CN114853798A - Pyrrole ring tridentate metal complex and application thereof - Google Patents
Pyrrole ring tridentate metal complex and application thereof Download PDFInfo
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- CN114853798A CN114853798A CN202210634088.7A CN202210634088A CN114853798A CN 114853798 A CN114853798 A CN 114853798A CN 202210634088 A CN202210634088 A CN 202210634088A CN 114853798 A CN114853798 A CN 114853798A
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 51
- 125000000168 pyrrolyl group Chemical group 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052735 hafnium Chemical group 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical group 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 13
- 239000005977 Ethylene Substances 0.000 abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004711 α-olefin Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000003780 insertion Methods 0.000 abstract description 6
- 230000037431 insertion Effects 0.000 abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 229920006124 polyolefin elastomer Polymers 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 150000001875 compounds Chemical group 0.000 description 33
- 238000000921 elemental analysis Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- MNKCGUKVRJZKEQ-MIXQCLKLSA-N (1z,5z)-cycloocta-1,5-diene;iridium;methanol Chemical compound [Ir].[Ir].OC.OC.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 MNKCGUKVRJZKEQ-MIXQCLKLSA-N 0.000 description 2
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 2
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002518 isoindoles Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 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
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention provides a pyrrole ring tridentate metal complex which has a structure shown in a formula I. The invention takes a novel pyrrole ring-containing tridentate fourth subgroup metal complex as a main catalyst and takes alkyl aluminoxane or modified alkyl aluminoxane or boron auxiliary agent system as a cocatalyst for catalyzing copolymerization reaction of ethylene and alpha-olefin. The novel pyrrole ring-containing tridentate fourth subgroup metal complex provided by the invention has the advantages of good thermal stability, high catalytic activity and the like, and can be used as a main catalyst for catalyzing olefin polymerization reaction, so that the copolymerization reaction of ethylene and 1-octene can be efficiently catalyzed, and the polyolefin elastomer material with high molecular weight and high comonomer insertion rate can be obtained.
Description
Technical Field
The invention belongs to the technical field of olefin polymer catalysts, and particularly relates to a pyrrole ring tridentate metal complex and application thereof, in particular to a novel pyrrole ring tridentate-containing fourth subgroup metal complex and application thereof in catalyzing olefin polymerization, particularly ethylene and alpha-olefin copolymerization.
Background
The polyolefin product has the advantages of rich raw materials, low price, easy production and processing, good mechanical property, excellent performance and the like, and the development level of the polyolefin industry directly represents the development level of the national petrochemical industry for the most widely applied synthetic resin materials in the production and the life at present.
The olefin polymerization catalyst directly determines the internal structure and the appearance of a polyolefin product, and is the most core technology in the development process of the polyolefin industry; the non-metallocene catalyst has a single active center, relatively high activity, strong tolerance of central metal to heteroatoms, has the advantages of both the ZN catalyst and the metallocene catalyst, can catalyze homopolymerization and copolymerization of multiple series of olefin monomers, realizes accurate control on the molecular weight and the internal appearance of polyolefin products, enriches the types of the polyolefin products, and has very wide application prospects.
The method enriches the types of catalysts, improves the temperature resistance and activity of the catalysts, and catalytically prepares high molecular polymers and polymers with high monomer content, which become the hot spots of research in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a pyrrole ring tridentate metal complex and an application thereof, and the pyrrole ring tridentate metal complex provided by the present invention has characteristics of good temperature resistance and high catalytic activity as a catalyst, and an obtained polymer has characteristics of high molecular weight and high comonomer content.
The invention provides a pyrrole ring tridentate metal complex which has a structure shown in a formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Independently selected from alkyl or substituted alkyl, aryl or substituted aryl;
x is selected from halogen, alkyl or benzyl;
m is selected from transition metals of the fourth subgroup.
Preferably, said R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The alkyl in (A) is independently selected from C1-C12 alkyl.
Preferably, said R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The ring is C3-C6 alkyl ring or substituted alkyl ring, aryl ring or substituted aryl ring.
Preferably, said R is 1 Selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl and 9-anthryl.
Preferably, said R is 2 、R 3 Independently selected from H and methyl.
