CN117986290A - Preparation method of [ NOON ] tetradentate ligand fourth subgroup metal complex, catalyst for olefin polymerization and polyolefin - Google Patents
Preparation method of [ NOON ] tetradentate ligand fourth subgroup metal complex, catalyst for olefin polymerization and polyolefin Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 43
- 239000003446 ligand Substances 0.000 title claims abstract description 41
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- 239000004711 α-olefin Substances 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- -1 chloro, methyl Chemical group 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 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 claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 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 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052735 hafnium Chemical group 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 13
- 229920006124 polyolefin elastomer Polymers 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000003780 insertion Methods 0.000 abstract description 7
- 230000037431 insertion Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 70
- 150000001875 compounds Chemical class 0.000 description 69
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 31
- 238000001914 filtration Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007818 Grignard reagent Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 150000004795 grignard reagents Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
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- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
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- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 230000006837 decompression Effects 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QGEFGPVWRJCFQP-UHFFFAOYSA-M magnesium;methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC=C1 QGEFGPVWRJCFQP-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
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Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the technical field of olefin polymerization catalysts, in particular to a [ NOON ] tetradentate ligand fourth subgroup metal complex, a catalyst for olefin polymerization and a preparation method of polyolefin. The complex provided by the invention is used for catalyzing the polymerization of ethylene and/or alpha-olefin, and can obtain the polyolefin elastomer with high molecular weight and high copolymerization insertion rate. The catalyst for olefin polymerization provided by the invention takes the complex as a main catalyst, has high catalytic activity and polymer structure controllability, and has low cocatalyst consumption, and polyolefin elastomer (POE) can be prepared by high-activity catalytic copolymerization of ethylene and alpha-olefin through optimizing catalyst substituent groups and polymerization conditions. In the experiment of the invention, the olefin polymerization catalyst using the [ NOON ] tetradentate ligand fourth subgroup metal complex of the invention as a main catalyst is used for preparing polyolefin, and the insertion rate is as high as 11.5mol%.
Description
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, in particular to a [ NOON ] tetradentate ligand fourth subgroup metal complex, a catalyst for olefin polymerization and a preparation method of polyolefin.
Background
Polyolefin materials, such as polyethylene, polypropylene and ethylene/alpha-olefin copolymers, have many excellent properties, such as good chemical stability, corrosion resistance, harmlessness, low cost, etc. In the current industrial production, polyolefin products have a large specific gravity. For example, polyolefin elastomer (POE) is a thermoplastic elastomer produced by copolymerizing ethylene and an alpha-olefin, wherein the crystalline region of the polyethylene chain (resin phase) functions as a physical crosslinking point, has typical plastic properties, and after adding a certain amount of alpha-olefin (1-butene, 1-hexene, 1-octene, etc.), weakens the crystalline region of the polyethylene chain, forms an amorphous region exhibiting rubber elasticity (rubber phase), and gives the product the properties of an elastomer. POE has the dual characteristics of plastic and rubber and excellent comprehensive performance, so POE can be regarded as a bridge product of plastic and rubber.
The development of new polyolefin materials is closely related to the innovation of catalysts, and the appearance of Z-N catalysts enables polyethylene and polypropylene to be widely produced and applied; the advent of Methylaluminoxane (MAO) in the 80 s of the 20 th century has led to the application of metallocene catalysts in the industrial production of polyolefins, but the preparation process of metallocene catalysts is severe, which results in higher production cost of metallocene polyolefins, while non-metallocene catalysts with lower cost are becoming hot spots for polyolefin catalyst research in recent years.
The non-metallocene tridentate binuclear titanium catalyst disclosed by the invention in CN201410393654.5 can catalyze ethylene polymerization and ethylene and alpha-olefin copolymerization with high activity under the activation of MMAO to obtain a polymer with relatively high Mw and relatively narrow MWD, but the catalyst has poor catalytic life.
The modified high-efficiency Ziegler-Natta catalyst provided by CN101885793A can catalyze the polymerization of ethylene and alpha-olefin, but the catalyst has poor thermal stability and low copolymerization insertion rate of catalyzing ethylene and alpha-olefin, so that the novel non-metallocene catalyst is necessary to be continuously developed, the polymerization activity is improved, and the controllable production of the polymer structure is realized.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a [ NOON ] tetradentate ligand fourth subgroup metal complex, a catalyst for olefin polymerization and a method for preparing polyolefin, wherein the [ NOON ] tetradentate ligand fourth subgroup metal complex provided by the present invention is used for catalyzing polymerization of ethylene and/or α -olefin to obtain a polyolefin elastomer with high molecular weight and high copolymerization insertion rate.
