CN113248548A - Preparation method and application of single metallocene catalyst - Google Patents
Preparation method and application of single metallocene catalyst Download PDFInfo
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- JBISHCXLCGVPGW-UHFFFAOYSA-N 2,6-dichlorobenzenethiol Chemical compound SC1=C(Cl)C=CC=C1Cl JBISHCXLCGVPGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, styrene Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 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 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 abstract description 9
- 229920000098 polyolefin Polymers 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract 2
- 239000000178 monomer Substances 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a preparation method of a 2, 6-dichlorothiophenol coordinated single metallocene catalyst and an application of the catalyst in olefin polymerization. The invention introduces thiophenol ligand containing electron-withdrawing group, constructs novel single metallocene catalyst, can improve the coordination capability of monomer by introducing electron-withdrawing group, realizes high activity and high copolymerization capability, and prepares polyolefin copolymer with various structures. The novel single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good copolymerization performance, is suitable for preparing polyolefin resin by olefin polymerization, and the prepared polyolefin has higher molecular weight and comonomer insertion rate. Therefore, the single metallocene catalyst reported by the invention has original innovativeness, and can enhance the competitive power of China participating in the technical market of international high-end polyolefin high polymer materials.
Description
Technical Field
The invention relates to a preparation method of a single metallocene catalyst and an application of the single metallocene catalyst in olefin polymerization.
Background
Polyolefin is a synthetic polymer material with fastest development, maximum yield and extremely wide application in the current society. Commercial polyethylene Catalysts are Ziegler-Natta Catalysts (DE Pat 889229 (1953); IT Pat 545332(1956) and IT Pat 536899(1955)), Phillips Catalysts (Belg. Pat.530617(1955)) and metallocene Catalysts (W. Kaminsky, Metaorganic Catalysts for Synthesis and Polymerization, Berlin: Springer,1999), as well as highly efficient ethylene homo-and copolymerization Catalysts of the transition metal complex type which have been developed in recent years. Among them, metallocene catalysts have been receiving wide attention and developed rapidly because of their advantages such as high activity, high selectivity, and product diversity.
The invention discloses a preparation method of a thiophenol single metallocene catalyst containing an electron-withdrawing substituent and application of the thiophenol single metallocene catalyst in olefin polymerization. The invention introduces thiophenol ligand containing electron-withdrawing substituent, designs and synthesizes novel single metallocene catalyst, can conveniently regulate and control the catalytic performance of the single metallocene catalyst by changing the substituent, and prepares polyolefin high polymer materials with various structures and various performances. The novel single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good copolymerization performance, is suitable for preparing cycloolefin copolymer by copolymerization of olefin and cycloolefin, and the prepared polyolefin has higher molecular weight and comonomer insertion rate. Therefore, the single metallocene catalyst reported by the invention has original innovativeness, and can enhance the competitive power of China participating in the technical market of international high-end polyolefin high polymer materials.
Disclosure of Invention
The invention aims to provide a preparation method of a single metallocene catalyst and application of the single metallocene catalyst in olefin polymerization.
The invention provides a single metallocene catalyst shown in formulas I-V:
the invention provides a preparation method of the single metallocene catalyst, which comprises the following steps:
dissolving 2, 6-dichloro-thiophenol in 30-100mL of anhydrous solvent under the atmosphere of nitrogen, adding 1.0-1.5 molar equivalent of n-butyllithium, stirring for 6-12 hours, then adding 1 molar equivalent of a metallocene trichlorometal compound, and continuing stirring for 24 hours; removing the solvent under reduced pressure, and extracting with a good solvent to obtain the single metallocene catalyst.
In the preparation method, the anhydrous solvent is selected from benzene, toluene, xylene and n-hexane; the good solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane and toluene.
The invention also provides the application of the single metallocene catalyst shown in the formulas I-V in catalyzing olefin polymerization reaction.
In the application, the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, dicyclopentadiene and tetracyclododecene.
The catalyst is also added with a cocatalyst which is one or more of trifluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, aluminoxane, alkylaluminium and alkylaluminium chloride. The aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; the alkylaluminum chloride is diethylaluminum chloride, diethylaluminum sesquichloride or ethylaluminum dichloride.
