CN115894573A - Constrained geometry nitrogen-containing side arm metallocene indene metal derivative and synthesis method thereof - Google Patents
Constrained geometry nitrogen-containing side arm metallocene indene metal derivative and synthesis method thereof Download PDFInfo
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- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 29
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 94
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000005264 aryl amine group Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZWELHCJHLNGACT-UHFFFAOYSA-N 1H-indene titanium Chemical compound [Ti].C1C=CC2=CC=CC=C12 ZWELHCJHLNGACT-UHFFFAOYSA-N 0.000 description 3
- JHCDJGLUISUZEH-UHFFFAOYSA-N C(C)(C)(C)N.[Li] Chemical compound C(C)(C)(C)N.[Li] JHCDJGLUISUZEH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical class [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- FUXWSNBUHAEWQU-UHFFFAOYSA-N [Li].[Li].[Li] Chemical compound [Li].[Li].[Li] FUXWSNBUHAEWQU-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SXEBSPSTEUQPJM-UHFFFAOYSA-N oxolane;titanium Chemical compound [Ti].C1CCOC1 SXEBSPSTEUQPJM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention provides a constrained geometry nitrogen-containing side arm metallocene indene metal derivative and a synthesis method thereof, belonging to the technical field of olefin polymerization catalysts. The synthesis method comprises the following steps: 1) Under the protection of inert gas, lithium salt of a compound with a structure shown in a formula (I-1) and a compound with a structure shown in a formula (I-2) react in a first solvent to obtain a reaction solution containing the compound with the structure shown in the formula (II-1); 2) Adding lithium salt of a compound with a structure shown in a formula (II-2) into the reaction solution obtained in the step 1) for reaction, and then adding alkyl lithium for reaction to obtain reaction solution containing dilithium salt of the compound with the structure shown in the formula (III-1); 3) Adding metal salt into the reaction liquid obtained in the step 2), and simultaneously adding a second solvent for reaction to obtain an indene metallocene compound with a structure shown in a formula (III-2); the process effectively simplifies the reaction process and improves the product purity.
Description
Technical Field
The invention belongs to an olefin polymerization catalyst, and particularly relates to a constrained geometry nitrogen-containing side arm metallocene indene metal derivative and a synthesis method thereof.
Background
Polyolefin resins are widely used in various fields of daily life and industrial production. As an organic material, the material has the advantages of strong corrosion resistance, stable structural performance, easy processing and the like. At present, the demand of polyolefin resin products in China is huge and increased every year, and industrial production is facing the process transition from the traditional Z-N catalytic olefin polymerization technology to the metallocene catalytic olefin polymerization technology.
Compared with the Z-N catalyst, the metallocene catalyst has the advantages of single active center, high catalytic activity, narrow polymer molecular weight distribution, good copolymerization performance and the like. In the process of metallocene catalyst development, non-bridged bis-metallocenes, mono-metallocenes and Constrained Geometry (CGC) metallocene catalysts have been used in turn.
Among them, typical CGC metallocenes are excellent in performance in catalyzing homopolymerization and copolymerization of ethylene, and metallocene catalysts have also been developed from conventional cyclopentadiene derivatives to metallocene indene and metallocene fluorene derivatives. The production technology development of CGC metallocenes and the application of catalytic olefin polymerization were carried out by Dow and Exxon companies for the first time. For example, jerzy K (Jerzy K, nickias P N, join S, et al. Substitated group 4metal compounds, catalysts and therefor polymerization processes, EP1253158A1[ P ]. 2112.) in 2112; the group of (J Klosin, WJ Kruper, PN Nickias, JT pattern, DR Wilson.3-heterologous protected cyclic-catalysis metallic complexes and olefin polymerization processes:, TW455595B [ P ]. 2111) reported the synthesis of constrained geometry nitrogen-containing pendant arm metallocene catalysts and used for the polymerization of ethylene and alpha-olefins with good polymerization results.
However, the above reaction conditions are severe, the preparation process is complicated, and a heavy metal salt PbCl is used 2 The use of trivalent titanium compound and heavy metal lead salt can pollute the environment. In addition, when the synthesis of the bulky metallocene ligand is carried out (for example, aryl substitution), isomers are easily generated in the intermediate, and certain difficulties exist in the purification of the ligand.
Disclosure of Invention
The invention provides a method for synthesizing a constrained geometry nitrogen-containing side arm metallocene indene metal derivative, which is characterized in that the constrained geometry nitrogen-containing side arm metallocene metal derivative is synthesized by controlling the reaction sequence, the reaction conditions and the like of all raw materials and adopting an in-situ preparation process and a one-pot reaction method of zirconium, titanium and other metal salts, so that the reaction process is effectively simplified, and the product purity is improved.
