CN113788862A - Dinuclear metallocene compound and preparation method and application thereof - Google Patents
Dinuclear metallocene compound and preparation method and application thereof Download PDFInfo
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- CN113788862A CN113788862A CN202111122722.0A CN202111122722A CN113788862A CN 113788862 A CN113788862 A CN 113788862A CN 202111122722 A CN202111122722 A CN 202111122722A CN 113788862 A CN113788862 A CN 113788862A
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- metallocene compound
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- dinuclear metallocene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 16
- -1 C1-C8 alkyl silicon Chemical compound 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 abstract description 17
- 238000003780 insertion Methods 0.000 abstract description 13
- 230000037431 insertion Effects 0.000 abstract description 13
- 229920001577 copolymer Polymers 0.000 description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000012968 metallocene catalyst Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 17
- 238000000926 separation method Methods 0.000 description 17
- 238000001291 vacuum drying Methods 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 2
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- MDTDQDVMQBTXST-UHFFFAOYSA-K 2h-inden-2-ide;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C1=CC=C2[CH-]C=CC2=C1 MDTDQDVMQBTXST-UHFFFAOYSA-K 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- TURVPWZPNVDDMU-UHFFFAOYSA-N lithium;phenol Chemical compound [Li].[Li].OC1=CC=CC=C1.OC1=CC=CC=C1 TURVPWZPNVDDMU-UHFFFAOYSA-N 0.000 description 1
- XAVQZBGEXVFCJI-UHFFFAOYSA-M lithium;phenoxide Chemical compound [Li+].[O-]C1=CC=CC=C1 XAVQZBGEXVFCJI-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a dinuclear metallocene compound, and a preparation method thereof comprises the following steps: dissolving metal chloride in an anhydrous solvent under the atmosphere of nitrogen, cooling to-40 to-20 ℃, and uniformly stirring; then adding lithium salt into the reaction kettle at one time, and after the charging is finished, returning to the room temperature and continuing stirring for 16-24 hours to carry out reaction; after the reaction is finished, carrying out anhydrous and anaerobic filtration on the reaction solution, and collecting filtrate; drying the filtrate in vacuum to separate out solid; dissolving the solid in a small amount of anhydrous solvent, and standing at-40 to-20 ℃ to precipitate crystals; the crystals are then isolated and dried under vacuum to give the desired dinuclear metallocene compound. Compared with the prior art, the dinuclear metallocene compound can improve the catalytic activity and the insertion rate of cycloolefin monomers.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a dinuclear metallocene compound and a preparation method and application thereof.
Background
Cycloolefin copolymers have excellent light transmittance and high thermal stability, and therefore are widely used in the fields of optical lenses, medical packaging materials, and the like. Currently, most commercial cycloolefin copolymer products are obtained by copolymerizing an alpha olefin with a cycloolefin. According to the research, the cyclic olefin copolymer has high light transmittance and high heat resistance, and the ratio of the cyclic olefin structural unit in the polymer main chain is directly related. When the proportion of the cycloolefin structural unit is decreased, the heat resistance of the polymer becomes weak and the glass transition temperature is lowered. On the contrary, the heat resistance of the polymer is enhanced. On the other hand, as the proportion of the cyclic olefin structural units is reduced, the length of the alpha olefin segment is gradually increased, and at this time, partial polymer crystallization occurs in the polymer, so that the light transmittance of the polymer is greatly reduced, the haze is improved, and the application of the cyclic olefin copolymer in optical materials is influenced. Therefore, it is critical to maintain the excellent properties of the cycloolefin copolymer to properly increase the ratio of the cycloolefin unit in the cycloolefin copolymer.