In the polymerization reaction, the polymerization temperature is 0-180 ℃, the polymerization pressure is 0.1-5Mpa, and the polymerization solvent is one or more of toluene, hexane and heptane.
The invention provides a preparation method of a single metallocene catalyst and an application of the compound in catalyzing olefin polymerization. The novel single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good copolymerization performance, and is suitable for olefin homopolymerization and copolymerization reactions.
Drawings
FIG. 1 is a crystal structure diagram of catalyst I.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto. Embodiments of the present invention will allow those skilled in the art to more fully understand the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The invention is described below in terms of specific examples.
Example 1 preparation of a Monometallocene catalyst I
2, 6-dichlorothiophenol (1.79g,10mmol), 50mL of dried toluene and 4.4mL/12mmol of n-butyllithium were added slowly and stirred for 6 hours. Cyclopentadienyl titanium trichloride (2.19g,10mmol) was added and the reaction was stirred for 12 hours. The solvent was removed, extracted with toluene, filtered, and the solvent removed and drained to give 2.80g of the product in 77% yield.1H NMR(400MHz,CDCl3):δ7.48(d,J＝8.0Hz,2H),7.29(dd,J＝7.7,4.4Hz,1H),7.00(s,5H).13C NMR(CDCl3):δ137.97,130.89,128.82,123.52,120.80.Anal.Calcd for C11H8Cl4STi:C,36.51；H,2.23.Found:C,36.24；H,2.11.
Example 2 preparation of a Monometallocene catalyst II
2, 6-dichlorothiophenol (1.79g,10mmol), 50mL of dried toluene and 4.4mL/12mmol of n-butyllithium were added slowly and stirred for 6 hours. Indenyl titanium trichloride (2.69g,10mmol) was added and the reaction was stirred for 12 hours. The solvent was removed, extracted with toluene, filtered, and the solvent removed and drained to give 2.68g of product in 65% yield.1H NMR(400MHz,CDCl3):δ7.85(dd,J＝6.6,6.5Hz,2H),7.48(dd,J＝6.6,6.5Hz,2H),7.33(d,J＝8.4Hz,2H),7.28(d,J＝3.4Hz,2H),7.14(t,J＝8.4Hz,1H),6.95(t,J＝3.4Hz,1H).13C NMR(CDCl3):δ138.85,138.01,130.49,129.95,129.47,128.58,126.90,121.20,114.05.Anal.Calcd for C15H10Cl4STi:C,43.73；H,2.45.Found:C,43.56；H,2.24.
Example 3 preparation of a Monometallocene catalyst III
2, 6-Dichlorothiophenol (1.79g,10mmol), 50mL of dry toluene was added and 4.4m of toluene was added slowlyL/12mmol of n-butyllithium, and stirred for 6 hours. Pentamethyltitanium trichloride (2.90g,10mmol) was added thereto, and the reaction was stirred for 12 hours. The solvent was removed, extracted with toluene, filtered, and the solvent removed and drained to give the product 3.55g, 82% yield.1H NMR(400MHz,CDCl3):δ7.35(d,J＝8.0Hz,2H),7.14(t,J＝8.0Hz,1H),2.37(s,15H).13C NMR(CDCl3):δ138.76,138.42,134.42,129.82,128.48,14.23.Anal.Calcd for C16H18Cl4STi:C,44.48；H,4.20.Found:C,44.21；H,4.02.