The invention provides a synthesis method of a constrained geometry nitrogen-containing side arm metallocene indene metal derivative, which comprises the following steps:
1) Under the protection of inert gas, lithium salt of a compound with a structure shown in a formula (I-1) and a compound with a structure shown in a formula (I-2) react in a first solvent to obtain a reaction solution containing the compound with the structure shown in the formula (II-1);
2) Adding lithium salt of a compound with a structure shown in a formula (II-2) into the reaction liquid obtained in the step 1) for reaction to obtain reaction liquid containing the compound with the structure shown in the formula (III-1), and adding alkyl lithium for reaction to obtain reaction liquid containing dilithium salt of the compound with the structure shown in the formula (III-1);
3) Adding metal salt into the reaction liquid obtained in the step 2), and simultaneously adding a second solvent for reaction to obtain an indene metallocene compound with a structure shown in a formula (III-2);
wherein the content of the first and second substances,
R 1 independently selected from nitrogen-containing groups, R 2 Independently selected from hydrogen, methyl;
R 3 、R 4 each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 5 independently selected from substituted or unsubstituted alkyl, aryl;
m is independently selected from titanium, zirconium, hafnium.
Further, R 1 Independently selected from nitrogenous alkyl groups or arylamine groups.
Further, the metal salt includes titanium tetrachlorobis (tetrahydrofuran), zirconium tetrachloride, or hafnium tetrachloride.
Further, the molar ratio of the lithium salt of the compound having the structure represented by the formula (I-1) to the compound having the structure represented by the formula (I-2) is 1:1-5.
Further, the molar ratio of the lithium salt of the compound having the structure represented by the formula (II-1) to the lithium salt of the compound having the structure represented by the formula (II-2) is 1:1-5;
preferably, the molar ratio of the compound having the structure represented by formula (III-1) to the alkyllithium is 1.
Further, the molar ratio of the dilithium salt to the metal salt of the compound having the structure represented by the formula (III-1) is 1:1-5.
Further, the first solvent comprises at least one of aromatic hydrocarbon, ether and alkane solvents;
preferably, the alkane solvent comprises at least one of toluene, tetrahydrofuran, diethyl ether and n-hexane;
more preferably, the alkane solvent is n-hexane;
the second solvent comprises tetrahydrofuran.
Further, in the step 1) and the step 2), the reaction temperature is-78-111 ℃;
in the step 3), the reaction temperature is-31-1 ℃.
Further, the inert gas includes at least one of nitrogen, helium, or argon.
The invention also provides a constrained geometry nitrogen-containing side arm metallocene catalyst derivative synthesized by any one of the synthesis methods.
The invention has the following advantages:
the production process of the metallocene indene metal derivative with the limited geometrical configuration and the nitrogen-containing side arm adopts a one-pot preparation technology, has simple route, does not need intermediate separation, effectively reduces required equipment, reduces equipment investment, and simultaneously obviously improves the purity of the obtained product. In addition, the production process has the advantages of cheap and easily-obtained raw materials, relatively mild reaction conditions, good reaction stability and selectivity, good atom economy and accordance with sustainable green chemistry.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic spectrum of a compound corresponding to Compound 4b prepared in comparative example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of a compound corresponding to Compound 5b prepared in comparative example 1 of the present invention;
FIG. 3 is a nuclear magnetic spectrum of a compound corresponding to Compound 4b prepared in example 2 of the present invention;
FIG. 4 NMR chart of a compound corresponding to Compound 5b prepared in example 2 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the prior art, a compound amino ligand with a structure shown in a formula (II-2) reacts with a compound with a structure shown in a formula (I-2) after being subjected to a reaction with a large steric hindrance, and then reacts with a compound with a structure shown in a formula (I-1), so that different isomers are easily generated, and the purification is difficult. And use of TiCl 3 (THF) 3 Reacting with lithium salt of compound with structure shown in formula (III-1), and adding PbCl 2 The oxidation of the trivalent titanium can be incomplete, byproducts are generated, and the heavy metal pollution problem exists.
