CN110105473B - Plate type alpha-diimine catalyst and preparation method and application thereof - Google Patents
Plate type alpha-diimine catalyst and preparation method and application thereof Download PDFInfo
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- CN110105473B CN110105473B CN201910440633.7A CN201910440633A CN110105473B CN 110105473 B CN110105473 B CN 110105473B CN 201910440633 A CN201910440633 A CN 201910440633A CN 110105473 B CN110105473 B CN 110105473B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- 239000003446 ligand Substances 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229920000098 polyolefin Polymers 0.000 abstract description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 abstract description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- 239000005977 Ethylene Substances 0.000 description 19
- 239000004698 Polyethylene Substances 0.000 description 16
- -1 polyethylene Polymers 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- KZLCCMBSJDXNDG-UHFFFAOYSA-N azepan-1-yl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)N1CCCCCC1 KZLCCMBSJDXNDG-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010516 chain-walking reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7004—Neutral ligand
- C08F4/7006—NN
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a plate type alpha-diimine catalyst and a preparation method and application thereof, wherein the catalyst has the following structural general formula:
wherein M is a central metal atom; r1And R2Is methyl, chlorine or bromine; bridging group
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation, and particularly relates to a plate-type alpha-diimine catalyst as well as a preparation method and application thereof.
Background
Polyolefins are the most widely used polymeric materials with the greatest production yields, and can be used to prepare food packaging, medical devices, optical components, and the like. In recent years, the annual output and annual consumption of polyolefin in China are steadily improved, but the annual import quantity is gradually improved. The main reason is that the intensification degree of the polyolefin industry in China is low, and the products tend to be low-end. In order to improve the global competitiveness of the polyolefin industry in China, the yield and productivity of high-end polyolefin products in China need to be improved, and the most important and effective way in this aspect is to design and develop a novel high-efficiency olefin polymerization catalyst.
The late transition metal catalyst has strong tolerance, can catalyze the copolymerization of ethylene or propylene and various monomers, and has attracted extensive attention in scientific research and industrial production. Among them, the diamine-type late transition metal catalyst exhibits very excellent performance in catalyzing homopolymerization and copolymerization of ethylene or propylene. And the diimine ligand is simple to synthesize, and the substituent group can be flexibly regulated and controlled, so that the diimine ligand is an ideal olefin polymerization catalyst. However, most of the existing catalysts still cannot effectively improve the content, molecular weight and other application properties of the functional sequences in the polymer, and further cannot prepare high-end polyethylene products with excellent properties.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a plate-type alpha-diimine catalyst, a preparation method and application thereof, and solves the problems of low molecular weight and high branching degree of a polymerization product and the like caused by poor catalytic performance of the existing olefin polymerization catalyst.
In order to achieve the purpose, the invention adopts the following scheme: a plate type alpha-diimine catalyst has a structural general formula as follows:
wherein M is a central metal atom; r1And R2Is methyl, chlorine or bromine; bridging group
Is phenyl, benzoquinone, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tetrahydrothiophene, tetrahydrofuran or tetrahydropyrrole; r is an aliphatic group or an aromatic group.
The plate type structure of the catalyst of the invention is that a rigid framework is utilized to construct a double-layer ligand framework which is parallel to each other, and the restriction effect of the rigid framework on the conformation of the catalyst can effectively improve the steric hindrance environment around an active center, thereby inhibiting the coordination-dissociation exchange reaction in the polymerization reaction process, improving the functional sequence content and molecular weight of a catalytic product, and reducing the branching degree.
Preferably, the fatty group is one of the following structures:
preferably, the aromatic group is one of the following structures:
preferably, the central metal atom is palladium, nickel, cobalt, iron or copper.
The invention also provides a preparation method of the plate type alpha-diimine catalyst, which comprises the following steps:
1) preparation of plate-type α -diimine ligands: reacting 5,7,12, 14-tetrahydro-18 lambda 5,19 lambda 5-5, 14; adding 7, 12-bis ([1,2] phenylene) pentacene-6, 13,18, 19-tetraone and 2, 6-diisopropylaniline into a solvent, uniformly mixing, then reacting at 30-120 ℃ for 4-72 h, concentrating a reaction system after the reaction is finished, and recrystallizing and purifying to obtain a solid, namely the plate-type alpha-diimine ligand;
2) preparation of plate-type α -diimine catalyst: mixing the plate-type alpha-diimine ligand prepared in the step 2) with metal pre-prepared salt, adding a solvent, stirring and reacting at-78-120 ℃ for 1-24 h, filtering out a suspension, taking a filtrate, concentrating, recrystallizing and purifying to obtain a solid, namely the plate-type alpha-diimine catalyst.
