CN117467055B - Metallocene catalyst and preparation method and application thereof - Google Patents
Metallocene catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000012968 metallocene catalyst Substances 0.000 title abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 71
- 239000002904 solvent Substances 0.000 abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 abstract description 10
- 239000003446 ligand Substances 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 55
- 239000000047 product Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 29
- 239000005977 Ethylene Substances 0.000 description 29
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 27
- 239000012190 activator Substances 0.000 description 18
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 12
- NDJMNNSJDIFFTH-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 NDJMNNSJDIFFTH-UHFFFAOYSA-L 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229920006124 polyolefin elastomer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- OZIJRVRERJTEGQ-UHFFFAOYSA-N dimethyl-bis(2-methyl-4-phenyl-1h-inden-1-yl)silane Chemical compound CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Si](C)(C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 OZIJRVRERJTEGQ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ASGNRCDZSRNHOP-UHFFFAOYSA-N 2-methyl-4-phenyl-1h-indene Chemical compound C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 ASGNRCDZSRNHOP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- -1 alkyl lithium Chemical compound 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical group [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 1
- NJKDOKBDBHYMAH-UHFFFAOYSA-N dibutyl(dichloro)silane Chemical compound CCCC[Si](Cl)(Cl)CCCC NJKDOKBDBHYMAH-UHFFFAOYSA-N 0.000 description 1
- UOZZKLIPYZQXEP-UHFFFAOYSA-N dichloro(dipropyl)silane Chemical compound CCC[Si](Cl)(Cl)CCC UOZZKLIPYZQXEP-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a metallocene catalyst, a preparation method thereof and application thereof in olefin copolymerization. In the preparation method of the metallocene catalyst, the target product with high yield and high selectivity is obtained by changing the synthesis conditions of the ligand. The catalyst system of the olefin copolymer provided by the invention fully activates the catalyst shown in the formula II by using the catalyst active agent, so that the efficient olefin copolymerization reaction is completed; at the same time, the use of benzene solvents is reduced as much as possible.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a metallocene catalyst, a preparation method thereof and application thereof in olefin copolymerization.
Background
The catalyst has a decisive influence on the structural properties of the olefin polymer product. Compared with the traditional Ziegler-Natta catalyst, the metallocene catalyst has obvious advantages in the production of polyolefin products of special types such as POE and the like.
The rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst disclosed in the prior art has good olefin copolymerization properties. However, the synthesis methods reported so far have drawbacks, in particular the synthesis of the ligand thereof, dimethyl bis (2-methyl-4-phenylindenyl) silane, which are more disadvantageous.
In the prior art prior to the present invention, most ligand synthesis methods were those reported by reference WALTER SPALECK et al (Organometallics 1994,13 (3), 954-963). The process requires a reaction at high temperature (80 ℃) and may produce isomers. Meanwhile, other synthesis methods, such as those reported by Li Huayi et al (dinuclear metallocene supported catalyst, preparation method and application thereof, CN111116789 a), adopt a single solvent (toluene) in the synthesis process, and require recrystallization in the post-treatment process, which is not only unfavorable for improving the yield, but also difficult to stir, and unfavorable for mass production.
On the other hand, the use of catalytic activators has been mentioned in the prior art as an efficient means of obtaining polyolefin products of the specific type, such as POE. However, how to select a proper catalyst activator to improve the copolymerization performance of special polyolefin products such as POE and the like in the production of a catalyst system and simplify the preparation process is a technical problem to be solved in the field.
Disclosure of Invention
In order to improve at least one of the above technical problems, the present invention provides a highly efficient synthesis method of a metallocene catalyst. And provides the application of the metallocene catalyst for efficiently obtaining POE products in solution polymerization under the combined action of the catalyst and the activator.
The first aspect of the invention provides a process for the preparation of a compound of formula I comprising the steps of: mixing a compound of the formula A, a first organic solvent and an alkyl metal reagent, and reacting to obtain a product I; the first and second organic solvents are mixed with dialkyl dichlorosilane, and the compound shown in the formula I is obtained through reaction;
The compound of formula a has the structure shown below:
The compound of formula I has the structure shown below:
the first organic solvent is selected from nonpolar aprotic solvents, and the second organic solvent is selected from toluene and/or tetrahydrofuran.