Preferably, said R is 4 ～R 7 Independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
Preferably, said R is 1 And R 2 Form an aryl ring, R 2 And R 3 Form an aryl ring, R 4 And R 5 Forming an aryl ring.
Preferably, M is selected from titanium, zirconium or hafnium.
Preferably, X is selected from Cl, methyl, benzyl.
The invention provides a polymer which is prepared by taking the pyrrole ring tridentate metal complex in the technical scheme as a catalyst.
The invention provides a novel pyrrole ring-containing tridentate fourth subgroup metal complex, and the compound structure is reasonably modified, so that the complex has the characteristics of good temperature resistance, high catalytic activity, high polymer molecular weight and high comonomer content when being used as a catalyst.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a complex formula 3 prepared in example 3 of the present invention;
FIG. 2 is a NMR chart of the complex formula 13 prepared in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a pyrrole ring tridentate metal complex which has a structure shown in a formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Independently selected from alkyl or substituted alkyl, aryl or substituted aryl;
x is selected from halogen, alkyl or benzyl;
m is selected from transition metals of the fourth subgroup.
In the present invention, said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The alkyl in (A) is preferably independently selected from C1-C12, more preferably independently selected from C2-C10, more preferably independently selected from C3-C8, and most preferably independently selected from C4-C6.
In the present invention, said R 1 Preferably selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 9-anthryl.
In the present invention, said R 2 、R 3 Preferably independently selected from H and methyl.
In the present invention, said R 4 ～R 7 Preferably independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
In the present invention, said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Preferably into a ring, preferablyForm an alkyl ring or substituted alkyl ring, aryl ring or substituted aryl ring of C3-C6; more preferably R 1 And R 2 Form an aryl ring, R 2 And R 3 Form an aryl ring, R 4 And R 5 Forming an aryl ring.
In the present invention, the M is preferably selected from titanium, zirconium or hafnium, more preferably Zr, Hf.
In the present invention, said X is preferably selected from Cl, methyl, benzyl.
In the present invention, the pyrrole ring tridentate metal complex is preferably one selected from formulae 1 to 20:
the preparation method of the pyrrole ring tridentate metal complex is not particularly limited, and the pyrrole ring tridentate metal complex can be prepared by various compound synthesis methods well known to those skilled in the art according to the compound structures, and can be prepared by the methods in the embodiments of the invention.
The invention provides a polymer which is prepared by taking the pyrrole ring tridentate metal complex in the technical scheme as a catalyst.
In the present invention, the pyrrole ring tridentate metal complex is the same as that described in the above technical scheme, and is not described herein again.
In the present invention, the method for preparing the polymer preferably comprises:
under the action of main catalyst and cocatalyst, ethylene and alpha-olefin are copolymerized to obtain the polymer.
In the invention, the main catalyst is the pyrrole ring tridentate metal complex in the technical scheme.
In the invention, the cocatalyst is selected from one or more of alkyl aluminoxane, modified alkyl aluminoxane, halogenated alkyl aluminum and alkyl aluminum, and more preferably selected from methyl aluminoxane or modified methyl aluminoxane. In the present invention, the co-catalyst preferably further contains a boron-containing substance, preferably selected from triphenylcarbenium-tetrakis (pentafluorophenyl) borate.
In the present invention, the molar ratio of Al in the co-catalyst to the metal element in the main catalyst is preferably (5 to 5000): 1, more preferably (10 to 4000): 1, more preferably (20 to 3000): 1, more preferably (30 to 2000): 1, more preferably (40 to 1000): 1, more preferably (50 to 800): 1, more preferably (100 to 600): 1, more preferably (200 to 500): 1, most preferably (300-400): 1.
In the present invention, the molar ratio of boron in the cocatalyst to the metal element in the main catalyst is preferably (0.1 to 2): 1, more preferably (0.5 to 2): 1, more preferably (1-2): 1, most preferably 1.5: 1.
In the present invention, the alpha-olefin is preferably selected from 1-octene.
In the present invention, the α -olefin is preferably dissolved in a solvent, preferably an isoparaffin (Isopar E); the concentration of the alpha-olefin in the solution is preferably 0.1-5 mol/L, more preferably 0.5-4 mol/L, more preferably 1-3 mol/L, and most preferably 1 mol/L.