Catalysts reported to be applicable to the copolymerization of alpha-olefin and cyclic olefin include Ziegler-Natta catalyst, metallocene catalyst, late transition metal catalyst, etc. The metallocene catalyst has the characteristics of high catalytic activity, single active center, capability of effectively catalyzing and synthesizing olefin copolymer with narrow relative molecular weight distribution and uniform composition distribution, and the like, so the metallocene catalyst is used as a first-choice catalyst for catalyzing the copolymerization of alpha olefin and cycloolefin. For example, patent application No. CN201710933992.7 (publication No. CN109627366A) patent application No. CN201710933992.7, a metallocene catalyst and its application in preparation of cyclic olefin copolymer, reports a catalytic system with structure of zirconocene dichloride/MAO, etc., which can catalyze copolymerization of ethylene and cyclic olefin monomer. However, the catalytic activity of the reaction is low due to the large steric hindrance of the metallocene ligand, and the insertion rate of the cycloolefin monomer is also low.
In addition, in the reports available for the synthesis of cyclic olefin copolymers at present, the metallocene catalyst used for catalyzing polymerization is generally a mononuclear metallocene catalyst. Meanwhile, in the experiment of catalyzing the copolymerization of alpha olefin and cycloolefin by using the metallocene catalyst, the problems of low catalytic activity, low insertion rate of cycloolefin monomers, low glass transition temperature of the obtained polymer and the like still exist, and the application range of the polymer is limited.
With the recent economic development, the demand for high-performance cycloolefin copolymers has been increasing. Therefore, the development of highly active metallocene catalysts for the catalytic synthesis of cycloolefin copolymers is an important issue of current interest.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a dinuclear metallocene compound capable of improving catalytic activity and insertion rate of cycloolefin monomer in view of the current state of the art.
The second technical problem to be solved by the present invention is to provide a method for preparing the above dinuclear metallocene compound.
The third technical problem to be solved by the present invention is to provide an application of the above dinuclear metallocene compound.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a dinuclear metallocene compound characterized by the general formula:
in the formula I, M is one of Ti, Zr and Hf;
cyclopentadiene-R1 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
cyclopentadiene-R2 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
r3 is one of C1-C8 straight chain or branched chain alkyl, C7-C21 single aryl alkyl or double aryl alkyl, C1-C8 alkyl silicon base;
the group A is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group B is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group C is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group D is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl.
Preferably, the general formula is:
further, the cyclopentadiene-R1 is cyclopentadienyl or pentamethylcyclopentadienyl; the cyclopentadiene-R2 is cyclopentadienyl or pentamethylcyclopentadienyl.
Still further, the dinuclear metallocene compound is one of the following formulas C-1, C-2 and C-3;
the technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the dinuclear metallocene compound is characterized by comprising the following steps: dissolving metal chloride in an anhydrous solvent under the atmosphere of nitrogen, cooling to-40 to-20 ℃, and uniformly stirring; then adding lithium salt into the reaction kettle at one time, and after the charging is finished, returning to the room temperature and continuing stirring for 16-24 hours to carry out reaction; after the reaction is finished, carrying out anhydrous and anaerobic filtration on the reaction solution, and collecting filtrate; drying the filtrate in vacuum to separate out solid; dissolving the solid in a small amount of anhydrous solvent, and standing at-40 to-20 ℃ to precipitate crystals; then separating the crystal, and drying in vacuum to obtain the required dinuclear metallocene compound;
the metal chloride has the general formula:
wherein the cyclopentadiene-R1 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
m is one of Ti, Zr and Hf;
the lithium salt has the general formula:
wherein R3 is one of C1-C8 straight chain or branched chain alkyl, C7-C21 single aryl alkyl or double aryl alkyl, C1-C8 alkyl silicon base;
the group A is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group B is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group C is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group D is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl.
Preferably, the molar ratio of the added metal chloride to the added lithium salt is 1: 0.5-0.55.
Preferably, the anhydrous solvent is at least one of anhydrous diethyl ether, tetrahydrofuran, toluene, xylene and dichloromethane.
The technical scheme adopted by the invention for solving the third technical problem is as follows: the application of the dinuclear metallocene compound is characterized in that: the dinuclear metallocene compound is applied to catalyzing the copolymerization reaction of alpha olefin and cycloolefin.