According to an embodiment of the invention, the compound of formula I is dimethyl bis (2-methyl-4-phenylindenyl) silane.
According to an embodiment of the invention, the non-polar aprotic solvent is selected from n-hexane and/or toluene, preferably a mixed solvent of n-hexane and toluene.
According to an embodiment of the invention, the metal alkyl reagent is selected from alkyl lithium, such as C 1～6 alkyl lithium, exemplified by butyl lithium.
According to an embodiment of the invention, the compound of formula a, the first organic solvent and the metal alkyl reagent are mixed in such a way that: the compound of formula A is first dissolved in a first organic solvent and then the metal alkyl reagent is added dropwise to the solution.
According to an embodiment of the invention, the reaction conditions to obtain said product one comprise: the reaction is carried out at room temperature for at least 10 hours, for example for 12 hours, 18 hours or 20 hours at room temperature.
According to an embodiment of the invention, the preparation process further comprises a post-treatment of the first product, for example washing the first product with a first organic solvent.
According to an embodiment of the invention, the product one is a lithium salt of a compound of formula a.
According to an embodiment of the present invention, the second organic solvent is a mixed solvent of toluene and tetrahydrofuran, for example, the volume ratio of toluene to tetrahydrofuran is (5-25): 1, and exemplary are 10:1, 15:1, and 20:1.
According to an embodiment of the invention, the dialkyldichlorosilane is selected from the group consisting of di-C 1～6 alkyldichlorosilanes, such as dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane or dibutyldichlorosilane.
According to an embodiment of the invention, the product one, the second organic solvent and the dialkyldichlorosilane are mixed in such a way that: the first product is dissolved in a second organic solvent, the solution is cooled to below 5℃ (e.g., -2-5℃), and dialkyldichlorosilane is added to the solution.
According to an embodiment of the present invention, the reaction conditions to obtain the compound of formula I comprise: reacting at room temperature for at least 10 hours, for example, reacting at room temperature for 12 hours, 18 hours or 20 hours; preferably, after the reaction is completed, the reaction is quenched by the addition of water.
In a second aspect, the present invention provides a process for the preparation of a compound of formula II, comprising a process for the preparation of a compound of formula I as described above;
the compound of formula II has the structure shown below:
According to an embodiment of the invention, the compound of formula II is rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride.
According to an embodiment of the invention, the preparation method comprises the steps of: reacting a compound of formula I with a metal alkyl reagent and zirconium tetrachloride to obtain the compound of formula II; the compound of the formula I is prepared by the preparation method of the compound of the formula I.
According to an embodiment of the invention, the preparation method comprises the steps of: the method comprises the steps of mixing a compound of a formula I, a first organic solvent and an alkyl metal reagent, and reacting to obtain a first product; the first product, the second organic solvent and zirconium tetrachloride are mixed and reacted to obtain the compound of the formula II.
According to an embodiment of the invention, the metal alkyl reagent, the first organic solvent, and the second organic solvent all have the options as indicated above.
According to an embodiment of the invention, the compound of formula I, the first organic solvent and the metal alkyl reagent are mixed in such a way that: the method comprises the steps of firstly dissolving a compound of the formula I in a first organic solvent, and then dropwise adding a metal alkyl reagent into the solution.
According to an embodiment of the invention, the reaction conditions to obtain the first product comprise: the reaction is carried out at room temperature for at least 10 hours, for example for 12 hours, 18 hours or 20 hours at room temperature.
According to an embodiment of the invention, the preparation process further comprises a post-treatment of the first product, for example washing the first product with a first organic solvent.
According to an embodiment of the invention, the first product is a dilithium salt of a compound of formula I.
According to an embodiment of the invention, the first product, the second organic solvent and zirconium tetrachloride are mixed in such a way that: the first product is first dissolved in a second organic solvent, the solution is cooled to below-30℃ (e.g., -35℃), and zirconium tetrachloride is added to the solution.