One embodiment of the invention provides a method for synthesizing a constrained geometry nitrogen-containing side-arm metallocene indene metal derivative, which comprises the following steps:
1) Under the protection of inert gas, lithium salt of a compound with a structure shown in a formula (I-1) and a compound with a structure shown in a formula (I-2) react in a first solvent to obtain a reaction solution containing the compound with the structure shown in the formula (II-1);
2) Adding lithium salt of the compound with the structure shown in the formula (II-2) into the reaction solution obtained in the step 1) for reaction to obtain reaction solution containing the compound with the structure shown in the formula (III-1), and adding alkyl lithium for reaction to obtain reaction solution containing dilithium salt of the compound with the structure shown in the formula (III-1);
3) Adding metal salt into the reaction liquid obtained in the step 2), and simultaneously adding a second solvent for reaction to obtain an indene metallocene compound with a structure shown in a formula (III-2);
wherein, the first and the second end of the pipe are connected with each other,
R 1 independently selected from nitrogen-containing groups, R 2 Independently selected from hydrogen and methyl;
R 3 、R 4 each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 5 independently selected from substituted or unsubstituted alkyl, aryl;
m is independently selected from titanium, zirconium, hafnium.
The production process of the constrained geometry nitrogen-containing side arm metallocene metal derivative provided by the embodiment of the invention adopts a one-pot preparation technology, does not need intermediate separation, can greatly reduce required equipment, reduces equipment investment, and has certain industrial application value. The production process effectively solves the technical problem that the existing process is easy to produce by-products such as isomers and the like, and the obtained product has high purity.
The production process provided by the embodiment of the invention has cheap and easily obtained raw materials, and adopts cheap tetravalent metal salt MCl 4 (M = Ti, zr, hf), has a price advantage. For example, in the synthesis of the cyclopentadienyl titanium derivatives, tiCl is used 4 (THF) 2 Than TiCl 3 (THF) 3 Is cheaper, and simultaneously avoids the heavy metal oxidant PbCl 2 The subsequent heavy metal environmental pollution problem is avoided by using the method.
The production process provided by the embodiment of the invention can be used for synthesizing various CGC cyclopentadienyl indene compounds and derivatives, and has good universality. The obtained CGC cyclopentadienyl indene titanium compound is used for copolymerization experiments of ethylene and alpha-olefin, and has excellent copolymerization performance and catalyst activity.
In one embodiment of the present invention, R 1 Independently selected from nitrogen-containing alkyl or arylamine groups.
In one embodiment of the present invention, the metal salt comprises titanium tetrachlorobis (tetrahydrofuran), zirconium tetrachloride, or hafnium tetrachloride.
In particular, the metal salt also includes a titanium tetrahydrofuran adduct formed in situ in the reactor.
In one embodiment of the present invention, the molar ratio of the lithium salt of the compound having the structure represented by formula (I-1) to the compound having the structure represented by formula (I-2) is 1:1-5. Preferably, the molar ratio of the lithium salt of the compound having the structure represented by formula (I-1) to the compound having the structure represented by formula (I-2) is 1:1-1.15.
In one embodiment of the present invention, the molar ratio of the lithium salt of the compound having the structure represented by formula (II-1) to the lithium salt of the compound having the structure represented by formula (II-2) is 1:1-5. Preferably, the molar ratio of the lithium salt of the compound having the structure represented by the formula (II-1) to the lithium salt of the compound having the structure represented by the formula (II-2) is 1:1-1.15.
It is to be noted that, since the present invention adopts the one-pot method for the reaction, the molar amount of the compound having the structure represented by the formula (II-1) herein is calculated in accordance with the theoretical value.
In one embodiment of the present invention, the molar ratio of the compound having a structure represented by formula (III-1) to the alkyllithium is 1. Preferably, the molar ratio of the compound having the structure represented by the formula (III-1) to the alkyllithium is 1.
It is to be noted that, since the reaction is carried out by the one-pot method in the present invention, the molar amount of the compound having the structure represented by the formula (III-1) herein is also calculated in accordance with the theoretical value.
In one embodiment of the present invention, the molar ratio of the dilithium salt to the metal salt of the compound having the structure represented by formula (III-1) is 1:1-5. Preferably, the molar ratio of the dilithium salt to the metal salt of the compound having the structure represented by the formula (III-1) is 1:1-1.15.
It is to be noted that, since the reaction is carried out by the one-pot method in the present invention, the molar amount of the dilithium salt of the compound having the structure represented by the formula (III-1) herein is also calculated in accordance with the theoretical value.
In an embodiment of the present invention, the first solvent includes at least one of aromatic hydrocarbon, ether and alkane solvents. Preferably, the alkane solvent comprises at least one of toluene, tetrahydrofuran, diethyl ether and n-hexane. More preferably, the alkane solvent is n-hexane.
In an embodiment of the present invention, the second solvent includes tetrahydrofuran. According to the embodiment of the invention, the second solvent is tetrahydrofuran, and the product obtained is higher in purity.
In one embodiment of the invention, in the step 1) and the step 2), the reaction temperature is-78-111 ℃.
Preferably, in step 1) and step 2), the reaction temperature is 31-35 ℃.