Preferably, the copolymerization comprises the following steps: under the anhydrous and oxygen-free conditions, carrying out solution polymerization reaction on alpha olefin, cycloolefin, metallocene compound and cocatalyst in an organic solvent; the polymerization time is 5-10 min, the polymerization temperature is 60-100 ℃, and the polymerization pressure is 0.1-5 Mpa; after the reaction is finished, quenching the reaction product by using acidified ethanol, settling and separating the reaction product, and drying the reaction product in vacuum to obtain the required cyclic olefin copolymer.
Further, the alpha olefin is at least one of ethylene, propylene, butene, hexene, octene and decene;
the cycloolefin is at least one of cyclopentene, cyclohexene, norbornene and tetracyclododecene;
the cocatalyst is at least one of Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), Ethylaluminoxane (EAO) and isobutylaluminoxane (i-BAO);
the organic solvent is at least one of directly-connected aliphatic hydrocarbon, cyclic aliphatic hydrocarbon and aromatic hydrocarbon;
the molar ratio of the metal aluminum in the cocatalyst to the metal element in the dinuclear metallocene compound is 100-20000: 1;
compared with the prior art, the invention has the advantages that:
(1) the novel dinuclear metallocene compound designed and synthesized by the application is a kind of single metallocene compound, not only maintains the characteristics of high catalytic activity, single active center and the like of the metallocene catalyst, but also reduces the steric hindrance near the catalytic site, and can effectively improve the insertion rate of cycloolefin monomers; therefore, when the dinuclear metallocene compound is used for catalyzing the copolymerization of the cycloolefin, the catalyst has higher catalytic activity and higher insertion rate of the cycloolefin monomer;
(2) most of the reported dinuclear metallocene catalysts have the characteristic of low activity compared with the corresponding mononuclear metallocene catalysts because bridging groups have strong rigidity and large steric hindrance and double metal centers are far away and ligands are difficult to rotate freely; in addition, bridging groups of part of dinuclear metallocene catalysts have complex structures and are difficult to synthesize, so that the development and application of the metallocene catalysts are limited;
on one hand, the rigidity of the bridging group is reduced by introducing the flexible connecting group into the bridging group, so that two metal centers are close to each other in spatial distance to generate a synergistic effect, and the catalytic activity of the dinuclear metallocene compound is higher than that of the corresponding mononuclear metallocene compound;
(3) according to the metallocene compound designed by the application, electron-withdrawing substituents such as halogen and the like are introduced to a ligand, so that the balance is obtained between a steric hindrance effect and an electronic effect, the characteristic of high catalytic activity of a metallocene catalyst is kept, and the insertion rate of a cycloolefin monomer is improved;
(4) the preparation method provided by the application has the advantages of easily available raw materials and convenience in synthesis;
(5) the binuclear metallocene compound is used as a catalyst in the copolymerization reaction of alpha olefin and cycloolefin, so that the insertion rate of the cycloolefin monomer can be greatly improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example a 1:
(1) preparation of dinuclear metallocene Compound A-1:
under nitrogen atmosphere, 5mmol of cyclopentadienyl titanium trichloride (CpTiCl)3) Dissolving in 50mL of anhydrous toluene, cooling to-30 ℃, and stirring; then 2.5mmol of dilithium bisphenol A is added in one portion; returning to room temperature and continuing stirring for 24 h; after the reaction is finished, carrying out anhydrous and oxygen-free filtration on the reaction solution, and collecting filtrate; the filtrate is dried in vacuum to separate out solid; dissolving the solid in a small amount of anhydrous toluene, and standing at-40 to-20 ℃ to separate out crystals; then separating the crystal and drying in vacuum to obtain the corresponding dinuclear metallocene compound A-1 with the yield of 78 percent,1H NMR(CDCl3，δ，ppm)：6.65-6.98(M,8H,C6H4),6.72(S,10H,C5H5),1.59(S,6H,C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 μmol metallocene compound A-1 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 2:
(1) preparation of dinuclear metallocene Compound A-2:
the differences from example A1 are: in the synthesis raw material of dinuclear metallocene compound A-2, indenyl titanium trichloride is selected to replace CpTiCl3Simultaneously, tetramethyl bisphenol A dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 75 percent,1H NMR(CDCl3，δ，ppm)：6.82-7.37(M,12H),6.46(d,4H,Ind),6.18(t,2H,Ind),2.19(S,12H,C6H2(CH3)2),1.58(S,6H,C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then 4.8mmol of MAO and 1.2 mu mol of metallocene compound A-2 are added in turn, ethylene is charged rapidly, the pressure is increased to 0.6MPa, and the reaction is continued for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 3:
(1) preparation of dinuclear metallocene Compound A-3:
the differences from example A1 are: in the synthesis raw material of dinuclear metallocene compound A-3, pentamethylcyclopentadienyl titanium trichloride is selected to replace CpTiCl3Simultaneously, 4' -diphenylmethylene bisphenol dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 68 percent,1H NMR(CDCl3，δ，ppm)：7.09-7.26(M,10H,C6H5),6.65-6.82(M,8H,C6H4),1.95(S,30H,C5(CH3)5)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 90 ℃, and uniformly stirring; then adding 1.2mmol MAO and 1.2 mu mol metallocene compound A-3 in turn, rapidly charging ethylene, increasing the pressure to 3MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 4:
(1) preparation of dinuclear metallocene Compound A-4:
the differences from example A1 are: in the raw materials for synthesizing the dinuclear metallocene compound A-4, 4' -methylene bis (2, 6-di-tert-butylphenol) dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 72 percent,1H NMR(CDCl3，δ，ppm)：7.02(d,4H,C6H2),6.72(S,10H,C5H5),5.02(S,2H,CH2),1.42(S,36H,C(CH3)3)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 100 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 mu mol metallocene compound A-4 in turn, rapidly charging ethylene, increasing the pressure to 5MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 5:
(1) preparation of dinuclear metallocene Compound A-5:
the differences from example A1 are: dinuclear metallocene compound A-5, tetramethyl bisphenol A dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 70 percent,1H NMR(CDCl3，δ，ppm)：7.06(S,4H,C6H2),6.72(S,10H,C5H5),2.19(S,12H,C6H2(CH3)2),1.58(S,6H,C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 mu mol metallocene compound A-5 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 6:
(1) preparation of dinuclear metallocene Compound A-5: in keeping with example a 5;
(2) preparation of propylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 60 ℃, and uniformly stirring; then sequentially adding 3.6mmol of MMAO and 1.2 mu mol of metallocene compound A-5, rapidly charging propylene to increase the pressure to 0.1MPa, and continuing to react for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the propylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example a 7:
(1) preparation of dinuclear metallocene Compound A-5: in keeping with example a 5;
(2) preparation of ethylene/tetracyclododecene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of tetracyclododecene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 7.2mmol MAO and 1.2 mu mol metallocene compound A-5 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/tetracyclododecene copolymer is obtained after the precipitation separation and vacuum drying.
Example A8:
(1) preparation of dinuclear metallocene Compound A-5: in keeping with example a 5;
(2) preparation of ethylene/tetracyclododecene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of tetracyclododecene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then sequentially adding 12mmol of MMAO and 1.2 mu mol of metallocene compound A-5, rapidly charging ethylene, raising the pressure to 2MPa, and continuing to react for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/tetracyclododecene copolymer is obtained after the precipitation separation and vacuum drying.