The invention provides a [ NOON ] tetradentate ligand fourth subgroup metal complex, which has the structure of formula (I):
Wherein, R 1、R2 and R 3 are independently hydrogen, halogen, alkyl of C 1～C20, cycloalkyl of C 1～C20, alkoxy of C 1～C10, perfluoroalkyl of C 1～C10, phenyl, or substituted phenyl;
X is halogen, methyl or benzyl;
And M is a fourth subgroup transition metal.
Preferably, R 1 and R 2 of the present invention are independently hydrogen, fluoro, chloro, methyl, methoxy, trifluoromethyl, isopropyl, tert-butyl, phenyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl; r 3 is hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl or phenyl. In certain embodiments of the invention, R 1 and R 2 are independently hydrogen, methyl or tert-butyl; and R 3 is hydrogen, methyl, ethyl, isopropyl or cyclohexyl. Preferably, X in the present invention is chlorine, bromine or methyl. In certain embodiments of the invention, X is chloro or methyl. Preferably, M in the present invention is titanium, zirconium or hafnium.
In certain embodiments of the present invention, the complex having the structure of formula (I) is specifically a complex having the structure shown in F1-F10:
f1: r 1 = hydrogen, R 2 = hydrogen, R 3 = methyl, M = Ti, X = methyl;
F2: r 1 = hydrogen, R 2 = methyl, R 3 = ethyl, M = Ti, X = Cl;
F3: r 1 =methyl, R 2 =hydrogen, R 3 =hydrogen, m=zr, x=methyl;
F4: r 1 = methyl, R 2 = hydrogen, R 3 = ethyl, M = Zr, X = methyl;
And F5: r 1 = tert-butyl, R 2 = methyl, R 3 = isopropyl, M = Zr, X = Cl;
f6: r 1 = methyl, R 2 = tert-butyl, R 3 = cyclohexyl, M = Zr, X = methyl;
F7: r 1 = methyl, R 2 = hydrogen, R 3 = isopropyl, M = Hf, X = methyl;
F8: r 1 =methyl, R 2 =hydrogen, R 3 =ethyl, m=hf, x=cl;
F9: r 1 = hydrogen, R 2 = tert-butyl, R 3 = cyclohexyl, M = Hf, X = methyl;
F10: r 1 = methyl, R 2 = methyl, R 3 = cyclohexyl, M = Hf, X = Cl.
The invention provides a preparation method of the [ NOON ] tetradentate ligand fourth subgroup metal complex, which comprises the following steps:
S1) reacting a compound with a structure shown in a formula A with CH 3OCH2 Cl to obtain a compound with a structure shown in a formula B;
Wherein, R 1 and R 2 are the same as R 1 and R 2 in the [ NOON ] tetradentate ligand fourth subgroup metal complex, and are not described again;
S2) reacting the compound with the structure shown in the formula C with the compound with the structure shown in the formula B obtained in the step S1) to obtain a compound with the structure shown in the formula D;
Wherein, R 3 is the same as R 3 in the [ NOON ] tetradentate ligand fourth subgroup metal complex, and is not described in detail;
S3) carrying out heating reflux reaction on the compound with the structure shown in the formula D and obtained in the step S2) to obtain a compound with the structure shown in the formula E;
S4) MG 4 and the compound with the structure shown in the formula E obtained in the step S3) are subjected to the reaction to obtain a compound with the structure shown in the formula F;
Wherein, M in the MG 4 is the same as M in the [ NOON ] tetradentate ligand fourth subgroup metal complex, and is not described in detail; g in the MG 4 is halogen, specifically chlorine or bromine; x in the compound with the structure shown in the formula F is the same as X in the [ NOON ] tetradentate ligand fourth subgroup metal complex, and is not repeated.
Firstly, reacting a compound with a structure shown in a formula A with CH 3OCH2 Cl to obtain a compound with a structure shown in a formula B; specifically, the method comprises the steps of reacting a compound with a structure shown in a formula A with a catalyst in a solvent under anhydrous and anaerobic conditions, adding CH 3OCH2 Cl into the reaction product, and sequentially filtering, extracting and drying the reaction product to obtain the compound with the structure shown in the formula B. The temperature of the reaction is room temperature, specifically 25 ℃, the reaction time is 2 hours, and in certain embodiments of the invention, the reaction amount of the compound of the structure shown in formula a is 1.0 to 2.0 equivalents, preferably 1.0 equivalents; the reaction amount of CH 3OCH2 Cl is 1.0-2.5 equivalents, preferably 1.1 equivalents; the equivalent weight of the catalyst is 1.0 to 2.0 equivalents, preferably 1.1 equivalents. In certain embodiments of the invention, the catalyst is NaH and the solvent is THF.