Thus, the plate type alpha-diimine catalyst prepared by the invention introduces aromatic group or aliphatic group with large steric hindrance into nitrogen atoms on one side of imine, increases steric hindrance around a metal center, improves the electron density of the metal center of the catalyst, is beneficial to the insertion of ethylene, thereby improving the catalytic performance of the catalyst and obtaining a polymer with high molecular weight. Meanwhile, the branching degree of the polyethylene is reduced by the inhibition effect of the large steric hindrance group on the chain walking reaction.
Preferably, the metal pre-complex salt is a palladium salt, a nickel salt, a cobalt salt, an iron salt or a copper salt.
Preferably, the 5,7,12, 14-tetrahydro-18 λ 5,19 λ 5-5, 14; the molar ratio of the 7, 12-bis ([1,2] phenylene) pentacene-6, 13,18, 19-tetraone to the 2, 6-diisopropylaniline is 1: 4-1: 8.
Preferably, the molar ratio of the plate-type alpha-diimine ligand to the metal pre-complex salt is 1:1 to 2: 1.
Preferably, the solvent is toluene or dichloromethane.
The invention also provides the application of the plate type alpha-diimine catalyst in olefin polymerization. The monomer in the olefin polymerization reaction is one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornene, dicyclopentadiene, 1, 4-butadiene and styrene.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the plate type alpha-diimine catalyst, the aromatic group or the aliphatic group with large steric hindrance is introduced into the nitrogen atom on one side of imine, so that the steric hindrance around the metal center is increased, the electron density of the metal center of the catalyst is optimized, the catalytic performance of the catalyst is improved, and the polymer with high molecular weight is obtained. Meanwhile, the inhibition of the large steric hindrance group on the coordination-dissociation exchange reaction can effectively improve the functional sequence content of the polymer, and the inhibition of the large steric hindrance group on the chain walking reaction can effectively reduce the branching degree of the polyethylene.
2. The plate-type alpha-diimine catalyst is prepared from low-price alpha-diketone, arylamine, fatty amine and the like serving as raw materials through efficient condensation and coordination reactions, and has the advantages of low cost of the raw materials, short synthetic route, high reaction yield, easiness in realization of industrial production and good application prospect.
3. The plate-type alpha-diimine catalyst has high catalytic activity in catalyzing olefin polymerization reaction, and can be used for catalyzing to obtain a functionalized polyolefin material with high molecular weight, low branching degree, high polar group content and highly controllable structure and performance.
Drawings
FIG. 1 is a NMR spectrum of an α -bis (2, 6-diisopropyl) benzimine ligand prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
1) Preparation of α -bis (2, 6-diisopropyl) benzimine ligand:
100mL of toluene and 0.005mol of 5,7,12, 14-tetrahydro-18. lambda. having a plate-type structure were charged in a reaction flask connected to a water separator5,19λ5-5, 14; 7, 12-bis ([1,2]]Phenylene bridge) pentacene-6, 13,18, 19-tetraone and 0.020mol of 2, 6-diisopropylaniline are heated to 120 ℃ and reacted for 24 h. After the reaction, the solution was concentrated to 30mL and crystallized in a refrigerator, and the obtained crystal substance was changed to a plate-type α -bis (2, 6-diisopropyl) benzimine ligand.
The resulting ligand was subjected to nmr mass spectrometry as shown in fig. 1.
From the figure, it can be derived that the structure of the ligand is shown below:
2) Preparation of plate type alpha-bis [ (2, 6-diisopropyl) benzimine ] palladium (II) catalyst
Adding 30mL of dichloromethane into a reaction bottle, then adding 0.005mol of plate type alpha-bis (2, 6-diisopropyl) phenylimine ligand and 0.005mol of (COD) PdClMe, reacting for 12h at 30 ℃, concentrating to 5mL after the reaction is finished, and adding 20mL of n-hexane for recrystallization and purification to obtain powdery solid, namely the plate type alpha-bis [ (2, 6-diisopropyl) phenylimine ] palladium (II) catalyst.
3) Catalytic copolymerization of ethylene and methyl acrylate
50mL of toluene, 0.8g of methyl acrylate, 0.1mmol of NaBAF as a cocatalyst and 0.02mmol of plate-type α -bis [ (2, 6-diisopropyl) phenylimine are injected into a 100mL stainless steel autoclave in this order under a dry nitrogen atmosphere]And (2) preparing a palladium (II) catalyst, regulating the pressure of ethylene in the autoclave to 10MPa, keeping the pressure until the polymerization is finished, reacting at 50 ℃ for 30min, stopping supplying ethylene gas, discharging unreacted ethylene gas in the autoclave through a gas release valve, pouring the polymerization system into a mixed solution of 300mL of ethanol and 30mL of concentrated hydrochloric acid to terminate the reaction, filtering and collecting white polyethylene solid, and drying in vacuum at 60 ℃ to constant weight. The polyethylene yield obtained was 1.1g and the catalyst activity was 0.11X 106gPE/molPdH, the molecular weight of the polymerization product is 45000,1the degree of branching of the polymer was 57C/1000C as determined by H-NMR, and the polar group content was 0.8 mol%.