In one embodiment of the invention, in the step 3), the reaction temperature is-31-1 ℃. The low temperature is more favorable for the reaction of the metal salt and the dilithium salt of the compound with the structure shown in the formula (III-1).
In one embodiment of the invention, in the step 1), the step 2) and the step 3), the reaction time is 3-48 hours. Preferably, in step 1), step 2), step 3), the reaction time is 6 to 8 hours.
In an embodiment of the present invention, the inert gas includes at least one of nitrogen, helium or argon. The synthesis method discussed in the embodiment of the invention is sensitive to water and oxygen, and the inert gas is stable and does not participate in chemical reaction.
In one embodiment of the invention, the method further comprises the step 4), after the reaction is finished, removing the solvent in vacuum, extracting the product, and purifying the product.
Specifically, the step 4) specifically comprises the following steps: and (3) vacuumizing the reaction liquid obtained in the step 3), removing all solvents, extracting residues by using an aromatic hydrocarbon solvent, vacuumizing again, removing the aromatic hydrocarbon solvent, and washing the residual solid by using an alkane solvent to obtain the metallocene indene metal compound with the structure shown in the formula (III-2).
An embodiment of the invention also provides a constrained geometry nitrogen-containing side-arm metallocene catalyst derivative synthesized by any one of the synthesis methods.
The present invention will be described in detail with reference to examples.
Example 1The synthesis of nitrogen-containing side-arm-base monoindene titanium catalyst in limited geometric configuration includes the following steps:
step 1):
compound 1a (484.3 mg, 2.61mmol) was placed in a 111ml eggplant type bottle at room temperature under a nitrogen atmosphere, 41ml of n-hexane was added, and a 2.4M n-butyllithium hexane solution (1.14mL, 2.74mmol) was added under stirring and stirred for 6 hours to obtain yellow precipitate 2a. Taking Me 2 SiCl 2 (337.4mg, 2.61mmol) was slowly added dropwise to the reaction solution, the solution changed from a yellow suspension to a brown cloudy solution, and 3a was formed after stirring overnight. After sampling, the hexane solvent was drained, and the result of 3a nuclear magnetic analysis was: 1 H NMR(411MHz,C 6 D 6 )δ7.59(t,J＝7.1Hz,2H),7.23–7.12(m,2H),5.12(d,J＝2.4Hz,1H),3.51(d,J＝2.1Hz,1H),3.12(t,J＝6.4Hz,4H),1.54–1.45(m,5H),1.12(s,3H),-1.11(s,3H).
step 2):
under nitrogen atmosphere, adding equimolar tert-butylamine lithium into 111ml of eggplant-shaped bottle hexane solution for generating compound intermediate 3a, stirring and reacting for 8 hours, and sampling nuclear magnetic monitoring reaction to complete the reaction to generate cyclopentadienyl ligand 4a. The nuclear magnetic characterization data are as follows: 1 H NMR(411MHz,C 6 D 6 )δ7.75(t,J＝6.5Hz,1H),7.66(d,J＝7.1Hz,1H),7.36–7.23(m,2H),5.44(d,J＝2.2Hz,1H),3.47(d,J＝1.5Hz,1H),3.29(dd,J＝12.9,6.5Hz,5H),1.68–1.61(m,5H),1.17–1.19(m,9H),1.13(s,3H),1.11(s,3H).
step 3):
adding 2.1eq n-butyllithium hexane solution into 111ml eggplant-shaped flask hexane solution for generating compound intermediate 4a under nitrogen atmosphere, stirring overnight to generate a large amount of lithium dilithium salt of yellow precipitate 4a, cooling the reaction solution to-21 deg.C, and adding equimolar TiCl 4 (THF) 2 Solid, the color of the solution changed from yellow to dark black, slowly warmed to room temperature, stirred overnight, the solvent was removed in vacuo, the lithium salt was filtered off by toluene extraction, toluene was removed by distillation under reduced pressure, recrystallized, and washed with n-hexane to give a black solid 5a in 74.8% yield. Nuclear magnetic characterization was as follows: 1 H NMR(411MHz,C 6 D 6 )δ7.38(d,J＝8.8Hz,2H),6.89–6.78(m,2H),5.43(s,1H),3.33(s,2H),2.97(s,2H),1.22(s,4H),1.16(s,9H),1.42(s,3H),1.32(s,3H).