According to an embodiment of the present invention, the reaction conditions to obtain the compound of formula II comprise: reacting at room temperature for at least 10h, for example, reacting at room temperature for 12h, 18h, 20h, 24h; preferably, after the reaction is completed, filtering a reaction product, concentrating filtrate, and cooling to obtain a solid which is the compound of the formula II; preferably, the cooling time is at least 10 hours, for example, room temperature reaction 12 hours, 18 hours or 20 hours.
The invention also provides a catalyst system for preparing olefin copolymer, which comprises a main catalyst and a catalytic activator, wherein the main catalyst is a compound shown as a formula II, and the catalytic activator is borate, preferably tetra (pentafluorophenyl) borate.
The inventors found that the progress of the copolymerization reaction can be greatly promoted by adding a catalyst activator (generally, tetrakis (pentafluorophenyl) borate is preferable) in the solution polymerization reaction. However, tetrakis (pentafluorophenyl) borate is used as an anion, and the corresponding cations are widely varied. Among these, the influence on the solubility of the catalyst activator and the copolymerization performance of the main catalyst is different from one cation to another. The proper catalyst activator is selected to activate the main catalyst to fully exert the copolymerization performance and the catalytic activity of the zirconocene catalyst and maximally realize the dissolution of the active center of the activated catalyst in the polymerization solvent (namely alkane solvent).
In some embodiments, the catalyst activator is selected from one or more of triphenylcarbon tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, N-bishexacosanilinium tetrakis (pentafluorophenyl) borate.
According to an embodiment of the invention, the ratio of the molar amount of B element in the catalyst to the molar amount of Zr element in the procatalyst is (0.5-10): 1, such as (1-5): 1, exemplary 2:1.
According to an embodiment of the invention, the catalyst system further comprises a cocatalyst, such as an aluminum alkyl, exemplified by triisobutylaluminum.
According to an embodiment of the invention, the ratio of the molar amount of the metal element (e.g. Al) of the cocatalyst to the molar amount of Zr element in the procatalyst is (20-10000): 1, such as (100-1000): 1, exemplary 600:1.
According to a preferred embodiment of the present invention, the catalyst system consists of a compound of formula II, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triisobutylaluminum.
According to a preferred embodiment of the invention, the catalyst system consists of a compound of formula II, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate and triisobutyl aluminum.
According to an embodiment of the present invention, the olefin copolymer is a copolymer of an alpha-olefin and ethylene, for example, the alpha-olefin is selected from one or more of 1-butene, 1-pentene, 1-hexene, 1-octene, etc.
Preferably, the compound of formula II is prepared by the preparation method of the compound of formula II.
According to an embodiment of the present invention, the olefin copolymer may be a polyolefin elastomer (POE).
The invention also provides a preparation method of the olefin copolymer, and the olefin copolymer is prepared by the catalyst system.
According to an embodiment of the invention, the olefin copolymer has the definition as indicated above.
According to an embodiment of the invention, the preparation method comprises the steps of: the alpha-olefin and ethylene are polymerized in the presence of the above catalyst system to obtain the olefin copolymer.
The inventor found that the catalyst activator (such as tris (pentafluorophenyl) boron) used in the prior art can only be dissolved in benzene solvent, and the solvents used in the continuous POE production process are all mixed alkane solvents, obviously, the introduction of benzene solvent can increase the process and separation difficulty.
According to an embodiment of the invention, the polymerization system further comprises a solvent, for example at least an alkane solvent, preferably a C 5～16 alkane, exemplified by n-hexane; in some embodiments, the solvent may also contain (small amounts of) toluene, for example, a mixed solvent of n-hexane and toluene.
According to an embodiment of the invention, the preparation method comprises the steps of:
(1) Mixing the solvent, the alpha-olefin and the cocatalyst, and adding the mixture into a polymerization kettle;
(2) Heating the polymerization kettle, and introducing ethylene into the polymerization kettle for boosting;
(3) Mixing the main catalyst, the catalytic activator and the solvent to obtain an activated catalyst solution;
(4) And (3) rapidly pumping the activated catalyst solution into the polymerization kettle in the step (2), introducing ethylene again to maintain the pressure in the polymerization kettle, and cooling after the reaction is completed to obtain the olefin copolymer.
Advantageous effects
First, the preparation method of the compound of the formula I provided by the invention not only improves the selectivity of the compound of the formula I, but also improves the overall yield. Based on the above, the invention simultaneously improves the enantioselectivity of the catalyst synthesis shown in the formula II.