In the present invention, the ratio of the amount of the solution formed by the main catalyst and the α -olefin is preferably (2 to 3) μmol: (350-450) mL, more preferably (2.4-2.6) μmol: (380 to 420) mL, most preferably 2.5. mu. mol: 400 mL.
In the invention, the pressure of ethylene in the copolymerization reaction process is preferably 0.1-10 MPa, more preferably 1-8 MPa, more preferably 2-6 MPa, and most preferably 2-4 MPa.
In the invention, the temperature of the copolymerization reaction is preferably 60-210 ℃, more preferably 80-200 ℃, more preferably 100-180 ℃, more preferably 120-160 ℃, and most preferably 140 ℃; the time of the copolymerization reaction is preferably 3 to 40min, more preferably 5 to 30min, more preferably 10 to 20min, and most preferably 15 min.
The invention provides a pyrrole ring IIIThe structure of the dentate metal complex is convenient to modify; the catalyst has good temperature resistance and can keep high catalytic activity under the high-temperature condition; catalyzing the copolymerization reaction of ethylene and 1-octene to obtain polymer product with high molecular weight and high comonomer insertion rate. The experimental results show that: the molecular weight of a polymer obtained by the copolymerization of ethylene and 1-octene under the catalysis of the complex provided by the invention can reach 39.2 x 10 4 g/mol, the molar insertion rate of 1-octene is up to 16.7%.
Example 1
The ligand with the structure of the formula II is prepared according to the following synthetic route:
in the structure of formula II R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Cyclic structures formed without direct connection to each other, in particular compounds of formulae L1 to L9:
the preparation process comprises the following steps:
R 1 pyrrole starting materials such as H, methyl and isopropyl are directly available;
R 1 the process for the preparation of the pyrrole compounds of the formula C, i.e. the phenyl, anthracenyl, is as follows:
dripping a compound (pyrrole, 40mmol) of the formula A into 100mL of dry tetrahydrofuran suspension which is cooled to 0 ℃ in advance and contains NaH (40mmol) under a nitrogen atmosphere, and raising the temperature to room temperature for reaction for 5 hours after the addition is finished; then adding zinc chloride (40mmol) into the mixture in batches, and reacting for 20min after the addition is finished; then, 2- (dicyclohexylphosphino) biphenyl (0.4mmol) and tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added thereto in this order 2 (dba) 3 (ii) a 0.2mmol), reacting for 10 min; and then adding R thereto 1 Heating and refluxing-reacting-Br (bromobenzene or 9-bromoanthracene; 10mmol) for 24 h; after the reaction is finished, cooling to room temperature, adding ethyl acetate (200mL) and water (20mL), filtering to remove insoluble substances, then adding 100mL of water, separating to retain an organic phase, extracting the aqueous phase for 3 times by using ethyl acetate, combining the organic phases, adding anhydrous magnesium sulfate, drying, filtering, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the compound (R) of the formula C 1 Phenyl, anthracenyl).
The specific preparation method of the intermediate compound shown in the formula D is as follows:
under nitrogen atmosphere, a 250mL Schlenck flask was charged with the compound of formula C (20mmol), n-hexane (100mL), and methoxy (cyclooctadiene) iridium (I) dimer (i.e., [ Ir (COD) OMe)] 2 (ii) a 0.3 mmol), a compound of formula G (pinacolborane; 30mmol), 4 '-di-tert-butyl-2, 2' -bipyridine (i.e.: dibbpy; 0.6mmol), stirring and reacting for 10min, then adding pyrrole (10mL), heating and refluxing for reaction for 24 h; after the reaction is finished, the reaction product is cooled to room temperature, ethyl acetate (200mL) and methanol (20mL) are added into the reaction product, the mixture is stirred for 20min to completely quench the reaction, then 100mL of water is added into the reaction product, the organic phase is separated and retained, the aqueous phase is extracted for 3 times by ethyl acetate, the organic phase is combined, anhydrous magnesium sulfate is added for drying, the filtration is carried out, the solvent is removed by rotary evaporation, and the crude product is purified by column chromatography (an eluent is dichloromethane: petroleum ether ═ 1:3) to obtain the compound of the formula D.
