under vacuum, that is, catalyst 42 was 241 mg, yield: 85%.
  • the structural formula of the catalyst 43 is:
  • reaction tube 25 mL reaction tube was placed in a glove box, anhydrous FeCl 2 (100.0 mg, 0.80 mmol) was dissolved in 5 mL of dichloromethane, and a solution of the ligand L24 (208.5 mg, 0.80 mmol) in dichloromethane (5 mL) was added dropwise at room temperature. After stirring for 48 h, a large amount of precipitate was precipitated. The mixture was filtered under argon atmosphere, and the solid was washed with n-hexane (10 mL ⁇ 2), and dried purple complex 43 under vacuum, that is, catalyst 43 was 240 mg, yield: 78%.
  • the structural formula of the catalyst 44 is:
  • reaction tube 25 mL reaction tube was placed in a glove box, anhydrous FeCl 2 (100.0 mg, 0.80 mmol) was dissolved in 5 mL of dichloromethane, and a solution of ligand L25 (165.9 mg, 0.80 mmol) in dichloromethane (5 mL) was added dropwise at room temperature. After stirring for 48 h, a large amount of precipitate was precipitated. It was filtered under an argon atmosphere, and the solid was washed with n-hexane (10 mL ⁇ 2), and dried purple complex 44 under vacuum, that is, catalyst 44 was 160 mg, yield: 60%.
  • the structural formula of the catalyst 45 is:
  • reaction tube 25 mL reaction tube was placed in a glove box, anhydrous FeCl 2 (100.0 mg, 0.80 mmol) was dissolved in 5 mL of dichloromethane, and a solution of ligand L26 (94.0 mg, 0.40 mmol) in dichloromethane (5 mL) was added dropwise at room temperature. After stirring for 48 h, a large amount of precipitate was precipitated. It was filtered under an argon atmosphere, and the solid was washed with n-hexane (10 mL ⁇ 2), and dried purple complex 45 under vacuum, i.e., catalyst 45 was 128 mg, yield: 66%.
  • the structural formula of the catalyst 64 is:
  • the structural formula of the catalyst 65 is:
  • the structural formula of the catalyst 2 is:
  • the structural formula of the catalyst 67 is:
  • the structural formula of the catalyst 30 is:
  • the structural formula of the catalyst 31 is:
  • the structural formula of the catalyst 32 is:
  • the structural formula of the catalyst 78 is:
  • the structural formula of the catalyst 28 is:
  • the structural formula of the catalyst 34 is:
  • the structural formula of the catalyst 36 is:
  • the structural formula of the catalyst 37 is:
  • the structural formula of the catalyst 38 is:
  • the structural formula of the catalyst 77 is:
  • Example 27 Under a argon atmosphere, 5 mL of anhydrous toluene was sequentially added to a 25 mL Schlenk tube, and trimethylaluminum (4 mmol, 500 eq.), isoprene (2 mL, 20.0 mmol) was added.
  • Example 28 Under a argon atmosphere, 5 mL of anhydrous toluene was sequentially added to a 25 mL Schlenk tube, and triethylaluminum (4 mmol, 500 eq.), isoprene (2 mL, 20.0 mmol) was added.
  • Example 29 Under a argon atmosphere, 5 mL of anhydrous toluene was added in a 25 mL Schlenk tube, and triisobutylaluminum (4 mmol, 500 eq.), isoprene (2 mL, 20.0 mmol) was added.
  • Example 31 Under a argon atmosphere, 5 mL of anhydrous toluene, methylaluminoxane MAO (4 mmol, 500 eq.), and isoprene 2 mL (20.0 mmol) were sequentially added to a 25 mL Schlenk tube.
  • the obtained polymer was washed twice with ethanol and vacuum-dried for 24 hours to obtain an elastomer polymer. Yield: >99%.
  • the GPC test data showed that the number average molecular weight of the polymer was 4.9 ⁇ 10 4 and the polydispersity coefficient was 3.2.
  • the obtained polymer was washed twice with ethanol and vacuum-dried for 24 hours to obtain an elastomer polymer. Yield: >99%.
  • the GPC test data showed that the number average molecular weight of the polymer was 5.4 ⁇ 10 4 and the polydispersity coefficient was 3.2.