Example 4 Monometallocene catalyst I catalyzed ethylene polymerization
A350 mL polymerization flask with magnetic stirrer was dried continuously at 120 ℃ for 6hrs, evacuated while hot and charged with N2Replace qi for 3 times. 0.72mg (2. mu. mol) of catalyst I was added, followed by B (C)6F5)3And MAO, such that Al/Ti is 200 and B/Ti is 1.2. Then, vacuum was applied and ethylene was substituted 3 times. 50ml of toluene was injected by a syringe, and the reaction was vigorously stirred at 30 ℃ for 10min while maintaining an ethylene pressure of 5 atm. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity 0.51X 106g·mol-1(Ti)·h-1. Polymer Mw＝429kg·mol-1，Mw/Mn＝4.1。
Example 5 Monometallocene catalyst II catalyzed ethylene polymerization
The polymerization process and reaction conditions were the same as in example 4, and the catalyst used was II. Polymerization Activity 1.08X 106g·mol-1(Zr)·h-1. Polymer Mw＝32.9kg·mol-1，Mw/Mn＝1.5。
Example 5 Monometallocene catalyst I catalysis of copolymerization of ethylene and 1-octene
A350 mL polymerization flask with magnetic stirrer was dried continuously at 120 ℃ for 6hrs, evacuated while hot and charged with N2Replace qi for 3 times. 0.72mg (2. mu. mol) of catalyst I was added, followed by B (C)6F5)3And MAO, such that Al/Ti is 200 and B/Ti is 1.2. Then vacuumizedAnd replaced 3 times with ethylene. 50ml of toluene was injected by a syringe, 50mmol of 1-octene was added at 30 ℃ under an ethylene pressure of 5atm, and the reaction was vigorously stirred for 1 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity 9.3X 106g·mol-1(Ti)·h-1. Polymer Mw＝17.1kg·mol-1，Mw/MnThe 1-octene content in the copolymer was 15.0 mol%, 7.2.
Example 6 catalysis of copolymerization of ethylene and norbornene by Monometallocene catalyst III
A350 mL polymerization flask with magnetic stirrer was dried continuously at 120 ℃ for 6hrs, evacuated while hot and charged with N2Replace qi for 3 times. 0.72mg (2. mu. mol) of catalyst I was added, followed by B (C)6F5)3And MAO, such that Al/Ti is 200 and B/Ti is 1.2. Then, vacuum was applied and ethylene was substituted 3 times. 50ml of toluene was injected by a syringe, 100mmol of norbornene was added thereto at 30 ℃ and ethylene pressure of 5atm was maintained, and the reaction was vigorously stirred for 10 min. Neutralizing the reaction solution with 5% ethanol solution acidified by hydrochloric acid to obtain polymer precipitate, washing with ethanol for several times, vacuum drying to constant weight, and weighing. Polymerization Activity 6.8X 106g·mol-1(Ti)·h-1. Polymer Mw＝25.5kg·mol-1，Mw/MnThe norbornene content in the copolymer was 45.0 mol% as 3.0.
Claims (8)
1. The structure of the single metallocene catalyst is shown in formulas I-V.
2. A method for preparing the single metallocene catalyst of claim 1, comprising the steps of:
dissolving 2, 6-dichloro-thiophenol in 30-100mL of anhydrous solvent under the atmosphere of nitrogen, adding 1.0-1.5 molar equivalent of n-butyllithium, stirring for 6-12 hours, then adding 1 molar equivalent of a metallocene trichlorometal compound, and continuing stirring for 24 hours; removing the solvent under reduced pressure, and extracting with a good solvent to obtain the single metallocene catalyst.
3. The method of claim 2, wherein: the anhydrous solvent is selected from benzene, toluene, xylene and n-hexane; the good solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane and toluene.
4. A process for carrying out an olefin polymerization reaction, characterized by: the catalyst for the reaction is a mono-metallocene catalyst as described in claim 1.
5. The method of claim 4, wherein: the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, dicyclopentadiene and tetracyclododecene.
6. The method of claim 4, wherein: the catalyst is also added with a cocatalyst which is one or more of trifluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, aluminoxane, alkylaluminium and alkylaluminium chloride.
7. The method of claim 6, wherein: the aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; the alkylaluminum chloride is diethylaluminum chloride, diethylaluminum sesquichloride or ethylaluminum dichloride.
8. The method of claim 4, wherein: the polymerization temperature is 0-180 deg.C, polymerization pressure is 0.1-5Mpa, and polymerization solvent is one or more of toluene, hexane and heptane.
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Cited By (2)
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| CN114890987A (en) * | 2022-04-13 | 2022-08-12 | 万华化学集团股份有限公司 | Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof |
| CN115651011A (en) * | 2022-09-08 | 2023-01-31 | 黄河三角洲京博化工研究院有限公司 | Compound for catalyst, preparation method, olefin polymerization catalyst and application |
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| CN115651011A (en) * | 2022-09-08 | 2023-01-31 | 黄河三角洲京博化工研究院有限公司 | Compound for catalyst, preparation method, olefin polymerization catalyst and application |
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