Example C1:
(1) preparation of dinuclear metallocene Compound C-1:
the differences from example A1 are: in the raw materials for synthesizing the dinuclear metallocene compound C-1, tetrachlorobisphenol dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the example A1; the yield is 78 percent,1H NMR(CDCl3，δ，ppm)：7.06(S,4H,C6H2),6.72(S,10H,C5H5),1.59(S,6H,C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 mu mol metallocene compound C-1 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example C2:
(1) preparation of dinuclear metallocene Compound C-2:
the differences from example A1 are: in the raw materials for synthesizing the dinuclear metallocene compound C-2, 3 '-dimethyl-5, 5' -dichlorobisphenol A dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 73 percent,1H NMR(CDCl3，δ，ppm)：6.82-7.01(M,4H,C6H2),6.74(S,10H,C5H5),2.15(S,6H,C6H2(CH3)),1.59(S,6H,C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 100 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 μmol metallocene compound C-2 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example C3:
(1) preparation of dinuclear metallocene Compound C-3:
the differences from example A1 are: in the raw material for synthesizing the dinuclear metallocene compound C-3, pentamethylcyclopentadienyl titanium trichloride is selected to replace CpTiCl3Meanwhile, 3' -dichlorobisphenol A dilithium is selected to replace bisphenol A dilithium, and the rest is consistent with the embodiment A1; the yield is 80 percent,1H NMR(CDCl3，δ，ppm)：6.78-7.03(M,6H,C6H3),1.98(S,30H,C5(CH3)5),1.60(S,6H C(CH3)2)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 mu mol metallocene compound C-3 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example C4:
(1) preparation of dinuclear metallocene Compound C-1: in keeping with example C1;
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 1.2mmol of MAO and 1.2 mu mol of metallocene compound C-1 in sequence, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Example C5:
(1) preparation of dinuclear metallocene Compound C-1: in keeping with example C1;
(2) preparation of ethylene/tetracyclododecene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of tetracyclododecene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then 4.8mmol of MAO and 1.2 mu mol of metallocene compound C-1 are added in turn, ethylene is charged rapidly, the pressure is increased to 0.6MPa, and the reaction is continued for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/tetracyclododecene copolymer is obtained after the precipitation separation and vacuum drying.
Example C6:
(1) preparation of dinuclear metallocene Compound C-1: in keeping with example C1;
(2) preparation of propylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 1.2 mu mol metallocene compound C-1 in turn, rapidly charging propylene, increasing the pressure to 0.1MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the propylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Comparative example 1:
(1) preparation of mononuclear metallocene Compound D-1:
under nitrogen atmosphere, 5mmol of CpTiCl3Dissolving in 50mL of anhydrous ether, cooling to-30 ℃, and stirring; then 5mmol of lithium phenoxide was added in one portion; returning to room temperature and continuing stirring for 24 h; after the reaction is finished, carrying out anhydrous and oxygen-free filtration on the reaction solution, and collecting filtrate; the filtrate is dried in vacuum to separate out solid; dissolving the solid in a small amount of mixed solution of anhydrous ether and anhydrous n-hexane, and standing at the temperature of between 40 ℃ below zero and 20 ℃ below zero to separate out crystals; the crystals were subsequently isolated and dried in vacuo to give the corresponding mononuclear metallocene compound D-1 in 78% yield,1H NMR(CDCl3，δ，ppm)：6.94-7.30(m,5H,C6H5),6.80(s,5H，C5H5)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 2.4 μmol metallocene compound D-1 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Comparative example 2:
(1) preparation of mononuclear metallocene Compound D-2:
under nitrogen atmosphere, 5mmol of CpTiCl3Dissolving in 50mL of anhydrous ether, cooling to-30 ℃, and stirring; then, adding 5mmol of 2, 6-dichlorophenol lithium at one time; returning to room temperature and continuing stirring for 24 h; after the reaction is finished, carrying out anhydrous and oxygen-free filtration on the reaction solution, and collecting filtrate; the filtrate is dried in vacuum to separate out solid; dissolving the solid in a small amount of mixed solution of anhydrous ether and anhydrous n-hexane, and standing at the temperature of between 40 ℃ below zero and 20 ℃ below zero to separate out crystals; the crystals were subsequently isolated and dried in vacuo to give the corresponding mononuclear metallocene compound D-2 in a yield of 72%,1H NMR(CDCl3，δ，ppm)：7.30(d,2H,C6H3),6.94(t,1H,C6H3),6.80(s,5H，C5H5)；
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 2.4 μmol metallocene compound D-2 in turn, rapidly charging ethylene, increasing the pressure to 0.6MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
Comparative example 3:
(1) the catalytic experiment was carried out with the commercially available catalyst rac-dimethylsilylbis (1-indenyl) zirconium dichloride (D-3);
(2) preparation of ethylene/norbornene copolymer: under the anhydrous and anaerobic conditions, adding 0.4mol of norbornene into a 500mL reaction kettle, continuously adding toluene until the total volume is 250mL, heating to 80 ℃, and uniformly stirring; then adding 3.6mmol MAO and 2.4 μmol metallocene compound D-3 in turn, rapidly charging ethylene, increasing the pressure to 4MPa, and continuing the reaction for 10 min; after the reaction is finished, the reaction is quenched by acidified ethanol, and the ethylene/norbornene copolymer is obtained after the precipitation separation and vacuum drying.