example 2The synthesis of nitrogen-containing side-arm-base monoindene titanium catalyst in limited geometric configuration includes the following steps:
step 1):
compound 1a (411mg, 2.1mmol) was placed in a 111mL eggplant-shaped bottle at room temperature under a nitrogen atmosphere, 41mL of n-hexane was added, and a 2.4M n-butyllithium hexane solution (1.92mL, 2.215mmol) was added with stirring and stirred for 6 hours to obtain yellow precipitate 2a. Taking Ph 2 SiCl 2 (337.4mg, 2.61mmol) was slowly added dropwise to the reaction solution, the solution changed from a yellow suspension to a brown cloudy solution, and 3b was formed after stirring overnight. After sampling, the hexane solvent was drained. 3b nuclear magnetism is characterized by 1 H NMR(411MHz,CDCl 3 )δ7.49(dd,J＝11.4,7.4Hz,3H),7.45–7.37(m,3H),7.35(d,J＝7.2Hz,2H),7.35(d,J＝7.2Hz,2H),7.31(s,2H),7.32–7.24(m,2H),7.29–7.17(m,3H),7.24–7.18(m,1H),7.11(t,J＝7.4Hz,1H),7.11(t,J＝7.4Hz,1H),5.21(d,J＝2.1Hz,1H),4.17(s,1H),3.31(dd,J＝14.4,6.5Hz,2H),3.22–3.19(m,2H),1.95–1.78(m,4H).
Step 2):
under nitrogen atmosphere, to 111ml of a hexane solution in a eggplant-shaped bottle to produce the intermediate 3b of the compound, lithium tert-butylamido was added in an equimolar amount, the reaction was stirred for 6 hours, and the completion of the reaction was monitored by sampling nuclear magnetism to produce the cyclopentadienyl ligand 4b. The nuclear magnetic diagram of the obtained product is shown in FIG. 3, and the nuclear magnetic characterization data is as follows: 1 H NMR(411MHz,C 6 D 6 )δ7.71(dd,J＝6.4,2.9Hz,2H),7.63–7.48(m,5H),7.19(dd,J＝7.4,4.6Hz,4H),7.15–7.17(m,5H),5.47(d,J＝2.1Hz,1H),4.15(d,J＝1.2Hz,1H),3.11(q,J＝7.1Hz,2H),3.11–2.89(m,2H),1.54(dd,J＝12.8,5.8Hz,4H),1.18(s,9H).
and step 3):
adding 2.1 times of n-butyllithium hexane solution into 111ml of eggplant-shaped flask hexane solution for generating compound intermediate 4b under nitrogen atmosphere, stirring overnight to generate a large amount of lithium salt of yellow precipitate 4b, cooling the reaction solution to-21 deg.C, and adding equimolar TiCl 4 (THF) 2 Solid, the color of the solution changed from yellow to dark black, slowly warmed to room temperature, stirred overnight, the solvent was removed in vacuo, the lithium salt was filtered off by toluene extraction, toluene was removed by distillation under reduced pressure, recrystallized, and washed with n-hexane to give a black solid 5b in 75% yield. The nuclear magnetic diagram of the obtained product is shown in FIG. 4, and the nuclear magnetic characteristics are as follows: 1 H NMR(411MHz,C 6 D 6 )δ8.11(ddd,J＝9.4,7.6,2.7Hz,4H),7.58(d,J＝8.7Hz,1H),7.41–7.24(m,7H),7.18–6.99(m,1H),6.89–6.79(m,1H),5.91(s,1H),3.51(s,2H),3.11(s,2H),1.61(s,9H),1.41(s,4H).
example 3The synthesis of nitrogen-containing side-arm-base monoindene titanium catalyst in limited geometric configuration includes the following steps:
step 1):
compound 1a (511mg, 2.62mmol) was placed in a 111mL eggplant-shaped bottle at room temperature under a nitrogen atmosphere, 61mL of n-hexane was added thereto, and a 2.5M n-butyllithium hexane solution (1.11mL, 2.75mmol) was added thereto under stirring and stirred for 6 hours to obtain yellow precipitate 2a. Taking Ph 2 SiCl 2 (372.3 mg, 2.88mmol) was slowly added dropwise to the reaction solution which changed from a yellow suspension to a brown cloudy solution and stirred overnight to yield 3b. After sampling, the hexane solvent was drained. 3b nuclear magnetic characterization was 1H NMR (411mhz, cdcl3) δ 7.49 (dd, J =11.4,7.4hz, 3H), 7.45-7.37 (m, 3H), 7.35 (d, J =7.2hz, 2h), 7.31 (s, 2H), 7.32-7.24 (m, 2H), 7.29-7.17 (m, 3H), 7.24-7.18 (m, 1H), 7.11 (t, J =7.4hz, 1h), 5.21 (d, J =2.1hz, 1h), 4.17 (s, 1H), 3.31 (dd, J =14.4, 6.5hj), 3.22-3.19H, 1.95, 1H (m, 4H).