Secondly, the catalyst system of the olefin copolymer provided by the invention fully activates the catalyst shown in the formula II by using a catalyst activator, so that the efficient olefin copolymerization reaction is completed; meanwhile, the catalyst activator is applicable to an alkane solvent system for olefin copolymerization reaction, and the use of benzene solvents is reduced as much as possible.
Drawings
FIG. 1 is a chart showing the NMR spectrum of dimethyl bis (2-methyl-4-phenylindenyl) silane 1 H obtained by the method of example 1;
FIG. 2 is a chart showing the NMR spectrum of dimethyl bis (2-methyl-4-phenylindenyl) silane 1 H obtained by the method of comparative example 1.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
The embodiment 1 of the invention provides a preparation method of a dimethyl di (2-methyl-4-phenyl indenyl) silane ligand, which comprises the following specific preparation process and test results:
In a glove box, 1.51g of 2-methyl-4-phenylindene was introduced into a 100mL Schlemk flask, followed by 20mL of n-hexane, and the mixture was dissolved with stirring. 3.65mL of n-butyllithium solution was added dropwise under an ice bath while keeping the reaction system under nitrogen protection. After the completion of the dropwise addition, the mixture was slowly returned to room temperature, and stirring was continued overnight. The precipitated solid lithium salt was filtered off again and washed with n-hexane. After drying, the lithium salt was transferred to a 100mL Schlenk reaction flask, and 20mL toluene and 2mL Tetrahydrofuran (THF) were added and thoroughly stirred. Thereafter, the mixture was cooled to zero, and 0.47g of Me 2SiCl2 was added dropwise. After the completion of the dropwise addition, the temperature was gradually returned to room temperature, and the mixture was stirred overnight. After the reaction, deionized water is added, stirring is carried out for 3 hours, an organic phase is separated, the target product is obtained through medium-pressure preparation chromatography after spin drying, and 1.30g of product is obtained through total separation, and the yield is 76.0%.
As shown in fig. 1 ,1H NMR(CDCl3):d(ppm)7.35-7.56(m,12H),7.26-7.30(m,2H),7.16-7.21(m,2H),6.81(d,J＝6.72Hz,2H),3.81(s,2H),2.21(d,J＝32.24Hz,6H),-0.19--0.16(m,6H).
Example 2
For the amplification reaction of example 1, the addition amount of 2-methyl-4-phenylindene was changed to 9.06g, and the remaining corresponding materials were all increased in equal proportion based on this. The final isolation gave 7.31g of product in 71.2% yield.
Comparative example 1
The synthesis and characterization of Organometallics 1994,13 (3), 954-963 are carried out by the method of reference.
In a glove box, 1.51g of 2-methyl-4-phenylindene was introduced into a 100mL Schlenk flask, and 20mL of toluene and 1mL of tetrahydrofuran were further added thereto, followed by stirring to dissolve the mixture. 3.2mL of n-butyllithium solution was slowly added dropwise at room temperature, and stirring was continued for 10min. Thereafter, the reaction was carried out at 80℃for 1 hour. Cooled to-35℃and 0.47g of Me 2SiCl2 were added dropwise at this temperature. After the completion of the dropwise addition, the temperature was raised to 80℃and the reaction was carried out for 1 hour. After the reaction, 20mL of deionized water is added, the mixture is stirred for 3 hours, an organic phase is separated, and after spin drying, a target product is obtained through medium-pressure preparation chromatography, and 1.23g of the product is obtained through total separation, and the yield is 71.9%. However, the impurity peaks for a group of isomers are evident from its 1 H NMR spectrum.
The main product peaks are the same as in example 1, and the main impurities can be seen from the enlarged view, with more obvious shifts of 3.55(s), 2.14(s) and 2.09(s), and the impurity content is 15.7% calculated from the integral data.
Comparative example 2
The synthesis and characterization are carried out by referring to a dinuclear metallocene supported catalyst, a preparation method and application thereof, and a method of Chinese patent application with publication number of CN 111116789A.