  • Example 34 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.8 mmol, 100 eq.), and isoprene 2 mL (20.0 mmol) were sequentially added.
  • Example 35 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.16 mmol, 20 eq.), and isoprene 2 mL (20.0 mmol) were sequentially added.
  • Example 36 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.08 mmol, 10 eq.), and isoprene 2 mL (20.0 mmol) were sequentially added.
  • Example 38 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.8 mmol, 100 eq.), catalyst 76 prepared in Example 2 (3.2) were sequentially added.
  • Example 39 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.1 mmol, 100 eq.), catalyst 76 prepared in Example 2 (0.4) were sequentially added.
  • MAO 0.8 mmol, 2 mL (20 mmol) of isoprene
  • Example 43 Under a argon atmosphere, in a 25 mL Schlenk tube, 5 mL of anhydrous toluene, methylaluminoxane MAO (0.8 mmol, 100 eq.), and isoprene 2 mL (20.0 mmol) were sequentially added.
  • Example 47 Catalyst 76 (3.2 mg, 8 ⁇ mol) prepared in Example 2, 2 mL of anhydrous toluene, AlMe 3 (160 ⁇ mol, 20 equiv.), were sequentially added to a 25 mL Schlenk tube under an argon atmosphere.
  • the GPC test data showed that the number average molecular weight of the polymer was 3.6 ⁇ 10 4 and the polydispersity coefficient was 2.8. The proportion of different structures: cis-1, 4 structure accounted for 57%, 3,4 structure accounted for 43%.
  • Example 48 In a 25 mL Schlenk tube, a catalyst 76 (3.2 mg, 8 ⁇ mol), anhydrous toluene 2 mL, AlEt 3 (160 ⁇ mol, 20 equiv.), and stirred in a 25 mL Schlenk tube were added in an argon atmosphere. 2 min, 2 mL of toluene solution containing [Ph 3 C][B(C 6 F 5 ) 4 ] (7.4 mg, 8 ⁇ mol, 1 equiv.) was added, and after stirring for 2 min, 2 mL (20.0 mmol) of isoprene was added at 25 ° C.
  • the GPC test data showed that the number average molecular weight of the polymer was 1.3 ⁇ 10 4 and the polydispersity coefficient was 4.2.
  • the proportion of different structures cis-1, 4 structure accounted for 57%, 3,4 structure accounted for 43%.
  • Example 49 Under a argon atmosphere, a catalyst 76 (3.2 mg, 8 ⁇ mol), 1 mL of anhydrous toluene, and Al(i-Bu) 3 (160 ⁇ mol,) were sequentially added to a 25 mL Schlenk tube.
  • the GPC test data showed that the number average molecular weight of the polymer was 2.1 ⁇ 10 4 and the polydispersity coefficient was 3.0. The proportion of different structures: cis-1, 4 structure accounted for 61%, 3,4 structure accounted for 39%.
  • Example 50 In a 25 mL Schlenk tube, a catalyst 76 (3.2 mg, 8 ⁇ mol), anhydrous toluene 1 mL, MAO (160 ⁇ mol, 20 equiv.), stirred for 2 min, was added in a 25 mL Schlenk tube under argon atmosphere. 4 mL of toluene solution containing [Ph 3 C][B(C 6 F 5 ) 4 ] (7.4 mg, 8 ⁇ mol, 1 equiv.) was added, and after stirring for 2 min, 2 mL (20.0 mmol) of isoprene was added at 25 ° C.
  • the obtained polymer was washed twice with ethanol and dried in vacuo for 24h to give an elastomer polymer. Yield: >99%.
  • the GPC test data showed that the number average molecular weight of the polymer was 2.4 ⁇ 10 4 and the polydispersity coefficient was 2.6.
  • the proportion of different structures cis-1, 4 structure accounted for 55%, 3,4 structure accounted for 45%.
  • Example 51 Under a argon atmosphere, a catalyst 72 (3.8 mg, 8 ⁇ mol) prepared in Example 3, 1 mL of anhydrous toluene, AlMe 3 (160 ⁇ mol, 20 equiv.), was sequentially added to a 25 mL Schlenk tube.