Step 2):
under nitrogen atmosphere, 111mL of eggplant-shaped bottle hexane solution in which the intermediate compound 3b was formed was added with equal moles of cyclopentylamine lithium, stirred and reacted for 8 hours, and the reaction was monitored by sampling nuclear magnetism and completed to form the metallocene 4c. The nuclear magnetic characterization data are as follows: 1 H NMR(411MHz,C 6 D 6 )δ7.75–7.59(m,5H),7.37(d,J＝7.6Hz,1H),7.22(dd,J＝4.9,1.6Hz,3H),7.19(dd,J＝6.3,2.6Hz,3H),7.17(t,J＝7.4Hz,1H),5.49(d,J＝2.2Hz,1H),4.12(d,J＝1.5Hz,1H),3.21–3.15(m,5H),1.71–1.58(m,2H),1.58–1.51(m,4H),1.43(dd,J＝8.7,4.3Hz,2H),1.31–1.17(m,3H),1.12–1.11(m,2H).
and step 3):
under nitrogen atmosphere, to form compound intermediate4c of 111ml of eggplant-shaped bottle hexane solution is added with 2.1 times of n-butyllithium n-hexane solution, after stirring overnight, a large amount of yellow precipitate 4c of dilithium salt is generated, the reaction solution is cooled to-31 ℃, and equimolar TiCl is added 4 (THF) 2 The solid, the color of the solution changed from yellow to dark black, slowly warmed to room temperature, stirred overnight, the solvent was removed in vacuo, the toluene extracted and the lithium salt filtered off, the toluene distilled off under reduced pressure, recrystallized, washed with n-hexane to give a black solid 5c in 79% yield. The nuclear magnetism was characterized as follows: 1 H NMR(411MHz,C 6 D 6 )δ8.17–8.11(m,2H),7.97(dd,J＝6.7,2.8Hz,2H),7.61(d,J＝8.8Hz,1H),7.37–7.32(m,2H),7.32(s,1H),7.31–7.26(m,4H),6.99(dd,J＝16.7,8.8Hz,3H),6.85–6.79(m,1H),5.85(s,1H),3.58(t,J＝6.5Hz,1H),3.45(d,J＝8.2Hz,2H),3.18(s,2H),2.19(s,2H),1.86(dd,J＝12.5,9.1Hz,3H),1.58(s,3H),1.41(d,J＝7.1Hz,6H).
example 4The synthesis of nitrogen-containing side-arm cyclopentadienyl titanium catalyst in limited geometrical configuration includes the following steps:
step 1):
compound 1a (311mg, 1.62mmol) was placed in a 111ml eggplant type bottle at room temperature under a nitrogen atmosphere, 41ml of n-hexane was added, and a 2.5M n-butyllithium hexane solution (1.72mL, 1.78mmol) was added under stirring and stirred for 6 hours to obtain yellow precipitate 2a. Taking Me 2 SiCl 2 (219mg, 1.62mmol) was slowly added dropwise to the reaction solution, the solution changed from a yellow suspension to a brown cloudy solution, and 3a was formed after stirring overnight. After sampling, the hexane solvent was drained, and the result of 3a nuclear magnetic analysis: 1 H NMR(411MHz,C 6 D 6 )δ7.59(t,J＝7.1Hz,2H),7.23–7.12(m,2H),5.12(d,J＝2.4Hz,1H),3.51(d,J＝2.1Hz,1H),3.12(t,J＝6.4Hz,4H),1.54–1.45(m,5H),1.12(s,3H),-1.11(s,3H).
step 2):
under nitrogen atmosphere, adding equimolar tert-butylamine lithium into 111ml of eggplant-shaped bottle hexane solution for generating compound intermediate 3a, stirring and reacting for 8 hours, and sampling nuclear magnetic monitoring reaction to complete the reaction to generate cyclopentadienyl ligand 4a. The nuclear magnetic characterization data are as follows: 1 HNMR(411MHz,C 6 D 6 )δ7.75(t,J＝6.5Hz,1H),7.66(d,J＝7.1Hz,1H),7.36–7.23(m,2H),5.44(d,J＝2.2Hz,1H),3.47(d,J＝1.5Hz,1H),3.29(dd,J＝12.9,6.5Hz,5H),1.68–1.61(m,5H),1.17–1.19(m,9H),1.13(s,3H),1.11(s,3H).