After the compound with the structure shown in the formula B is obtained, the compound with the structure shown in the formula C and the obtained compound with the structure shown in the formula B are reacted to obtain the compound with the structure shown in the formula D. Specifically, a compound having a structure represented by formula C and the obtained compound having a structure represented by formula B are reacted in a solvent under a protective gas atmosphere, and then dried and recrystallized in this order to obtain a compound having a structure represented by formula D. The reaction amount of the compound of the structure represented by formula C of the present invention is 1.0 to 1.5 equivalents, preferably 1.1 equivalents. The reaction amount of the compound of the structure shown in the formula B is 2.0 equivalents. The temperature of the reaction is room temperature, and the room temperature is the same as the above temperature and is not repeated; the reaction time was 2h. In certain embodiments of the present invention, the shielding gas of the present invention is nitrogen; the solvent is THF.
After the compound with the structure shown in the formula D is obtained, the obtained compound with the structure shown in the formula D is subjected to a heating reflux reaction to obtain the compound with the structure shown in the formula E. Specifically, the obtained compound of the structure shown in the formula D and hydrochloric acid are subjected to heating reflux reaction in a solvent, and then are sequentially dried and recrystallized to obtain the compound of the structure shown in the formula E. The reaction amount of the compound of the structure represented by formula D of the present invention is 1.0 equivalent. The reaction amount of the hydrochloric acid is 6.0 equivalents. The temperature of the heating reflux reaction is 120 ℃ and the time is 3 hours.
After the compound with the structure shown in the formula E is obtained, MG 4 and the obtained compound with the structure shown in the formula E are subjected to the preparation method to obtain the compound with the structure shown in the formula F. Specifically, under anhydrous and anaerobic conditions, MG 4 and the obtained compound with the structure shown in the formula E are dissolved in a solvent at low temperature, a Grignard reagent is added or not added, and then the reaction is carried out for 1h at room temperature, so that the compound with the structure shown in the formula F is obtained. More specifically, if the Grignard reagent is added, the reaction is carried out for 1h at a low temperature after the Grignard reagent is added; the grignard reagent is a methylated grignard reagent, such as methyl magnesium bromide diethyl ether, or the grignard reagent is a benzylated grignard reagent, such as benzyl magnesium bromide. The reaction amount of the MG 4 is 1.0 equivalent; the reaction amount of the compound of the structure shown in the formula E is 1.0 equivalent. In the present invention, the Grignard reagent is added in an amount of 4.0 to 4.5 equivalents, preferably 4.4 equivalents. In certain embodiments of the invention, the low temperature is-35 ℃; the room temperature is the same as above, and will not be described again. In certain embodiments of the invention, the solvent is toluene.
The synthesis of the [ NOON ] tetradentate ligand fourth subgroup metal complex of the present invention is not limited to the aforementioned preparation method, and one skilled in the art may synthesize the [ NOON ] tetradentate ligand fourth subgroup metal complex by different methods according to existing chemical knowledge.
The invention also provides a catalyst for olefin polymerization, which comprises a main catalyst and a cocatalyst; the main catalyst comprises the [ NOON ] tetradentate ligand fourth subgroup metal complex.
In particular, the cocatalysts of the present invention are selected from one or more of modified or unmodified alkylaluminoxane, alkylaluminum, organoboron or organoborate. Preferably, the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, triisobutylaluminum, trioctylaluminum, perfluorophenyl boron, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dioctadecyl-methylammonium tetrakis (pentafluorophenyl) borate. In certain embodiments of the invention, the molar ratio of aluminum atoms in the promoter, boron atoms in the promoter, to metal atoms in the procatalyst is (5-1000): 0:1, or 0: (1-5): 1, or (5-1000): (1-5): 1, a step of; when boron-containing cocatalysts are used in the present invention, the use of aluminum-containing cocatalysts in combination is advantageous for impurity removal.
The invention also provides a preparation method of polyolefin, which comprises the following steps:
polymerizing at least one of ethylene or alpha-olefin under the action of a catalyst to obtain polyolefin;
the catalyst is the same as the catalyst for olefin polymerization, and will not be described in detail.