In a glove box, 1.51g of 2-methyl-4-phenylindene was introduced into a 100mL Schlenk flask, and 20mL of toluene was further added thereto, followed by stirring to dissolve the mixture. At zero degrees, 3.65mL of n-butyllithium solution was added dropwise. After returning to room temperature, stirring was continued overnight. Thereafter, the mixture was cooled to-20℃and 0.47g of Me 2SiCl2 was added dropwise. Gradually return to room temperature and react for 24 hours. After the reaction, 20mL of deionized water is added, the mixture is stirred for 3 hours, an organic phase is separated, and after spin drying, a target product is obtained through medium-pressure preparation chromatography, 612mg of the product is obtained through total separation, and the yield is 35.8%.
TABLE 1 difference in results between the inventive method and the comparative example
The ligand synthesis method shown in comparative example 1 produced isomers, and the ligand synthesis method shown in comparative example 2 gave very low yields of the target products, as shown in tables 1 and 2. The method of the embodiment 1-2 not only improves the selectivity of the ligand, but also improves the overall yield through controlling the temperature and the solvent condition and separating and purifying the lithium salt in the preparation process.
Example 3
The embodiment 3 of the invention provides a method for synthesizing a rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, which comprises the following specific preparation process and test result:
937.4mg of dimethyl bis (2-methyl-4-phenylindenyl) silane (prepared in example 2) was added to a 100mL Schlenk flask in a glove box, and a mixed solution of 10mL of ultra-dry toluene and 10mL of n-hexane was added and stirred well. At zero degree, 2.0mL n BuLi solution was added dropwise, and after the completion of the dropwise addition, the reaction was allowed to return to room temperature and allowed to react overnight. Filtering, washing the obtained filter cake with n-hexane, and collecting the filter cake to obtain the dilithium salt of silane. The dilithium salt was stirred well in 20mL of toluene solution, zrCl 4 was added slowly at-35℃and stirred overnight for 24 hours. And (3) filtering by diatomite, washing by toluene, concentrating the filtrate until solid is separated out, and standing overnight to obtain the rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst product. Total 570.0mg, yield 45.3%.
1H NMR(CDCl3):d(ppm)7.63-7.70(m,6H),7.35-7.46(m,8H),7.11-7.15(m,2H),6.97(s,2H),2.27(s,6H),1.36(s,6H).
Example 4
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerizer was heated to 120℃while the ethylene pressure in the polymerizer was increased to 2.5MPa. 1. Mu. Mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst and 2. Mu. Mol of triphenylcarbon tetrakis (pentafluorophenyl) borate were thoroughly dissolved in 30mL of toluene to form an activated catalyst solution (450 mL total volume of the polymerization system, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, and the resultant product was 67.2g in total.
Example 5
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerizer was heated to 120℃while the ethylene pressure in the polymerizer was increased to 2.5MPa. 1. Mu. Mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, 2. Mu. Mol of the catalyst activator N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 4. Mu. Mol of triisobutylaluminum were thoroughly dissolved in 20mL of toluene and 10mL of N-hexane to form an activated catalyst solution (total volume of the polymerization system 450mL, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, and the resultant product was 82.3g in total.
Example 6
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerizer was heated to 120℃while the ethylene pressure in the polymerizer was increased to 2.5MPa. Mu.mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, 2. Mu.mol of the catalyst activator N, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate, 4. Mu.mol of triisobutyl aluminum were dissolved thoroughly in 30mL of N-hexane to form an activated catalyst solution (450 mL total volume of the polymerization system, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, thus obtaining the product, 48.0g in total.
Example 7
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerizer was heated to 120℃while the ethylene pressure in the polymerizer was increased to 2.5MPa. Mu.mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, 2. Mu.mol of the catalyst activator N, N-bishexacosyl anilinium tetrakis (pentafluorophenyl) borate, 4. Mu.mol of triisobutylaluminum were thoroughly dissolved in 30mL of N-hexane to form an activated catalyst solution (total volume of polymerization system 450mL, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, and the resultant product was 65.1g in total.
Example 8
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerizer was heated to 120℃while the ethylene pressure in the polymerizer was increased to 2.5MPa. 1. Mu. Mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, 2. Mu. Mol of the catalyst activator N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, were thoroughly dissolved in 30mL of N-hexane to form an activated catalyst solution (450 mL total volume of the polymerization system, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, and the resultant product was 118.0g in total.