Example 2
1) Preparation of plate-type α -bis (2, 6-diisopropyl) benzimine ligand:
100mL of toluene and 0.005mol of 5,7,12, 14-tetrahydro-18. lambda. having a plate-type structure were charged in a reaction flask connected to a water separator5,19λ5-5, 14; 7, 12-bis ([1,2]]Phenylene bridge) pentacene-6, 13,18, 19-tetraone and 0.020mol of 2, 6-diisopropylaniline were heated to 120 ℃ and reacted for 72 h. After the reaction, the solution was concentrated to 30mL and crystallized in a refrigerator, and the obtained crystal substance was changed to a plate-type α -bis (2, 6-diisopropyl) benzimine ligand.
2) Preparation of plate type alpha-bis [ (2, 6-diisopropyl) benzimine ] nickel (II) catalyst
30mL of methylene chloride were charged into a reaction flask, followed by 0.005mol of plate-type α -bis (2, 6-diisopropyl) benzimine ligand and 0.005mol of (DME)2NiBr2Reacting at 30 ℃ for 1h, concentrating to 5mL after the reaction is finished, adding 20mL of n-hexane for recrystallization and purification, and obtaining a powdery solid, namely the plate-type alpha-bis [ (2, 6-diisopropyl) benzimine]A nickel (II) catalyst.
3) Catalytic ethylene polymerization
50mL of toluene, 0.1mmol of MAO as a cocatalyst and 0.02mmol of plate-type α -bis [ (2, 6-diisopropyl) phenylimine were injected into a 100mL stainless steel autoclave in this order under a dry nitrogen atmosphere]The pressure of ethylene in an autoclave was adjusted to 30MPa by using a nickel (II) catalyst and maintained until the polymerization was completed, the ethylene gas supply was stopped after 30 minutes of reaction at 100 ℃ and unreacted ethylene gas in the autoclave was discharged through a gas release valve, the polymerization system was poured into a mixed solution of 300mL of ethanol and 30mL of concentrated hydrochloric acid to terminate the reaction, and a white polyethylene solid was collected by filtration and dried in vacuum at 60 ℃ to a constant weight. The polyethylene yield obtained was 21.3g and the catalyst activity was 2.13X 106gPE/molPdH, the molecular weight of the polymerization product is 445000,1the degree of branching of the polymer was determined by H-NMR to be 27C/1000C.
Example 3
1) Preparation of alpha-diphenylimine ligand:
100mL of toluene and 0.005mol of 5,7,12, 14-tetrahydro-18. lambda. having a plate-type structure were charged in a reaction flask connected to a water separator5,19λ5-5, 14; 7, 12-bis ([1,2]]Phenylene bridge) pentacene-6, 13,18, 19-tetrone and 0.020mol aniline are heated to 120 ℃ to react for 24 h. After the reaction is finished, the reaction solution is concentrated to 30mL and is placed in a refrigerator for crystallization, and the obtained crystal substance is changed into a plate type alpha-diphenylimine ligand.
2) Preparation of plate type alpha-bis [ (2, 6-diisopropyl) benzimine ] palladium (II) catalyst
Adding 30mL of dichloromethane into a reaction bottle, then adding 0.005mol of plate-type alpha-diphenylimine ligand and 0.005mol of (COD) PdClMe, reacting for 24h at 30 ℃, concentrating to 5mL after the reaction is finished, and adding 20mL of n-hexane for recrystallization and purification to obtain powder solid, namely the plate-type alpha-diphenylimine palladium (II) catalyst.
3) Catalytic copolymerization of ethylene and methyl acrylate
Under the protection of dry nitrogen, 50mL of toluene, 0.8g of methyl acrylate, 0.1mmol of NaBAF as a cocatalyst and 0.02mmol of plate-type alpha-diphenylimine palladium (II) catalyst are injected into a 100mL stainless steel autoclave in sequence, the pressure of ethylene in the autoclave is adjusted to 10MPa and kept until the polymerization is finished, after the reaction is finished at 70 ℃, the supply of ethylene gas is stopped, unreacted ethylene gas in the autoclave is discharged through a gas release valve, then the polymerization system is poured into a mixed solution of 300mL of ethanol and 30mL of concentrated hydrochloric acid to stop the reaction, white polyethylene solid is collected by filtration, and the white polyethylene solid is dried in vacuum at 60 ℃ to constant weight. The polyethylene yield obtained was 0.86g and the catalyst activity was 0.86X 106gPE/molPdH, the molecular weight of the polymerization product is 35000,1the degree of branching of the polymer was determined by H-NMR to be 61C/1000C, and the polar group content was 0.4 mol%.