The results of the performance tests of all the above examples and comparative examples are shown in table 1.
Table 1:
the characterization method comprises the following steps:
(1) cyclic olefin monomer content in the polymer:
the content of cycloolefine in the polymer is measured by a nuclear magnetic resonance apparatus, the nuclear magnetic resonance method is that the polymer is dissolved in deuterated o-dichlorobenzene, hexamethyldisiloxane is taken as an internal standard, the measuring temperature is 120 ℃, and the carbon spectrum scanning times are 1000 times;
(2) and (3) calculating the catalytic activity:
the formula of the catalytic activity of the catalyst is as follows:
catalytic activity ═ polymer mass/(molar amount of Ti in the catalyst ×. polymerization time) (units kg/(mmol h));
(3) glass transition temperature:
the glass transition temperature was measured using a DSC instrument. The test method was to heat up from 40 ℃ to 300 ℃ at a rate of 20 ℃/min. Keeping the temperature at 300 ℃ for 5min, and then reducing the temperature to 40 ℃ at a speed of 20 ℃/min. The temperature was kept constant at 40 ℃ for 5min and then increased to 300 ℃ at 20 ℃/min. Keeping the temperature at 300 deg.C for 5min, and cooling to 40 deg.C at 20 deg.C/min.
As can be seen from table 1:
(1) as can be seen from comparison of comparative examples A-1 to A-8 and comparative example 1, and examples C-1 to C-6 and comparative example 2, dinuclear metallocene compounds exhibited higher catalytic activity in the experiment for catalyzing the copolymerization of alpha-olefin and cyclic olefin, as compared with the mononuclear metallocene compounds; meanwhile, the polymer obtained by catalysis has higher glass transition temperature, and the phenomena show that the dinuclear metallocene compound has special synergistic effect, so that the dinuclear metallocene compound has higher catalytic activity and insertion rate of cycloolefin monomers in the polymerization reaction;
(2) comparing each example with comparative example 3, it can be seen that, under the catalysis of the metallocene catalyst rac-dimethylsilylbis (1-indenyl) zirconium dichloride, the glass transition temperature of the obtained ethylene/norbornene copolymer is only 75 ℃, the monomer insertion rate is not more than 26.7%, while the insertion rate of the cycloolefin monomer of the ethylene/norbornene copolymer obtained by the catalysis of the metallocene catalyst is not less than 40%, and meanwhile, when the tetracyclododecene monomer with higher steric hindrance is used as the comonomer, the insertion rate of the cycloolefin monomer can also reach more than 35%; therefore, the single metallocene catalyst is more suitable for catalyzing the copolymerization of alpha olefin and cycloolefin monomer;
(3) it has been conventionally thought that in metallocene catalysts, the stronger the electron donating ability of the ligand, the more stable the cationic active site, thereby increasing the activity of the catalyst. However, in the present invention, it can be seen from the comparison between examples A1 to A8 and examples C1 to C6 that the introduction of an electron-withdrawing substituent such as halogen to the ligand greatly improves not only the catalytic activity of the metallocene catalyst but also the insertion rate of the cycloolefin monomer.