The specific preparation method of the intermediate compound shown in the formula F is as follows:
under nitrogen atmosphere, adding the compound of formula E (50mmol), the compound of formula D (50mmol), deoxygenated ethylene glycol dimethyl ether (200mL), deoxygenated deionized water (25mL), cesium carbonate (55mmol) and tetrakis (triphenylphosphine) palladium (5mmol) in sequence into a 500mL round-bottom flask, refluxing for 72h, cooling to room temperature, removing most of the solvent by rotary evaporation, adding 100mL diethyl ether and 100mL water, separating and retaining the organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate, drying, filtering, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the compound of formula F.
The specific preparation method of the intermediate compound shown in the formula J comprises the following steps:
dissolving a compound (50mmol) of a formula H in 100mL of dried tetrahydrofuran under a nitrogen atmosphere, cooling to-78 ℃, dropping 55mmol of n-butyllithium into the tetrahydrofuran, keeping the reaction at a low temperature for 0.5H, dropping triisopropyl borate (60mmol) into the tetrahydrofuran, removing the low temperature, raising the temperature to room temperature, continuing to react for 1H, adding 100mL of water and 100mL of diethyl ether, separating to keep an organic phase, continuing to extract the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate, drying, filtering, and removing the solvent by rotary evaporation to obtain a compound of a formula J.
The preparation method of the ligand with the structure shown in the formula II comprises the following steps:
under nitrogen atmosphere, adding a compound of formula F (50mmol), a compound of formula J (55mmol), deoxygenated ethylene glycol dimethyl ether (200mL), deoxygenated deionized water (25mL), cesium carbonate (55mmol) and tetrakis (triphenylphosphine) palladium (5mmol) into a 500mL round-bottom flask in sequence, heating and refluxing for 72h, cooling to room temperature, performing rotary evaporation to remove most of the solvent, adding 100mL diethyl ether and 100mL water, separating to keep an organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate for drying, filtering, performing rotary evaporation to remove the solvent, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the ligand of formula II.
Example 2
R in the ligand of formula II 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The structure of the ring structure is as shown in the formulas L10-L17:
the compound with the structure of the formula F is prepared according to the following synthetic route:
the specific method comprises the following steps:
R 1 pyrrole starting materials of H, methyl, isopropyl and tert-butyl; r 1 And R 2 Indole (compound of formula L7), R 2 And R 3 Isoindoles (compounds of formula L8) obtained by linking to form a ring can be purchased directly;
R 1 the process for the preparation of the pyrrole compounds of formula C, namely the phenyl, anthracenyl, is as follows:
dripping a compound (pyrrole, 40mmol) of the formula A into 100mL of dry tetrahydrofuran suspension which is cooled to 0 ℃ in advance and contains NaH (40mmol) under a nitrogen atmosphere, and raising the temperature to room temperature for reaction for 5 hours after the addition is finished; then adding zinc chloride (40mmol) into the mixture in batches, and reacting for 20min after the addition is finished; then, 2- (dicyclohexylphosphino) biphenyl (0.4mmol) and tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added thereto in this order 2 (dba) 3 (ii) a 0.2mmol), reacting for 10 min; and then adding R thereto 1 Heating and refluxing-reacting-Br (bromobenzene or 9-bromoanthracene; 10mmol) for 24 h; after the reaction is finished, cooling to room temperature, adding ethyl acetate (200mL) and water (20mL), filtering to remove insoluble substances, then adding 100mL of water, separating to retain an organic phase, extracting the aqueous phase for 3 times by using ethyl acetate, combining the organic phases, adding anhydrous magnesium sulfate, drying, filtering, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the compound (R) of the formula C 1 Phenyl, anthracenyl).