  • the GPC test data showed that the number average molecular weight of the polymer was 3.5 ⁇ 10 4 and the polydispersity coefficient was 2.4.
  • Example 52 Catalyst 2 (2.6 mg, 8 ⁇ mol) prepared in Example 2, 1 mL of anhydrous toluene, AlMe 3 (160 ⁇ mol, 20 equiv.), were sequentially added to a 25 mL Schlenk tube under an argon atmosphere.
  • the GPC test data showed that the number average molecular weight of the polymer was 5.1 ⁇ 10 4 and the polydispersity coefficient was 3.2. The proportion of different structures: cis-1, 4 structure accounted for 55%, 3,4 structure accounted for 45%.
  • Example 53 Under a argon atmosphere, a catalyst 73 (2.3 mg, 8 ⁇ mol) prepared in Example 4, 1 mL of anhydrous toluene, AlMe 3 (160 ⁇ mol, 20 equiv.), was sequentially added to a 25 mL Schlenk tube.
  • the GPC test data showed that the number average molecular weight of the polymer was 3.0 ⁇ 10 4 and the polydispersity coefficient was 2.8.
  • Example 54 Under a argon atmosphere, a catalyst 72 (2.2 mg, 8 ⁇ mol) prepared in Example 3, 1 mL of anhydrous toluene, AlMe 3 (160 ⁇ mol, 20 equiv.) was sequentially added to a 25 mL Schlenk tube.
  • the GPC test data showed that the number average molecular weight of the polymer was 2.9 ⁇ 10 4 and the polydispersity coefficient was 2.0.
  • Example 55 In a 25 mL Schlenk tube, catalyst 18 (2.5 mg, 8 ⁇ mol) prepared in Example 6, anhydrous toluene 1 mL, AlMe 3 (160 ⁇ mol, 20 equiv.), was added sequentially under an argon atmosphere.
  • the GPC test data showed that the number average molecular weight of the polymer was 3.4 ⁇ 10 4 and the polydispersity coefficient was 1.8.
  • the catalyst in the reaction system is a pyridinium-based iron or cobalt metal complex catalyst and a co-catalyst.
  • Three-component system Based on the above two-component system, a dealkylation reagent is added.
  • Pyridineimine-based iron or cobalt metal complex catalyst (8 ⁇ mol, 1 equiv.), anhydrous toluene 1 mL, MAO (40 ⁇ mol, 5 equiv.) were sequentially added to a 25 mL Schlenk tube under an argon atmosphere.
  • the method for synthesizing isoprene by using a pyridinium-based iron or cobalt metal complex catalyst according to any one of embodiments 31 to 55, respectively, is a pyridinium-based iron or cobalt metal complex 1 , 42, 43, 44, 45, 47, 64, 65, 66, 67, 28, 30, 31, 32, 33, 34, 36, 37, 38, 39 are catalysts, with corresponding cocatalysts and/or off
  • the alkylating agent and the solvent were subjected to catalytic polymerization to synthesize isoprene, and the results are shown in Table 1.

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Abstract

L'invention concerne un complexe métallique catalytique de pyridine-imine de fer ou de cobalt, un procédé de préparation associé, et une application de celui-ci, se rapportant au domaine de la synthèse chimique. Pour résoudre le problème existant lié à l'absence d'un catalyseur de polymérisation de diène conjugué hautement efficace, un complexe métallique catalytique de pyridine-imine de fer ou de cobalt est préparé par réaction d'un ligand de pyridine-imine avec un catalyseur métallique. Le complexe métallique catalytique de pyridine-imine de fer ou de cobalt, un cocatalyseur et un monomère d'isoprène sont synthétisés en polyisoprène au moyen d'une polymérisation catalytique. La présente invention est applicable à la production industrielle d'oléfines conjuguées.