Example 9
332ML of n-hexane, 85mL of 1-octene and 0.6mmol of triisobutylaluminum (molar ratio to catalyst 600:1) were introduced into a polymerization vessel at ordinary temperature. The polymerization vessel was heated to 120℃and the ethylene pressure in the polymerization vessel was increased to 2.5MPa. 1. Mu. Mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, 2. Mu. Mol of the catalyst activator N, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate, were thoroughly dissolved in 30mL of N-hexane to form an activated catalyst solution (450 mL total volume of the polymerization system, 1-octene concentration 1.22 mol/L). And then the activated catalyst solution is quickly pumped into a polymerization kettle to initiate polymerization, and an ethylene gas switch is opened to supplement ethylene at any time, so that the pressure of the polymerization kettle is maintained at 2.5MPa. The polymerization temperature was set at 120 ℃. After 30 minutes of reaction, the ethylene inlet switch and the kettle body heating switch are closed, the temperature is reduced to room temperature, and then the polymerization kettle is depressurized to normal pressure and then opened. The polymer was taken off and quenched with an acid-alcohol solution (volume ratio ethanol: hydrochloric acid=9:1). After filtration, the polymer was dried to constant weight, 106.4g of the resulting product was obtained.
The catalyst activities of examples 4 to 9 and the physicochemical properties of the polymers obtained are shown in Table 2. On the premise of reducing the use of benzene solvents as much as possible, the efficient polymerization reaction is realized.
TABLE 2 catalyst Activity and Polymer physicochemical Properties
Note that: the total polymerization volume is 450mL, the octene concentration is 1.22mol/L, the normal hexane, 1 mu mol of rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride catalyst, the ethylene pressure is 2.5MPa, the polymerization temperature is set at 120 ℃, the polymerization time is 30 minutes, al/Zr=600, and B/Zr=2.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A process for the preparation of a compound of formula I, characterized in that it comprises the steps of: mixing a compound of the formula A, a first organic solvent and an alkyl metal reagent, and reacting at room temperature to obtain a product I; mixing the first and second organic solvents with dimethyl dichlorosilane, and reacting at room temperature to obtain a compound shown in a formula I;
The compound of formula a has the structure shown below:
The compound of formula I has the structure shown below:
The first organic solvent is selected from n-hexane, the second organic solvent is a mixed solvent of toluene and tetrahydrofuran, and the volume ratio of toluene to tetrahydrofuran is (5-25): 1.
2. The method of claim 1, wherein the metal alkyl reagent is selected from the group consisting of lithium alkyls.
3. The process according to claim 1 or 2, wherein the compound of formula a, the first organic solvent and the metal alkyl reagent are mixed in such a way that: firstly, dissolving a compound of the formula A in a first organic solvent, and then, dropwise adding an alkyl metal reagent into the solution;
And/or, the reaction conditions for obtaining the product I comprise: the reaction is carried out at room temperature for at least 10 hours.
4. The preparation method according to claim 1 or 2, wherein the first and second organic solvents of the product and the dimethyldichlorosilane are mixed in the following manner: firstly, dissolving a first product in a second organic solvent, cooling the solution to below 5 ℃, and then adding dimethyl dichlorosilane into the solution;
and/or, the reaction conditions for obtaining the compound of formula I include: the reaction is carried out at room temperature for at least 10 hours.
5. A process for the preparation of a compound of formula II, comprising: reacting the compound of the formula I with a metal alkyl reagent and zirconium tetrachloride to obtain the compound of the formula II; the compound of formula I is obtained according to the process for the preparation of the compound of formula I as defined in any one of claims 1 to 4;
the compound of formula II has the structure shown below:
6. The preparation method according to claim 5, characterized in that the preparation method comprises the steps of: the method comprises the steps of mixing a compound of a formula I, a first organic solvent and an alkyl metal reagent, and reacting to obtain a first product; the first product, the second organic solvent and zirconium tetrachloride are mixed and reacted to obtain the compound of the formula II.
7. The method of claim 6, wherein the reaction conditions to obtain the first product and/or the compound of formula II comprise: the reaction is carried out at room temperature for at least 10 hours.
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