The polymerization of the invention is specifically to homopolymerize ethylene under the action of a catalyst; or alpha-olefin is homopolymerized under the action of a catalyst; or copolymerizing ethylene and alpha-olefin under the action of a catalyst; the temperature of the homo-polymerization or the copolymerization is 50-150 ℃, and the homo-polymerization or the copolymerization is carried out under the pressure of 0.1-5 MPa; the alpha-olefin is selected from one of propylene, 1-butene, 1-hexene, 1-octene and 1-decene. More specifically, the polymerization of the present invention is carried out in saturated alkanes; the saturated alkane is selected from one of n-pentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane, n-octane and isooctane.
When the preparation method of the polyolefin provided by the invention adopts a solution polymerization process to prepare the polymer, n-pentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane, n-octane and isooctane can be selected as solvents according to the needs. At least one of ethylene or alpha-olefin is polymerized under the action of a catalyst, wherein the polymerization temperature is 50-150 ℃, preferably 80-150 ℃, more preferably 100-150 ℃; the present invention pertains to solution polymerizations carried out at a pressure of 0.1 to 5MPa, preferably 1.5 to 5.0MPa, more preferably 3.5 to 5.0 MPa.
According to the different factors such as the catalyst, the monomer type and concentration, the reaction temperature and the like, the polymerization reaction time can be greatly different, and the copolymerization reaction of ethylene and 1-octene can take 5-30 minutes. In certain embodiments of the invention, the specific process of the invention for catalyzing the copolymerization of ethylene with 1-octene is: in the presence of ethylene, adding comonomer, main catalyst and cocatalyst into polymerization kettle, stirring at 50-150 deg.c for 5-30 min, and adding proper amount of ethanol to terminate the copolymerization. And cooling the reaction system to room temperature, filtering, and drying in vacuum to constant weight to obtain the polymer.
The invention provides a [ NOON ] tetradentate ligand fourth subgroup metal complex, a catalyst for olefin polymerization and a preparation method of polyolefin. The [ NOON ] tetradentate ligand fourth subgroup metal complex provided by the invention is used for catalyzing the polymerization of ethylene and/or alpha-olefin, so that the polyolefin elastomer with high molecular weight and high copolymerization insertion rate can be obtained. The catalyst for olefin polymerization provided by the invention takes the [ NOON ] tetradentate ligand fourth subgroup metal complex as a main catalyst, has high catalytic activity and polymer structure controllability, and has low cocatalyst consumption, and polyolefin elastomer (POE) can be prepared by high-activity catalytic copolymerization of ethylene and alpha-olefin through optimizing catalyst substituent groups and polymerization conditions. In the experiment of the invention, the olefin polymerization catalyst using the [ NOON ] tetradentate ligand fourth subgroup metal complex of the invention as a main catalyst is used for preparing polyolefin, and the insertion rate is as high as 11.5mol%.
Detailed Description
The invention discloses a [ NOON ] tetradentate ligand fourth subgroup metal complex, a catalyst for olefin polymerization and a preparation method of polyolefin. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a synthesis method of [ NOON ] tetradentate ligand fourth subgroup metal complex, which comprises the following specific synthetic route:
The specific preparation process of the novel polyolefin elastomer catalyst provided by the invention comprises the following steps:
(1) General procedure for ligand Synthesis
Under anhydrous and anaerobic conditions, 1.0-2.0 equivalents (preferably 1.0 equivalent) of compound A is weighed, a proper amount of THF is added for full dissolution, then 1.0-2.0 equivalents (preferably 1.1 equivalents) of NaH is added for reaction for 2 hours at room temperature, 1.0-2.5 equivalents of CH 3OCH2 Cl (preferably 1.1 equivalents) is added, the obtained mixture is filtered, after the filtrate is dried in a spinning way, dichloromethane and water are added for extraction, an organic phase is collected, anhydrous magnesium sulfate is dried, and the compound B is obtained after the filtrate is dried in a spinning way.
2.0 Equivalents of B are dissolved in a proper amount of THF under nitrogen atmosphere, then 1.0 to 1.5 equivalents (preferably 1.1 equivalents) of compound C are added for reaction for 3 hours at room temperature, after the reaction solution is dried by spinning, dichloromethane is added to dissolve the solid, n-hexane is added to recrystallize, and the solid compound D is obtained by filtration.
1.0 Equivalent of D is dissolved in a proper amount of THF, 6.0 equivalent of hydrochloric acid is added, the mixture is heated and refluxed for 1 hour, extraction is carried out by using ethyl acetate/water, the organic phase is dried and filtered, the solvent is pumped out, the solid is dissolved by a proper amount of dichloromethane, normal hexane is added for recrystallization, and the ligand compound E is obtained by filtration.