The specific preparation method of the intermediate compound shown in the formula D is as follows:
under nitrogen atmosphere, a 250mL Schlenck flask was charged with the compound of formula C (20mmol), n-hexane (100mL), and methoxy (cyclooctadiene) iridium (I) dimer (i.e., [ Ir (COD) OMe)] 2 (ii) a 0.3 mmol), a compound of formula G (pinacolborane; 30mmol), 4 '-di-tert-butyl-2, 2' -bipyridine (i.e.: dibbpy; 0.6mmol), stirring and reacting for 10min, then adding pyrrole (10mL), heating and refluxing for reaction for 24 h; after the reaction was completed, it was cooled to room temperature, ethyl acetate (200mL) and methanol (20mL) were added thereto, and stirred for 20min to completely quench the reaction, and then 100mL of water was added thereto, and the solution was separated and retainedThe organic phase and the aqueous phase are further extracted 3 times with ethyl acetate, the organic phases are combined, dried with anhydrous magnesium sulfate, filtered, the solvent is removed by rotary evaporation, and the crude product is purified by column chromatography (eluent dichloromethane: petroleum ether ═ 1:3) to give the compound of formula D.
The specific preparation method of the intermediate compound shown in the formula F is as follows:
under nitrogen atmosphere, adding the compound of formula E (50mmol), the compound of formula D (50mmol), deoxygenated ethylene glycol dimethyl ether (200mL), deoxygenated deionized water (25mL), cesium carbonate (55mmol) and tetrakis (triphenylphosphine) palladium (5mmol) in sequence into a 500mL round-bottom flask, refluxing for 72h, cooling to room temperature, removing most of the solvent by rotary evaporation, adding 100mL diethyl ether and 100mL water, separating and retaining the organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate, drying, filtering, removing the solvent by rotary evaporation, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the compound of formula F.
The preparation method of the ligand with the structure shown in the formula II comprises the following steps:
under nitrogen atmosphere, adding a compound of formula F (50mmol), 1-naphthalene boric acid (55mmol), deoxygenated ethylene glycol dimethyl ether (200mL), deoxygenated deionized water (25mL), cesium carbonate (55mmol) and tetrakis (triphenylphosphine) palladium (5mmol) into a 500mL round-bottom flask in sequence, heating and refluxing for 72h, cooling to room temperature, performing rotary evaporation to remove most of the solvent, adding 100mL diethyl ether and 100mL water, separating to keep an organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the organic phases, adding anhydrous magnesium sulfate for drying, filtering, performing rotary evaporation to remove the solvent, and purifying the crude product by column chromatography (eluent is ethyl acetate: petroleum ether ═ 1:30) to obtain the ligand of formula II.
Example 3
General preparation of Metal complexes (preparation of Metal methides, formulae C1-C9, C11-C18, C20):
dissolving 2mmol of ligand (one of formulas L1-L17) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution, removing low temperature, continuing to react for 3h at room temperature, and slowly transferring the solution to the reaction kettle by using a syringeMX first cooled to 0 ℃ 4 (2mmol, M ═ Hf or Zr, X ═ Cl) in a suspension of toluene (10mL), the reaction was carried out at 0 ℃ for 1.5 hours, and CH was added thereto 3 MgBr (6mmol), heating to 100 ℃ and continuing to react for 2 h; cooling to room temperature, filtering to remove insoluble substances, removing volatile components from the filtrate under vacuum, and recrystallizing the crude product (toluene/n-hexane ═ 1: 20) to obtain metal complexes of formulas C1-C9, C11-C18, and C20.
Example 4
General preparation of the Metal complexes (metal benzylates, preparation of the formulae C10, C19):
dissolving 2mmol of ligand (one of formulas L1-L17) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution, removing low temperature, continuing to react for 3h at room temperature, and slowly transferring to MX (MX) cooled to 0 ℃ in advance by using a syringe 4 (2mmol, M ═ Hf or Zr, X ═ Cl) in toluene (10mL), reacted at 0 ℃ for 1.5h, and PhCH was added thereto 2 MgBr (6mmol), heating to 100 ℃ and continuing to react for 2 h; cooling to room temperature, filtering to remove insoluble substances, removing volatile components from the filtrate under vacuum, and recrystallizing the crude product (toluene/n-hexane ═ 1: 20) to obtain metal complexes of formulas C10 and C19.
FIG. 1 is the NMR spectrum of the complex of formula 3 prepared in example 3, and FIG. 2 is the NMR spectrum of the complex of formula 13 prepared in example 3, and it can be seen from FIGS. 1 and 2 that the target structure product is synthesized.
