CN115010838A - Olefin polymerization method and polyolefin obtained by same - Google Patents
Olefin polymerization method and polyolefin obtained by same Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000005977 Ethylene Substances 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 83
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 8
- 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 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 76
- 229920000642 polymer Polymers 0.000 description 63
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000009826 distribution Methods 0.000 description 28
- 238000007334 copolymerization reaction Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- SSBZEFBGQCOEIH-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 SSBZEFBGQCOEIH-UHFFFAOYSA-L 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000004927 fusion Effects 0.000 description 10
- -1 cocatalyst Substances 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FIJCYJKSMYMTSS-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=C(C=CC=2C3=CC=C(C=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=C(C=CC=2C3=CC=C(C=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=CC=C1 FIJCYJKSMYMTSS-UHFFFAOYSA-L 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical compound C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- DFZYPLLGAQIQTD-UHFFFAOYSA-N 2,7-ditert-butyl-9h-fluorene Chemical group CC(C)(C)C1=CC=C2C3=CC=C(C(C)(C)C)C=C3CC2=C1 DFZYPLLGAQIQTD-UHFFFAOYSA-N 0.000 description 1
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- QGEFGPVWRJCFQP-UHFFFAOYSA-M magnesium;methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC=C1 QGEFGPVWRJCFQP-UHFFFAOYSA-M 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- 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
-
- 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
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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 an olefin polymerization method and polyolefin obtained by the same, wherein the polymerization method comprises the following steps: reacting ethylene and an optional comonomer in the presence of a catalyst composition, wherein the catalyst composition comprises a compound represented by formula (I) and alkylaluminoxane, and the ethylene partial pressure is 1-100 atm during polymerization, and the polymerization temperature is 120-220 ℃ to obtain polyolefin:
in the formula (I), R 1 Selected from hydrogen or C 1 ～C 10 Alkyl of R 2 Selected from aryl or substituted aryl, M is selected from elements of group IVB, and X is selected from halogen, alkyl or alkoxy. The method of the invention adopts a special catalyst, and finds that the high-efficiency catalytic polymerization at high temperature can be realized, namely the high-efficiency catalysis is kept at high temperature; thus, the viscosity of the polymerization system is reduced at high temperatures, and the viscosity can be significantly increasedHigh production efficiency.
Description
Technical Field
The invention relates to an olefin polymerization catalyst, in particular to an olefin polymerization method and polyolefin obtained by the olefin polymerization method.
Background
Most comonomers have relatively high molecular weights and boiling points, which are not generally applicable to gas phase and slurry processes for existing polymerization processes. For such comonomers, a solution polymerization process is generally required. Solution polymerization is a polymerization mode in which all reactants including catalyst, cocatalyst, monomer and other auxiliaries and additives can be dissolved or uniformly dispersed in a solvent system.
Since the polymer produced will also dissolve in the solvent, the high viscosity of the reaction system produced after the polymer is dissolved will have a significant effect on the heat, mass and motion transfer of the polymerization process, which in turn may affect the uniformity of the reaction. Reducing the viscosity of the polymerization system can be solved by reducing the solid content of the polymerization system, but this greatly reduces the production efficiency. Another method is to increase the polymerization temperature and to lower the viscosity of the high-temperature system at the same solids content.
For most catalysts, increasing the polymerization temperature within a certain range will decrease the polymerization activity, e.g. most metallocene catalysts have a sharp decrease in activity at polymerization temperatures above 100 ℃. Therefore, it is an important and practical object to realize the polymerization of olefins at high temperatures with high efficiency as follows.
Disclosure of Invention
In order to overcome the problems in the prior art, the present invention provides an olefin polymerization method and a polyolefin obtained by the same, wherein the method can realize the systematic polymerization at high temperature by using a metallocene catalyst with a special structure, and the metallocene catalyst can still maintain the high-efficiency olefin catalysis at high temperature.
An object of the present invention is to provide an olefin polymerization process comprising: reacting ethylene and optionally a comonomer in the presence of a catalyst composition to obtain a polyolefin, wherein the catalyst composition comprises a compound of formula (I):
in the formula (I), R 1 Selected from hydrogen or C 1 ～C 10 Alkyl of (a), each R 1 Identical or different, R 2 Selected from aryl or substituted aryl, each R 2 Identical or different, M is selected from elements of group IVB, X is selected from halogen, hydrocarbyl or hydrocarbyloxy, each X being identical or different.
The metallocene catalyst has high copolymerization efficiency and broad spectrum, so that the metallocene catalyst can catalyze and obtain a plurality of new copolymers, and compared with copolymers obtained by other catalysts, the copolymers have new compositions and structures, thereby possibly having new performances, and further realizing the application of polyolefin materials in new fields. Most of the polyolefin new materials are copolymerized with simple olefins such as ethylene or propylene by selecting comonomers with proper structures, and the structural compositions of the comonomers have diversity and special functionality, so that the polyolefin materials can be endowed with new compositions and properties. Meanwhile, the comonomer also generates a synergistic effect due to the fact that the comonomer enters a polyolefin molecular chain, and the quality of the polyolefin is greatly improved.