(2) General procedure for Complex Synthesis
Under anhydrous and anaerobic conditions, 1.0 equivalent of MCl 4 powder is weighed, a proper amount of toluene is added and stirred uniformly, the mixture is cooled to minus 35 ℃, 1.0 equivalent of ligand E is weighed, a proper amount of toluene is added and stirred uniformly, then the mixture is added into toluene solution of MCl 4, stirring is continued for 30min at low temperature, at this time, 4.0 to 4.5 equivalents of methyl magnesium bromide diethyl ether solution (preferably 4.4 equivalents) are slowly dripped into the system, the mixture is reacted for 1h at low temperature, the mixture is slowly warmed to room temperature, the reaction is continued for 1h at room temperature, a toluene solvent is pumped out by an oil pump in vacuum, a proper amount of toluene is added to dissolve the mixture, insoluble matters are removed by filtration, the filtrate is stirred rapidly, n-hexane is added dropwise until precipitation is generated, the mixture is frozen to minus 25 ℃ for about 2h, more white crystalline solid is separated out, the mixture is filtered, and colorless crystalline metal complex is obtained, and the mixture is placed into an oil bath pot at 60 ℃ and the solvent is pumped out in vacuum for 3h, and the obtained complex F.
The preparation of the [ NOON ] tetradentate ligand fourth subgroup metal complex of the present invention having the structure of formula (I) is performed according to the above-described method, specifically involving the preparation of complex F1, complex F3, complex F7, and complex F9:
Wherein, for complex F1, R 1 =hydrogen, R 2 =hydrogen, R 3 =methyl, m=ti, x=methyl;
For complex F3, R 1 =methyl, R 2 =hydrogen, R 3 =hydrogen, m=zr, x=methyl;
For complex F7, R 1 =methyl, R 2 =hydrogen, R 3 =isopropyl, m=hf, x=methyl;
For complex F9, R 1 =hydrogen, R 2 =tert-butyl, R 3 =cyclohexyl, m=hf, x=methyl;
the invention is further illustrated by the following examples:
Example 1
The synthesis of complex F1 was performed according to the following synthetic route:
(1) Synthesis of ligand E1
Under anhydrous and anaerobic conditions, weighing 10mmol of compound A1, adding a proper amount of THF for full dissolution, adding 11mmol of NaH, reacting for 2 hours at room temperature, adding 11mmol of CH 3OCH2 Cl, filtering the obtained mixture, spin-drying the filtrate, adding dichloromethane and water for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and spin-drying to obtain the compound B1.
Under nitrogen atmosphere, weighing and dissolving 6mmol of compound B1 in a proper amount of THF, then adding 6.6mmol of compound C1, reacting for 3 hours at room temperature, spin-drying the reaction liquid, adding dichloromethane to dissolve the solid, adding n-hexane to recrystallize, and filtering to obtain a solid compound D1.
2Mmol of compound D1 is weighed and dissolved in a proper amount of THF, 12mmol of hydrochloric acid is added, the mixture is heated and refluxed for 1h, extraction is carried out by using ethyl acetate/water, the organic phase is dried and filtered, the solvent is pumped out, the solid is dissolved by a proper amount of dichloromethane, normal hexane is added for recrystallization, and the ligand compound E1 is obtained by filtration.
(2) Synthesis of Complex F1
Under anhydrous and anaerobic conditions, weighing 10mmol of TiCl 4 powder, adding a proper amount of toluene, stirring uniformly, cooling to-35 ℃, simultaneously weighing 10mmol of ligand compound E1, adding a proper amount of toluene, stirring uniformly, adding into a toluene solution of TiCl 4, continuously stirring at low temperature for 30min, slowly dripping 44mmol of methyl magnesium bromide diethyl ether solution into the system, reacting at low temperature for 1h, slowly heating to room temperature, continuously reacting at room temperature for 1h, pumping toluene solvent by an oil pump in vacuum, adding toluene to dissolve the complex, filtering to remove insoluble matters, rapidly stirring filtrate, dropwise adding n-hexane into the filtrate until precipitation is generated, freezing to-25 ℃ for about 2h, precipitating more white crystalline solid, filtering to obtain colorless crystalline metal complex, placing the colorless crystalline metal complex into an oil bath at 60 ℃, pumping for 3h to pump solvent to obtain 2.48g of complex F1, and obtaining the yield: 52.8%, theoretical value of elemental analysis: c,63.84; h,6.43; n,5.96; elemental analysis actual measurement: c:63.72; h:6.63; n:5.56.