Example 4
1) Preparation of alpha-diphenylimine ligand:
100mL of toluene and 0.005mol of 5,7,12, 14-tetrahydro-18. lambda. having a plate-type structure were charged in a reaction flask connected to a water separator5,19λ5-5, 14; 7, 12-bis ([1,2]]Phenylene bridge) pentacene-6, 13,18, 19-tetrone and 0.020mol aniline are heated to 100 ℃ to react for 24 h. After the reaction is finished, the reaction solution is concentrated to 30mL and is placed in a refrigerator for crystallization, and the obtained crystal substance is changed into a plate type alpha-diphenylimine ligand.
2) Preparation of plate type alpha-bis [ (2, 6-diisopropyl) benzimine ] nickel (II) catalyst
30mL of methylene chloride were charged into a reaction flask, followed by 0.005mol of the plate-type α -diphenylimine ligand and 0.005mol of (DME)2NiBr2Reacting at 30 ℃ for 12h, concentrating to 5mL after the reaction is finished, and adding 20mL of n-hexane for recrystallization and purification to obtain a powder solid, namely the plate-type alpha-diphenylimine nickel (II) catalyst.
3) Catalytic ethylene polymerization
50mL of toluene, 0.1mmol of MAO as a cocatalyst and 0.02mmol of nickel plate-type alpha-diphenylimine (I) were injected into a 100mL stainless steel autoclave in this order under a dry nitrogen atmosphereI) And (3) preparing a catalyst, regulating the pressure of ethylene in the autoclave to be 30MPa, keeping the pressure until the polymerization is finished, reacting at 30 ℃ for 30min, stopping supplying ethylene gas, discharging unreacted ethylene gas in the autoclave through a gas release valve, pouring a polymerization system into a mixed solution of 300mL of ethanol and 30mL of concentrated hydrochloric acid to stop the reaction, filtering and collecting white polyethylene solid, and drying in vacuum at 60 ℃ to constant weight. The polyethylene yield obtained was 18.2g and the catalyst activity was 1.82X 106gPE/molPdH, the molecular weight of the polymerization product is 353000,1the degree of branching of the polymer was determined by H-NMR to be 28C/1000C.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, although the applicant has described the present invention in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention and shall be covered by the claims of the present invention.
Claims (10)
1. A plate type alpha-diimine catalyst is characterized in that the structural general formula is as follows:
wherein M is a central metal atom; r1And R2Is methyl, chlorine or bromine; bridging group
Is benzoquinone; r is an aliphatic group or an aromatic group.
2. The plate type α -diimine catalyst of claim 1, wherein said aromatic group is one of the following structures:
3. the plate type α -diimine catalyst of claim 1, wherein said aliphatic group is one of the following structures:
4. the plate type α -diimine catalyst of claim 1, wherein said central metal atom is palladium, nickel, cobalt, iron or copper.
5. The method for preparing the plate type α -diimine catalyst according to any one of claims 1 to 4, comprising the steps of:
1) preparation of plate-type α -diimine ligands: reacting 5,7,12, 14-tetrahydro-18 lambda 5,19 lambda 5-5, 14; adding 7, 12-bis ([1,2] phenylene) pentacene-6, 13,18, 19-tetraone and 2, 6-diisopropylaniline into a solvent, uniformly mixing, then reacting at 30-120 ℃ for 4-72 h, concentrating a reaction system after the reaction is finished, and recrystallizing and purifying to obtain a solid, namely the plate-type alpha-diimine ligand;
2) preparation of plate-type α -diimine catalyst: adding the plate-type alpha-diimine ligand prepared in the step 1) and metal pre-prepared salt into a solvent, uniformly mixing, stirring and reacting at-78-120 ℃ for 1-24 h, filtering out a suspension, taking a filtrate, concentrating, recrystallizing and purifying to obtain a solid, namely the plate-type alpha-diimine catalyst.
6. The method for preparing the plate-type alpha-diimine catalyst of claim 5, wherein the metal pre-complex salt is palladium salt, nickel salt, cobalt salt, iron salt or copper salt.
7. The method for preparing the plate-type α -diimine catalyst of claim 5, wherein the 5,7,12, 14-tetrahydro-18 λ 5,19 λ 5-5, 14; the molar ratio of the 7, 12-bis ([1,2] phenylene) pentacene-6, 13,18, 19-tetraone to the 2, 6-diisopropylaniline is 1: 4-1: 8.
8. The preparation method of the plate-type alpha-diimine catalyst of claim 5, wherein the molar ratio of the plate-type alpha-diimine ligand to the metal pre-complex salt is 1:1 to 2: 1.
9. The method for preparing the plate-type α -diimine catalyst of claim 5, wherein the solvent is toluene or dichloromethane.
10. Use of the plate type α -diimine catalyst of any one of claims 1 to 4 in olefin polymerization.
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