step 3)
Adding 2.1eq n-butyllithium hexane solution into 111ml hexane solution in eggplant-shaped bottle for generating compound intermediate 4a under nitrogen atmosphere, stirring overnight to generate large amount of lithium salt of yellow precipitate 4a, cooling the reaction solution to-31 deg.C, adding equimolar ZrCl 4 The solid, the color of the solution changed from yellow to yellow brown, slowly warmed to room temperature, stirred overnight, the solvent was removed in vacuo, the lithium salt was filtered off by toluene extraction, toluene was removed by distillation under reduced pressure, and washed with n-hexane to give a yellow crystalline solid 5d, 65.3% yield. Nuclear magnetic characterization was as follows: 1 HNMR(C 6 D 6 )δ1.51(s,3H),1.69(s,3H).1.33(s,9H),1.7-1.7(m,4H),3.1-3.2(m,2H),3.4-3.5(m,2H),5.59(s,1H).6.9-7.1(m,2H),7.6-7.7(m,1H),7.63(d,1H 3 J HH ＝8.5Hz).
comparative example 1A catalyst having the same structure as in example 2 was prepared, comprising the steps of:
under nitrogen atmosphere, to compound intermediate Ph 2 SiCl 2 (1g, 1.114mol) was added to 21ml of a hexane solution, lithium tert-butylamine (312mg, 1.114mol) was added thereto, and after stirring overnight, the lithium salt was filtered off, and the solvent was drained to give an oily product 1d in a yield of 91%.
1d (511mg, 1.724mmol), was added equimolar of the 1a lithium salt solid, the solution changed color from yellow to yellow-brown, stirred overnight, filtered and the solvent removed in vacuo to give product 4b. The nuclear magnetic results of the obtained product are shown in figure 1.
After addition of twice the amount of n-butyllithium solution to the product 4b, filtration and draining, the dilithium salt solid (487mg, 1.18mmol) was added to a solution containing an equimolar amount of TiCl 3 (THF) 3 THF, stirring for 2 hours, and adding PbCl 2 (155mg, 1.54mmol) the solution turned black from yellow, stirred overnight, added THF which was distilled off under reduced pressure, extracted with toluene, filtered and washed with n-hexane to give a black solid 5b in 71.3% yield. The nuclear magnetic results of the obtained product are shown in FIG. 2.
Comparing fig. 1-4, it can be seen that the ligand 4b nuclear magnetic diagram 1 synthesized by the method proposed in comparative example 1 is easy to have multi-peak of isomer at 4.1-5.5ppm, while the ligand 4b nuclear magnetic diagram 3 synthesized by the method of example can be seen to reduce the generation of isomeric peak at 4.1-5.5ppm, the catalyst 5b nuclear magnetic diagram 2 obtained by the method of comparative example is compared with the catalyst 5b nuclear magnetic diagram 4 at 7.1-8.5ppm,1.2-1.5ppm, the method of comparative example has many non-removable hetero peaks, which is the peak of the product of incomplete oxidation of trivalent titanium, at 4.1-5.5ppm, the peak of isomer is not completely removed, and the purity is lower.
Test example 1Ethylene-octene copolymerization experiment
Preferred catalysts for carrying out the experiment for polymerizing ethylene-octene according to the present invention are catalyst M1 (5 a) prepared in example 1 and catalyst M2 (5 b) prepared in example 2.
The instrument equipment comprises: high-temperature high-pressure batch reaction kettle, hot press, electronic densitometer, melt flow rate meter, high-temperature Gel Permeation Chromatograph (GPC).
Among experiments of ethylene-octene polymerization using M1 catalyst, experiments in which temperature factors affect polymerization of M1 and M2 catalysts (polymerization temperature is selected to be 91 ℃,121 ℃,141 ℃,161 ℃), in which pressure is 2MPa, octene concentration is 1.5M, catalyst concentration is 3.1umol, reaction time is 11min, total solvent amount is 31mL, and cocatalyst is [ Ph [ 3 C][B(C 6 F 5 ) 4 ]The concentration ratio is as follows: B/Ti =1.1, al/Ti =151, main catalyst pre-alkylation concentration ratio: al/Ti =5. The catalyst, cocatalyst and triisobutyl aluminum all adopt toluene solution.
The catalyst polymerization experiments were as follows:
preheating a pump-drainage reaction kettle at 151 ℃, replacing a reaction system with ethylene, adding 16.4mL of n-hexane, 7.1mL of octene and 4.5mL of triisobutyl aluminum in sequence when the temperature is reduced to below 61 ℃, stirring for 1 minute, and then adding 1mL of catalyst M1 (catalyst M2) and cocatalyst [ Ph ] in sequence 3 C][B(C 6 F 5 ) 4 ]And opening an ethylene flow valve, keeping the ethylene pressure of the system at 2MPa, and reacting for 11 minutes. And after the reaction is finished, adding a fire extinguishing agent. The polymer solution was precipitated with acidified ethanol. After drying, the pellets are pressed and subjected to analytical tests such as density, melt index determination, GPC, etc. The results are shown in tables 1 and 2, where table 1 is the catalytic characteristic data for M1 and table 2 is the catalytic characteristic data for M2.