In a preferred embodiment, in formula (I), R 1 Selected from hydrogen or C 1 ～C 5 Alkyl (e.g. C) 1 、C 2 、C 3 、C 4 Or C 5 ) Each R is 1 The same or different; r is 2 Selected from aryl, each R 2 The same or different; m is selected from Zr, Ti or Hf; x is selected from halogen and C 1 ～C 10 Alkyl (e.g. C) 1 、C 2 、C 3 、C 4 Or C 5 ) Or C 6 ～C 10 Aryl (e.g. C) 6 、C 7 、C 8 、C 9 Or C 10 ) Each X is the same or different.
In a further preferred embodiment, in formula (I), R 1 Selected from hydrogen or tert-butyl, each R 1 The same or different; r is 2 Selected from phenyl, each R 2 The same or different; m is selected from Zr; x is selected from chlorine atom, methyl, ethyl, n-butyl or benzyl, and each X is the same or different.
Metallocene catalysts generally exhibit higher activity at higher temperatures (e.g., 60-90 ℃) than at lower temperatures (e.g., 0-60 ℃ or even below 0 ℃). However, it is widely known that when the polymerization temperature is high (more than 100 ℃ C.), the polymerization activity is greatly lowered, and therefore, the polymerization temperature exceeding 100 ℃ C is rarely used for general polymerization studies. Therefore, the compound of formula (I) is not considered to be an effective polymerization catalyst at high temperature, and the inventors have surprisingly found through a lot of experiments that the catalyst can be carried out at high temperature by using the compound of formula (I), and the catalyst still has high activity at high temperature, thereby achieving unexpected technical effects.
In a preferred embodiment, the alkylaluminoxane has the structure according to formula (II) or formula (III):
in the formulae (II) and (III), R is selected from C 1 -C 12 Alkyl group of (A) or (B),Each R is the same or different; n is an integer of 4 to 30.
In a further preferred embodiment, in formula (II) and formula (III), R is selected from C 1 -C 5 Each R is the same or different; n is an integer of 10 to 30.
In a still further preferred embodiment, the alkylaluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
In a preferred embodiment, the molar ratio of the compound of formula (I) to the alkylaluminoxane in the catalyst composition is 1 (50-20000), preferably 1 (100-5000), and more preferably 1 (300-2000).
For example, the molar ratio of the compound of formula (I) to the alkylaluminoxane is 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:5000, 1:6000, 1:7000, 1:8000, 1:9000, 1:10000, 1: 20000.
In a preferred embodiment, the reaction is carried out in a solvent selected from toluene and/or C 3 ～C 18 Is a saturated alkane.
In a further preferred embodiment, the solvent is selected from toluene and/or C 5 ～C 8 Preferably toluene.
In a preferred embodiment, the polymerization is carried out at an ethylene partial pressure of 1 to 100 atmospheres, preferably 5 to 50 atmospheres, more preferably 5 to 30 atmospheres.
In a preferred embodiment, the polymerization temperature is 120-220 ℃, preferably 120-180 ℃, more preferably 120-160 ℃, such as 120-140 ℃ or 140-160 ℃. For example: 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, and the above points can be arbitrarily combined to form the polymerization temperature range.
According to the general knowledge of the skilled person, the compounds of formula (I) should be reacted below 100 ℃ since further increases in temperature may lead to a decrease in the catalytic activity of the catalyst. Thus, there has been no use to date for the polymerization of olefins at high temperatures using compounds of formula (I). However, the inventors have unexpectedly found that the compounds of formula (I) can be used at high temperatures and that they retain high catalytic activity at high temperatures. In addition, the inventors have found that polymerization at high temperatures also has the unexpected technical effect of significantly increasing the yield, i.e., the yield of polymer when polymerized at the high temperatures of the present invention is significantly higher than when polymerized at conventional temperatures below 100 ℃.
Specifically, if the polymerization is carried out at 70 to 100 ℃, the viscosity of the system may be high when the polymerization reaches 10%, and the reaction has to be stopped; however, if polymerization is carried out at a high temperature, the degree of polymerization can be as high as 80%, and the productivity is remarkably improved.
In a preferred embodiment, the comonomer is selected from C 3 ～C 10 The olefin (or terminal olefin).
In a further preferred embodiment, the comonomer is selected from at least one of 1-butene, 1-hexene and 1-octene.
Another object of the present invention is to provide a polyolefin obtained by the olefin polymerization method described in the first object of the present invention.
In a preferred embodiment, the polyolefin has a number average molecular weight of from 1 to 4 million.