The yields, yields and elemental analysis results of the metal complexes of formulae 1 to 20 prepared according to examples 3 and 4 are as follows:
a metal complex of the structure of formula 1 (Cat1), yield: 0.6865g, yield: 73.2%, elemental analysis: measured (calculated) C: 51.24(51.23) H: 4.72(4.73) N: 5.98 (5.97);
a metal complex of structure 2 (Cat2), yield: 0.8621g, yield: 82.1%, elemental analysis: measured (calculated) C: 54.90(54.91) H: 5.76(5.76) N: 5.34 (5.34);
a metal complex of structure 3 (Cat3), yield: 0.6937g, yield: 69.8%, elemental analysis: measured (calculated) C: 53.18(53.17) H: 5.27(5.27) N: 5.64 (5.64);
a metal complex of structure 4 (Cat4), yield: 0.8995g, yield: 77.4%, elemental analysis: measured (calculated) C: 57.95(57.87) H: 6.60(6.59) N: 4.82 (4.82);
a metal complex of structure 5 (Cat5), yield: 0.6880g, yield: 80.6%, elemental analysis: measured (calculated) C: 47.85(47.84) H: 3.78(3.78) N: 6.55 (6.56);
a structured metal complex of formula 6 (Cat6), yield: 0.5634g, yield: 63.9%, elemental analysis: measured (calculated) C: 49.11(49.04) H: 4.13(4.12) N: 6.36 (6.35);
a metal complex of structure 7 (Cat7), yield: 0.7418g, yield: 79.1%, elemental analysis: measured (calculated) C: 51.24(51.23) H: 4.73(4.73) N: 5.97 (5.97);
a structural metal complex of formula 8 (Cat8), yield: 0.6880g, yield: 68.4%, elemental analysis: measured (calculated) C: 54.96(54.93) H: 4.00(4.01) N: 5.58 (5.57);
a metal complex of structure 9 (Cat9), yield: 0.9709g, yield: 80.5%, elemental analysis: measured (calculated) C: 61.77(61.74) H: 4.02(4.01) N: 4.65 (4.65);
a structural metal complex of formula 10 (Cat10), yield: 1.0397g, yield: 83.7%, elemental analysis: measured (calculated) C: 61.89(61.88) H: 4.87(4.87) N: 4.51 (4.51);
a metal complex of structure of formula 11 (Cat11), yield: 0.7067g, yield: 74.1%, elemental analysis: measured (calculated) C: 52.92(52.89) H: 3.79(3.80) N: 5.88 (5.87);
a metal complex of structure 12 (Cat12), yield: 0.7187g, yield: 73.2%, elemental analysis: measured (calculated) C: 53.86(53.83) H: 4.10(4.11) N: 5.71 (5.71);
a metal complex of structure 13 (Cat13), yield: 0.7234g, yield: 69.7%, elemental analysis: measured (calculated) C: 55.59(55.55) H: 4.66(4.66) N: 5.40 (5.40);
a metal complex of structure 14 (Cat14), yield: 0.8656g, yield: 81.2%, elemental analysis: measured (calculated) C: 56.35(56.34) H: 4.92(4.92) N: 5.26 (5.26);
a structural metal complex of formula 15 (Cat15), yield: 0.7996g, yield: 72.3%, elemental analysis: measured (calculated) C: 58.69(58.65) H: 4.00(4.01) N: 5.07 (5.07);
a metal complex of structure 16 (Cat16), yield: 1.0136g, yield: 77.6%, elemental analysis: measured (calculated) C: 64.32(64.37) H: 4.02(4.01) N: 4.28 (4.29);
a structural metal complex of formula 17 (Cat17), yield: 0.7524g, yield: 71.4%, elemental analysis: measured (calculated) C: 56.90(56.98) H: 3.83(3.83) N: 5.32 (5.32);
a metal complex of structure 18 (Cat18), yield: 0.8494g, yield: 80.6%, elemental analysis: measured (calculated) C: 57.03(56.98) H: 3.84(3.83) N: 5.33 (5.32);
a structural metal complex of formula 19 (Cat19), yield: 1.0319g, yield: 75.3%, elemental analysis: measured (calculated) C: 64.90(64.86) H: 5.02(5.00) N: 4.10 (4.09);
a metal complex of structure 20 (Cat20), yield: 0.8088g, yield: 77.5%, elemental analysis: measured (calculated) C: 71.42(71.35) H: 5.82(5.80) N: 5.38 (5.37);
EXAMPLE 5 catalytic copolymerization of ethylene with 1-octene
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, vacuum air is pumped for 1h, the system is adjusted to the temperature condition required by polymerization, 0.1MPa ethylene gas is filled, mixed isoalkane (Isopar E) solution containing a certain amount of Modified Methylaluminoxane (MMAO) and alpha-olefin (1-octene) with a certain concentration is added into the polymerization kettle (the total volume of the final solution is 400 mL), the temperature is kept constant for a period of time, 3.5MPa ethylene gas is introduced, the solution is waited for 10min to ensure that ethylene is dissolved and balanced, then a main catalyst (when a boron cocatalyst is added, the main catalyst and the main catalyst are mixed and shaken uniformly in advance, and the mixture is kept stand for 5min) and stirred for a period of time. And (3) after the polymerization reaction is finished, discharging residual ethylene gas, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol with the volume ratio of 1:1, stirring for 5min, filtering, and drying the polymer product in a vacuum oven.