Example 2
The synthesis of complex F3 was performed according to the following synthetic route:
(1) Synthesis of ligand E3:
under anhydrous and anaerobic conditions, weighing 10mmol of compound A3, adding a proper amount of THF for full dissolution, adding 11mmol of NaH, reacting for 2 hours at room temperature, adding 11mmol of CH 3OCH2 Cl, filtering the obtained mixture, spin-drying the filtrate, adding dichloromethane and water for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and spin-drying to obtain the compound B3.
Under nitrogen atmosphere, weighing 6mmol of compound B3, dissolving in a proper amount of THF, then adding 6.6mmol of compound C3, reacting for 3 hours at room temperature, spin-drying the reaction liquid, adding dichloromethane to dissolve the solid, adding n-hexane to recrystallize, and filtering to obtain a solid compound D3.
2Mmol of compound D3 is weighed and dissolved in a proper amount of THF, 12mmol of hydrochloric acid is added, the mixture is heated and refluxed for 1h, extraction is carried out by using ethyl acetate/water, the organic phase is dried and filtered, the solvent is pumped out, the solid is dissolved by a proper amount of dichloromethane, normal hexane is added for recrystallization, and the ligand compound E3 is obtained by filtration.
(2) Synthesis of Complex F3
Under anhydrous and anaerobic conditions, weighing 10mmol of ZrCl 4 powder, adding a proper amount of toluene, stirring uniformly, cooling to-35 ℃, simultaneously weighing 10mmol of ligand E3, adding a proper amount of toluene, stirring uniformly, adding into HfCl 4 toluene solution, continuously stirring at low temperature for 30min, slowly dripping 44mmol of methyl magnesium bromide diethyl ether solution into the system, reacting at low temperature for 1h, slowly heating to room temperature, continuously reacting at room temperature for 1h, pumping toluene solvent by an oil pump in vacuum, adding toluene to dissolve the complex, filtering to remove insoluble matters, rapidly stirring filtrate, dropwise adding n-hexane into the filtrate until precipitation is generated, freezing to-25 ℃ for about 2h, precipitating more white crystalline solid, filtering to obtain colorless crystalline metal complex, placing the colorless crystalline metal complex into an oil bath at 60 ℃, pumping for 3h to pump the solvent to obtain 3.40g of complex F3, and obtaining the yield: 66.2%. Theoretical value of elemental analysis: c,58.45; h,5.89; n,5.45; elemental analysis actual measurement: c:58.55; h:5.76; n:5.87.
Example 3
The synthesis of complex F7 was performed according to the following synthetic route:
(1) Synthesis of ligand E7:
Under anhydrous and anaerobic conditions, weighing 10mmol of compound A7, adding a proper amount of THF for full dissolution, adding 11mmol of NaH, reacting for 2 hours at room temperature, adding 11mmol of CH 3OCH2 Cl, filtering the obtained mixture, spin-drying the filtrate, adding dichloromethane and water for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and spin-drying to obtain the compound B7.
Under nitrogen atmosphere, weighing and dissolving 6mmol of compound B7 in a proper amount of THF, then adding 6.6mmol of compound C7, reacting for 3 hours at room temperature, spin-drying the reaction liquid, adding dichloromethane to dissolve the solid, adding n-hexane to recrystallize, and filtering to obtain a solid compound D7.
2Mmol of compound D7 is weighed and dissolved in a proper amount of THF, 12mmol of hydrochloric acid is added, the mixture is heated and refluxed for 1h, extraction is carried out by using ethyl acetate/water, the organic phase is dried and filtered, the solvent is pumped out, the solid is dissolved by a proper amount of dichloromethane, normal hexane is added for recrystallization, and the ligand compound E7 is obtained by filtration.
(2) Synthesis of Complex F7
Under anhydrous and anaerobic conditions, weighing 10mmol of HfCl 4 powder, adding a proper amount of toluene, stirring uniformly, cooling to-35 ℃, simultaneously weighing 10mmol of ligand compound E7, adding a proper amount of toluene, stirring uniformly, adding into a toluene solution of HfCl 4, continuously stirring at low temperature for 30min, slowly dripping 44mmol of methyl magnesium bromide diethyl ether solution into the system, reacting at low temperature for 1h, slowly heating to room temperature, continuously reacting at room temperature for 1h, pumping toluene solvent by an oil pump in vacuum, adding toluene to dissolve the complex, filtering to remove insoluble matters, rapidly stirring filtrate, dropwise adding n-hexane into the filtrate until precipitation is generated, freezing to-25 ℃ for about 2h, precipitating more white crystalline solid, filtering to obtain colorless crystalline metal complex, placing the colorless crystalline metal complex into an oil bath at 60 ℃, pumping for 3h to pump the solvent to obtain 3.41g of complex F7, and obtaining the yield: 49.8%, theoretical value of elemental analysis: c,54.34; h,6.18; n,4.09; elemental analysis actual measurement: : c:55.02; h:6.27; n:4.56.