The above description is only a few specific embodiments of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A dinuclear metallocene compound characterized by the general formula:
in the formula I, M is one of Ti, Zr and Hf;
cyclopentadiene-R1 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
cyclopentadiene-R2 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
r3 is one of C1-C8 straight chain or branched chain alkyl, C7-C21 single aryl alkyl or double aryl alkyl, C1-C8 alkyl silicon base;
the group A is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group B is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group C is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group D is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl.
2. The dinuclear metallocene compound according to claim 1, characterized by the general formula:
3. the dinuclear metallocene compound according to claim 2, characterized in that: the cyclopentadiene-R1 is cyclopentadienyl or pentamethylcyclopentadienyl; the cyclopentadiene-R2 is cyclopentadienyl or pentamethylcyclopentadienyl.
4. The dinuclear metallocene compound according to claim 3, characterized in that: the dinuclear metallocene compound is one of the following formulas C-1, C-2 and C-3;
5. a method for preparing the dinuclear metallocene compound according to any one of claims 1 to 4, characterized by comprising the steps of: dissolving metal chloride in an anhydrous solvent under the atmosphere of nitrogen, cooling to-40 to-20 ℃, and uniformly stirring; then adding lithium salt into the reaction kettle at one time, and after the charging is finished, returning to the room temperature and continuing stirring for 16-24 hours to carry out reaction; after the reaction is finished, carrying out anhydrous and anaerobic filtration on the reaction solution, and collecting filtrate; drying the filtrate in vacuum to separate out solid; dissolving the solid in a small amount of anhydrous solvent, and standing at-40 to-20 ℃ to precipitate crystals; then separating the crystal, and drying in vacuum to obtain the required dinuclear metallocene compound;
the metal chloride has the general formula:
wherein the cyclopentadiene-R1 is one of substituted or unsubstituted cyclopentadienyl, fluorenyl and indenyl;
m is one of Ti, Zr and Hf;
the lithium salt has the general formula:
wherein R3 is one of C1-C8 straight chain or branched chain alkyl, C7-C21 single aryl alkyl or double aryl alkyl, C1-C8 alkyl silicon base;
the group A is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group B is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group C is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl;
the group D is one of halogen, hydrogen and C1-C8 straight chain or branched chain alkyl.
6. The method of claim 5, wherein: the molar ratio of the added metal chloride to the added lithium salt is 1: 0.5-0.55.
7. The method of claim 5, wherein: the anhydrous solvent is at least one of anhydrous ether, tetrahydrofuran, toluene, xylene and dichloromethane.
8. Use of the dinuclear metallocene compound according to any one of claims 1 to 4, characterized in that: the dinuclear metallocene compound is applied to catalyzing the copolymerization reaction of alpha olefin and cycloolefin.
9. Use according to claim 8, characterized in that: the copolymerization reaction comprises the following steps: under the anhydrous and oxygen-free conditions, carrying out solution polymerization reaction on alpha olefin, cycloolefin, metallocene compound and cocatalyst in an organic solvent; the polymerization time is 5-10 min, the polymerization temperature is 60-100 ℃, and the polymerization pressure is 0.1-5 Mpa; after the reaction is finished, quenching the reaction product by using acidified ethanol, settling and separating the reaction product, and drying the reaction product in vacuum to obtain the required cyclic olefin copolymer.
10. Use according to claim 9, characterized in that: the alpha olefin is at least one of ethylene, propylene, butene, hexene, octene and decene;
the cycloolefin is at least one of cyclopentene, cyclohexene, norbornene and tetracyclododecene;
the cocatalyst is at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane;
the organic solvent is at least one of directly-connected aliphatic hydrocarbon, cyclic aliphatic hydrocarbon and aromatic hydrocarbon;
the molar ratio of the metal aluminum in the cocatalyst to the metal element in the dinuclear metallocene compound is 100-20000: 1.
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