TABLE 1 catalytic Property data for M1
TABLE 2 catalytic Property data for M2
Claims (10)
1. A method for synthesizing a constrained geometry nitrogen-containing side-arm metallocene derivative comprises the following steps:
1) Under the protection of inert gas, lithium salt of a compound with a structure shown in a formula (I-1) and a compound with a structure shown in a formula (I-2) react in a first solvent to obtain a reaction solution containing the compound with the structure shown in the formula (II-1);
2) Adding lithium salt of a compound with a structure shown in a formula (II-2) into the reaction liquid obtained in the step 1) for reaction to obtain reaction liquid containing the compound with the structure shown in the formula (III-1), and adding alkyl lithium for reaction to obtain reaction liquid containing dilithium salt of the compound with the structure shown in the formula (III-1);
3) Adding metal salt into the reaction liquid obtained in the step 2), and simultaneously adding a second solvent for reaction to obtain an indene metallocene compound with a structure shown in a formula (III-2);
wherein, the first and the second end of the pipe are connected with each other,
R 1 independently selected from nitrogen-containing groups, R 2 Independently selected from hydrogen and methyl;
R 3 、R 4 each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 5 independently selected from substituted or unsubstituted alkyl, aryl;
m is independently selected from titanium, zirconium, hafnium.
2. The method of synthesis according to claim 1,
R 1 independently selected from nitrogenous alkyl groups or arylamine groups.
3. The method of synthesis according to claim 1,
the metal salt comprises titanium tetrachlorobis (tetrahydrofuran), zirconium tetrachloride or hafnium tetrachloride.
4. The method of synthesis according to claim 1,
the molar ratio of the lithium salt of the compound having the structure represented by formula (I-1) to the compound having the structure represented by formula (I-2) is 1:1-5.
5. The method of synthesis according to claim 1,
the molar ratio of the lithium salt of the compound having the structure represented by the formula (II-1) to the lithium salt of the compound having the structure represented by the formula (II-2) is 1:1-5;
preferably, the molar ratio of the compound having the structure represented by formula (III-1) to the alkyllithium is 1.
6. The method of synthesis according to claim 1,
the molar ratio of the dilithium salt to the metal salt of the compound having the structure represented by the formula (III-1) is 1:1-5.
7. The method of synthesis according to claim 1,
the first solvent comprises at least one of aromatic hydrocarbon, ether and alkane solvents;
preferably, the alkane solvent comprises at least one of toluene, tetrahydrofuran, diethyl ether and n-hexane;
more preferably, the alkane solvent is n-hexane;
the second solvent comprises tetrahydrofuran.
8. The method of synthesis according to claim 1,
in the step 1) and the step 2), the reaction temperature is-78-111 ℃;
in the step 3), the reaction temperature is-31-1 ℃.
9. The method of synthesis according to claim 1,
the inert gas comprises at least one of nitrogen, helium or argon.
10. A constrained geometry nitrogen-containing pendant-arm metallocene catalyst derivative synthesized by the synthesis method of any of claims 1-9.
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| CN1230190A (en) * | 1996-08-08 | 1999-09-29 | 陶氏化学公司 | 3-heteroatom sustituted cyclopentadienyl-containing metal complexes and olefin polymerization process |
| WO2004044018A2 (en) * | 2002-11-07 | 2004-05-27 | Dow Global Technologies, Inc. | Process for homo- or copolymerization of conjugated dienes and in situ formation of polymer blends and products made thereby |
| CN105358586A (en) * | 2013-07-17 | 2016-02-24 | 埃克森美孚化学专利公司 | Cyclopropyl substituted metallocene catalysts |
| CN109312026A (en) * | 2016-06-15 | 2019-02-05 | Scg化学有限公司 | Catalyst composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1230190A (en) * | 1996-08-08 | 1999-09-29 | 陶氏化学公司 | 3-heteroatom sustituted cyclopentadienyl-containing metal complexes and olefin polymerization process |
| WO2004044018A2 (en) * | 2002-11-07 | 2004-05-27 | Dow Global Technologies, Inc. | Process for homo- or copolymerization of conjugated dienes and in situ formation of polymer blends and products made thereby |
| CN105358586A (en) * | 2013-07-17 | 2016-02-24 | 埃克森美孚化学专利公司 | Cyclopropyl substituted metallocene catalysts |
| CN109312026A (en) * | 2016-06-15 | 2019-02-05 | Scg化学有限公司 | Catalyst composition |
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