According to the general knowledge of those skilled in the art, the lower the polymerization temperature, the higher the molecular weight of the polymer, i.e., the average molecular weight of the polymer decreases greatly with the increase in the reaction temperature, and no high molecular weight polymer is obtained. However, after a lot of experiments, the inventors have found that polyolefins with high molecular weight and narrow molecular weight distribution can be obtained by olefin polymerization at high temperature using the compound of formula (I). Thus, the polymer preparation carried out by the preparation process described as one of the objects of the present invention achieves unexpected technical effects.
Specifically, the catalyst still maintains higher reaction activity at high temperature, and a high molecular weight polymer can be obtained at the high temperature of 120-220 ℃. Compared with the prior art, the method can raise the initial temperature of the polymer with the molecular weight reduced by the influence of the polymerization temperature. For example, in the prior art, the molecular weight of the polymer may be significantly reduced at a polymerization temperature of 100 ℃, and polymers with molecular weights of about 1 ten thousand or more and 1 ten thousand or more cannot be obtained. However, in the polymerization system of the present application, about 1 ten thousand or more and even more than 1 ten thousand of polymers can still be obtained at the polymerization temperature of 140 ℃ or even 160 ℃, and the molecular weight of the polymers can be obviously reduced only when the temperature exceeds 220 ℃.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method of the invention adopts a special catalyst, and finds that the high-efficiency catalytic polymerization at high temperature can be realized, namely the high-efficiency catalysis is kept at high temperature; thus, the viscosity of the polymerization system is reduced at high temperature, and the production efficiency can be obviously improved;
(2) although the method is carried out at the extreme high temperature, the repeatability is very high, and the effect is consistent after a plurality of times of experiments are carried out repeatedly by adopting the same method, so the method can be suitable for industrial popularization.
Drawings
FIG. 1 shows a Gel Permeation Chromatography (GPC) curve of the polyolefin obtained in example 13;
FIG. 2 shows a Differential Scanning Calorimetry (DSC) curve of the polyolefin obtained in example 8;
FIG. 3 shows a Differential Scanning Calorimetry (DSC) curve of the polyolefin obtained in example 12.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The starting materials used in the examples and comparative examples are, if not particularly limited, those disclosed in the prior art, and may be, for example, obtained as they are or prepared according to the production methods disclosed in the prior art.
Preparation of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride:
a.500 ml three-mouth bottle, under the atmosphere of anhydrous and nitrogen, adding 4.1 g of sodium methoxide, 50ml of ethanol and 12.5 g of benzophenone, and starting magnetic stirring. 10ml of cyclopentadiene was added thereto, and the reaction was stirred at room temperature for 120 hours. The orange solid was collected by filtration and, after repeated rinsing with anhydrous ethanol, the solid was washed with refluxing methanol (50 ml) for 1 hour. After cooling, the solid was collected by filtration. The solid was dried in vacuo for 48 hours. 13.4 g of (6, 6-diphenyl fulvene) is obtained;
b. a250 ml three-necked bottle which had been fully dried was subjected to vacuum nitrogen substitution three times, 2.89 g of fluorene was added, 50ml of dry, deoxidized and dehydrated ether was added, and electromagnetic stirring was started. The solution was cooled to 0 ℃ with an ice bath. 7.3 ml of n-butyllithium (2.5 mol of n-butyllithium per liter of hexane solution) was slowly added dropwise using a syringe over a period of about 5 minutes. After the dropwise addition, the temperature is naturally raised to room temperature, and the reaction is continued to be stirred for 24 hours in total. 4.0 g of 6, 6-diphenylfulvene was added and the reaction was stirred for a further 120 hours. The reaction was cooled to 0 ℃ with an ice bath, and 20 ml of water and then 10ml of aqueous ammonium chloride were added to the slow solution. Filtration gave a crude product which was washed in 150ml of boiling ethanol for 2 hours. The hot solution was filtered and the solid obtained was dried in vacuo. 6.43 g of a product (fluorenylcyclopentadienyl diphenylmethane) was obtained;
c. a250 ml three-necked flask after being fully dried is replaced by nitrogen in vacuum for three times, 4.30 g of fluorenyl cyclopentadienyl diphenylmethane is added, 30 ml of dry deoxidized anhydrous ether is added, and electromagnetic stirring is started. The solution was cooled to 0 ℃ with an ice bath. 9.0 ml of n-butyllithium (2.5 mol of n-butyllithium per liter of hexane solution) was slowly added dropwise using a syringe over a period of about 8 minutes. After the dropwise addition, the temperature is naturally raised to room temperature, and the reaction is continued to be stirred for 24 hours in total. Acetone was added to the reaction mixture using liquid nitrogen, the reaction mixture was cooled to a temperature below-80 ℃ and 2.50 g of zirconium tetrachloride solid was added and slowly warmed to room temperature with stirring. After 24 hours of reaction, all the solvent was removed in vacuo, extracted with dehydrated deoxydichloromethane, and freeze-crystallized to obtain 1.35 g of (diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) as a solid product.