The polymer prepared in example 5 was weighed, the molecular weight and the molecular weight distribution were measured, and the monomer insertion rate and the polymerization conditions were measured by high temperature carbon spectroscopy: the dosage of the main catalyst C1-C20 is 2.5 mu mol, the cocatalyst is MMAO-7, Al/M is 400, the concentration of 1mol/L octene is 1mol/L, the polymerization pressure is 3.5MPa, and the polymerization temperature is as follows: the polymerization time is 10min at 140 ℃; a molecular weight, molecular weight distribution determined by GPC; b by 13 C, CNMR measurement; c cocatalyst Ph 3 C[B(PhF 5 ) 4 ]And Al (iBu) 3 ，M/B/Al＝1:1.2:80。
The detection results are as follows:
from the above examples, the invention provides a novel pyrrole ring-containing tridentate fourth subgroup metal complex, which has good temperature tolerance, can maintain high catalytic activity at 140 ℃, is used as a main catalyst to catalyze the copolymerization of ethylene 1-octene, and has high activity and high polymer molecular weight and comonomer insertion rate. The experimental results show that: the molecular weight of a polymer obtained by the copolymerization of ethylene and 1-octene under the catalysis of the complex provided by the invention can reach 39.2 x 10 4 g/mol, the molar insertion rate of 1-octene is up to 16.7%.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A pyrrole ring tridentate metal complex having the structure of formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Independently selected from alkyl or substituted alkyl, aryl or substituted aryl;
x is selected from halogen, alkyl or benzyl;
m is selected from transition metals of the fourth subgroup.
2. The pyrrole ring tridentate metal complex according to claim 1, characterized in that R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The alkyl in (A) is independently selected from C1-C12 alkyl.
3. The pyrrole ring tridentate metal complex according to claim 1, characterized in that R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The ring is C3-C6 alkyl ring or substituted alkyl ring, aryl ring or substituted aryl ring.
4. The pyrrole ring tridentate metal complex according to claim 1, characterized in that R is 1 Selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, 1-naphthyl and 9-anthryl.
5. The pyrrole ring tridentate metal complex according to claim 1,wherein R is 2 、R 3 Independently selected from H and methyl.
6. The pyrrole ring tridentate metal complex according to claim 1, characterized in that R is 4 ～R 7 Independently selected from H, methyl, ethyl, propyl, isopropyl, tert-butyl.
7. A pyrrole ring tridentate metal complex according to claim 1, characterised in that the R is 1 And R 2 Form an aryl ring, R 2 And R 3 Form an aryl ring, R 4 And R 5 Forming an aryl ring.
8. A pyrrole ring tridentate metal complex according to claim 1, characterised in that M is selected from titanium, zirconium or hafnium.
9. The pyrrole ring tridentate metal complex according to claim 1, characterised in that X is selected from Cl, methyl, benzyl.
10. A polymer prepared by using the pyrrole ring tridentate metal complex according to any one of claims 1 to 9 as a catalyst.
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