Example 4
The synthesis of complex F9 was performed according to the following synthetic route:
(1) Synthesis of ligand E9:
Under anhydrous and anaerobic conditions, weighing 10mmol of compound A9, adding a proper amount of THF for full dissolution, adding 11mmol of NaH, reacting for 2 hours at room temperature, adding 11mmol of CH 3OCH2 Cl, filtering the obtained mixture, spin-drying the filtrate, adding dichloromethane and water for extraction, collecting an organic phase, drying by anhydrous magnesium sulfate, and spin-drying to obtain the compound B9.
Under nitrogen atmosphere, weighing 6mmol of compound B9, dissolving in a proper amount of THF, then adding 6.6mmol of compound C9, reacting for 3 hours at room temperature, spin-drying the reaction liquid, adding dichloromethane to dissolve the solid, adding n-hexane to recrystallize, and filtering to obtain a solid compound D9.
2Mmol of compound D9 is weighed and dissolved in a proper amount of THF, 12mmol of hydrochloric acid is added, the mixture is heated and refluxed for 1h, extraction is carried out by using ethyl acetate/water, the organic phase is dried and filtered, the solvent is pumped out, the solid is dissolved by a proper amount of dichloromethane, normal hexane is added for recrystallization, and the ligand compound E9 is obtained by filtration.
(2) Synthesis of Complex F9
Under anhydrous and anaerobic conditions, weighing 10mmol of HfCl 4 powder, adding a proper amount of toluene, stirring uniformly, cooling to-35 ℃, simultaneously weighing 10mmol of ligand compound E9, adding a proper amount of toluene, stirring uniformly, adding into a toluene solution of HfCl 4, continuously stirring at low temperature for 30min, slowly dripping 44mmol of methyl magnesium bromide diethyl ether solution into the system, reacting at low temperature for 1h, slowly heating to room temperature, continuously reacting at room temperature for 1h, pumping toluene solvent by an oil pump in vacuum, adding toluene to dissolve the complex, filtering to remove insoluble matters, rapidly stirring filtrate, dropwise adding n-hexane into the filtrate until precipitation is generated, freezing to-25 ℃ for about 2h, precipitating more white crystalline solid, filtering to obtain colorless crystalline metal complex, placing the colorless crystalline metal complex into an oil bath at 60 ℃, pumping for 3h to pump the solvent to obtain 4.08g of complex F9, and obtaining the yield: 45.9% of elemental analysis theory: c,55.31; h,6.34; n,3.15; elemental analysis actual measurement: : c:61.88; h:7.18; n:3.52.
Example 5
The 500mL high-pressure reaction kettle is dried in vacuum for 2 hours in advance, the kettle temperature is regulated to the polymerization temperature, ethylene gas is set to be 0.3MPa, 200mL of n-heptane and 70mL of 1-octene are firstly added, then 0.5Mmol of Methylaluminoxane (MMAO) is added, the temperature in the kettle is increased to 120 ℃, the ethylene pressure is regulated to be 2.5MPa after the temperature is increased to 120 ℃,2 mu mol of toluene solution of a main catalyst F3 is injected, the polymerization is carried out for 10 minutes, ethanol is added for quenching, the polymer is discharged from the bottom of the kettle after decompression, the obtained polymerization reaction liquid is poured into 500mL of ethanol, white solid is obtained through stirring, and the mixture is filtered, and is dried to constant weight in a vacuum oven, thus 6.46g of polymer is obtained. GPC measured molecular weight and molecular weight distribution gave 1-octene insertion by high temperature carbon spectroscopy (see Table 1 for details).
Example 6
The polymerization results were shown in Table 1, except that the main catalyst F3 was changed to F7 and the conditions were the same as those in example 5.
Example 7
The polymerization results were shown in Table 1, except that the main catalyst F3 was changed to F9 and the conditions were the same as those in example 5.
Example 8
Methyl Aluminoxane (MMAO) was changed to triisobutyl aluminum/triphenylcarbonium tetrakis (pentafluorophenyl) borate complex in which triisobutyl aluminum was 0.5mmol and triphenylcarbonium tetrakis (pentafluorophenyl) borate was 3. Mu. Mol, and the polymerization results were as described in Table 1, except that the conditions were the same as in example 5.