PCT/CN2018/096292 2018-04-28 2018-07-19 Complexe métallique catalytique de pyridine-imine de fer ou de cobalt, son procédé de préparation et son application Ceased WO2019205309A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
CN201810399964.6A CN108658850A (zh) 2018-04-28 2018-04-28 一种含氟吡啶亚胺类配体、其过渡金属配合物及其在聚异戊二烯合成中的应用
CN201810399947.2A CN108641026B (zh) 2018-04-28 2018-04-28 一种苄基亚胺吡啶铁配合物在异戊橡胶制备中的应用
CN201810400881.4 2018-04-28
CN201810399964.6 2018-04-28
CN201810400881.4A CN108586641B (zh) 2018-04-28 2018-04-28 一种催化异戊二烯聚合的高效铁系催化剂及其制备方法与应用
CN201810400796.8 2018-04-28
CN201810399947.2 2018-04-28
CN201810400838.8A CN108530571B (zh) 2018-04-28 2018-04-28 一种烷基吡啶亚胺铁系催化剂及其制备方法与应用
CN201810400838.8 2018-04-28
CN201810400796.8A CN108659055B (zh) 2018-04-28 2018-04-28 一种基于柔性骨架的铁配合物、其制备方法及其在异戊二烯聚合中的应用

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111233755A (zh) * 2020-01-16 2020-06-05 安徽大学 吡啶亚胺配体、基于其的吡啶亚胺钯配合物及其催化应用
CN112442092A (zh) * 2020-11-24 2021-03-05 中国科学院青岛生物能源与过程研究所 一种6-甲氧基吡啶亚胺铁配合物及其制备方法和其在制备高顺式聚共轭二烯中的应用
CN114685702A (zh) * 2022-04-07 2022-07-01 中国科学院青岛生物能源与过程研究所 一种用吡啶亚胺铁催化剂制备聚共轭二烯的方法及聚共轭二烯的应用
KR20220114951A (ko) * 2021-02-09 2022-08-17 경북대학교 산학협력단 환형올레핀계 단량체 중합용 이민계 리간드 함유 팔라듐 착체 촉매 및 이를 이용한 환형올레핀계 중합체의 제조방법
WO2022173280A1 (fr) * 2021-02-09 2022-08-18 경북대학교 산학협력단 Catalyseur complexe contenant un ligand à base d'imine pour la polymérisation d'un monomère oléfinique cyclique, et procédé de préparation de polymère oléfinique cyclique l'utilisant
CN115677787A (zh) * 2022-09-02 2023-02-03 云南师范大学 疏基吡啶钴配合物及其制备方法和应用

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CN111233755A (zh) * 2020-01-16 2020-06-05 安徽大学 吡啶亚胺配体、基于其的吡啶亚胺钯配合物及其催化应用
CN112442092A (zh) * 2020-11-24 2021-03-05 中国科学院青岛生物能源与过程研究所 一种6-甲氧基吡啶亚胺铁配合物及其制备方法和其在制备高顺式聚共轭二烯中的应用
KR20220114951A (ko) * 2021-02-09 2022-08-17 경북대학교 산학협력단 환형올레핀계 단량체 중합용 이민계 리간드 함유 팔라듐 착체 촉매 및 이를 이용한 환형올레핀계 중합체의 제조방법
WO2022173280A1 (fr) * 2021-02-09 2022-08-18 경북대학교 산학협력단 Catalyseur complexe contenant un ligand à base d'imine pour la polymérisation d'un monomère oléfinique cyclique, et procédé de préparation de polymère oléfinique cyclique l'utilisant
KR102520084B1 (ko) 2021-02-09 2023-04-10 경북대학교 산학협력단 환형올레핀계 단량체 중합용 이민계 리간드 함유 팔라듐 착체 촉매 및 이를 이용한 환형올레핀계 중합체의 제조방법
CN114685702A (zh) * 2022-04-07 2022-07-01 中国科学院青岛生物能源与过程研究所 一种用吡啶亚胺铁催化剂制备聚共轭二烯的方法及聚共轭二烯的应用
CN114685702B (zh) * 2022-04-07 2023-08-18 中国科学院青岛生物能源与过程研究所 一种用吡啶亚胺铁催化剂制备聚共轭二烯的方法及聚共轭二烯的应用
CN115677787A (zh) * 2022-09-02 2023-02-03 云南师范大学 疏基吡啶钴配合物及其制备方法和应用
CN115677787B (zh) * 2022-09-02 2024-04-26 云南师范大学 疏基吡啶钴配合物及其制备方法和应用

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