Example 9
The methylaluminoxane (MMAO) was changed to trioctylaluminum/N, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate complex, wherein trioctylaluminum was 0.5mmol, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate was 3. Mu. Mol, and the other conditions were in accordance with example 7, and the polymerization results are detailed in Table 1.
Example 10
The polymerization results are shown in Table 1, except that n-heptane is changed to n-hexane and the conditions are the same as in example 6.
Example 11
70ML of 1-octene was changed to 60mL of 1-hexene, and the other conditions were the same as in example 5, and the polymerization results were shown in Table 1.
Example 12
The polymerization temperature was changed from 120℃to 140℃and the other conditions were the same as in example 6, and the polymerization results are shown in Table 1.
Example 13
The polymerization pressure was changed from 2.5MPa to 3.5MPa, and the other conditions were the same as in example 6, and the polymerization results are shown in Table 1.
TABLE 1 ethylene/alpha-olefin copolymerization data
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A [ NOON ] tetradentate ligand fourth subgroup metal complex characterized in that it has the structure of formula (I):
Wherein, R 1、R2 and R 3 are independently hydrogen, halogen, alkyl of C 1～C20, cycloalkyl of C 1～C20, alkoxy of C 1～C10, perfluoroalkyl of C 1～C10, phenyl, or substituted phenyl;
X is halogen, methyl or benzyl;
And M is a fourth subgroup transition metal.
2. The complex of claim 1, wherein R 1 and R 2 are independently hydrogen, fluoro, chloro, methyl, methoxy, trifluoromethyl, isopropyl, t-butyl, phenyl, 3, 5-dimethylphenyl or 3, 5-di-t-butylphenyl;
R 3 is hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl or phenyl.
3. The complex of claim 1, wherein X is chloro, bromo or methyl;
and M is titanium, zirconium or hafnium.
4. The complex according to claim 1, wherein the complex having the structure of formula (I) is specifically a complex having the structure shown by the following F1 to F10:
f1: r 1 = hydrogen, R 2 = hydrogen, R 3 = methyl, M = Ti, X = methyl;
F2: r 1 = hydrogen, R 2 = methyl, R 3 = ethyl, M = Ti, X = Cl;
F3: r 1 =methyl, R 2 =hydrogen, R 3 =hydrogen, m=zr, x=methyl;
F4: r 1 = methyl, R 2 = hydrogen, R 3 = ethyl, M = Zr, X = methyl;
And F5: r 1 = tert-butyl, R 2 = methyl, R 3 = isopropyl, M = Zr, X = Cl;
f6: r 1 = methyl, R 2 = tert-butyl, R 3 = cyclohexyl, M = Zr, X = methyl;
F7: r 1 = methyl, R 2 = hydrogen, R 3 = isopropyl, M = Hf, X = methyl;
F8: r 1 =methyl, R 2 =hydrogen, R 3 =ethyl, m=hf, x=cl;
F9: r 1 = hydrogen, R 2 = tert-butyl, R 3 = cyclohexyl, M = Hf, X = methyl;
F10: r 1 = methyl, R 2 = methyl, R 3 = cyclohexyl, M = Hf, X = Cl.
5. A catalyst for olefin polymerization, characterized in that it comprises a main catalyst and a cocatalyst;
The procatalyst comprising the [ NOON ] tetradentate ligand fourth subgroup metal complex according to any one of claims 1-4.
6. The catalyst for olefin polymerization according to claim 5, wherein the cocatalyst is selected from one or more of modified or unmodified alkylaluminoxane, alkylaluminum, organoboron or organoborate.
7. The catalyst for olefin polymerization according to claim 6, wherein the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, triisobutylaluminum, trioctylaluminum, perfluorophenyl boron, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dioctadecyl-methylammonium tetrakis (pentafluorophenyl) borate.
8. The catalyst according to claim 6, wherein the molar ratio of aluminum atoms in the cocatalyst, boron atoms in the cocatalyst to metal atoms in the main catalyst is (5-1000): 0:1, or 0: (1-5): 1, or (5-1000): (1-5): 1.
9. A process for the preparation of a polyolefin, characterized by the steps of:
polymerizing at least one of ethylene or alpha-olefin under the action of a catalyst to obtain polyolefin;
The catalyst comprises a main catalyst and a cocatalyst; the procatalyst comprising the [ NOON ] tetradentate ligand fourth subgroup metal complex according to any one of claims 1-4.
10. The method of claim 9, wherein the polymerization temperature is 50-150 ℃;
the polymerization is carried out at a pressure of 0.1 to 5MPa.
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