Preparation of diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride:
the procedure is analogous to diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride except that the fluorene in step b is replaced with 2, 7-di-tert-butylfluorene.
Preparation of diphenylmethylene (cyclopentadienyl) (fluorenyl) dibenzylzirconium:
a250 ml three-necked flask which had been fully dried was purged with nitrogen gas under vacuum three times, 1113 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared above was added, 50ml of dry, deoxidized, dehydrated ether was added, and electromagnetic stirring was turned on. The solution was cooled to 0 ℃ with an ice bath. Using a syringe, 4.0 ml of benzylmagnesium chloride (1.0 mol of benzylmagnesium bromide per liter of ethereal solution) was slowly added dropwise over a period of about 5 minutes. After the dropwise addition, the temperature is naturally raised to room temperature, the reaction is continued to be stirred, and the reaction time is 24 hours in total. All solvents were removed in vacuo, extracted with dry, deoxygenated dry dichloromethane, and lyophilized to give 835 mg (diphenylmethylene (cyclopentadienyl) (fluorenyl) dibenzylzirconium) as a solid product).
Preparation of diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium):
a250 ml three-necked flask was fully dried, and vacuum-purged with nitrogen three times, and then, 1113 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared as described above was added thereto, 50ml of dry, deoxidized, dehydrated ether was added thereto, and electromagnetic stirring was turned on. The solution was cooled to 0 ℃ with an ice bath. 2.0 ml of n-butylmagnesium chloride (2.0 mol of n-butylmagnesium bromide per liter of ether solution) was slowly added dropwise using a syringe over a period of about 5 minutes. After the dropwise addition, the temperature is naturally raised to room temperature, the reaction is continued to be stirred, and the reaction time is 24 hours in total. All solvents were removed in vacuo, extracted with dry, deoxygenated, anhydrous dichloromethane, and freeze-crystallized to give 717 mg (diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium) as a solid product.
[ example 1 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 10 atm, and 0.1 ml of a catalyst solution in toluene [ containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared in example 1 ] was added to start timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmosphere, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. This gave 0.29 g of polymer having a number average molecular weight of 12300 and a molecular weight distribution of 2.3.
The process of example 1 was repeated several times, and the yields of the polymers obtained each time were almost identical, with the same effect, and applicable to industrial popularization.
[ example 2 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 1, except that the following conditions were changed:
0.2 ml of a toluene solution of the catalyst (containing 0.2. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added and the reaction time was 25 minutes, to give 0.28 g of a polymer having a number average molecular weight of 11500 and a molecular weight distribution of 2.2.
The melting point of the polymer was 116.8 ℃ and the enthalpy of fusion was 72.9 joules/gram as determined by differential scanning calorimetry.
The process of example 2 was repeated several times, and the yields of the polymers obtained each time were almost identical, with the same effect, and applicable to industrial popularization.
Example 3 copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 2, except that the following conditions were changed:
the amount of 1-hexene used was 0.36 ml and the reaction time was 21 minutes. This gave 0.34 g of polymer, had a number average molecular weight of 9600 and a molecular weight distribution of 2.1.
The melting point of the polymer was 107.4 ℃ and the enthalpy of fusion was 22.9 joules/gram as determined by differential scanning calorimetry.
The process of example 3 was repeated several times, and the polymers obtained each time had almost the same yield and the same effect, and were suitable for industrial popularization.
[ example 4 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 1 except that the following conditions were changed:
0.3 ml of a toluene solution of the catalyst (containing 0.3. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added; the reaction time was 24 minutes. 0.28 g of polymer was obtained, having a number average molecular weight of 10900 and a molecular weight distribution of 2.2.
The process of example 4 was repeated several times, and the polymers obtained each time had almost the same yield and the same effect, and were suitable for industrial popularization.
[ example 5 ] copolymerization of ethylene with 1-octene
The experimental procedure was the same as in example 2, except that the following conditions were changed:
the dosage of n-heptane is 2.5 ml; ethylene pressure was 5.5 atm; 1-hexene is not added, and 0.18 ml of 1-octene is added; the reaction time was 30 minutes. This gave 0.22 g of polymer having a number average molecular weight 8300 and a molecular weight distribution of 2.5.
The process of example 5 was repeated several times, and the yields of the polymers obtained each time were almost identical, with the same effect, and applicable to industrial popularization.
[ example 6 ] copolymerization of ethylene with 1-octene
The experimental procedure was the same as in example 5 except that the following conditions were changed:
the reaction time was 15 minutes, yielding 0.07 g of polymer, number average molecular weight 8700, molecular weight distribution 2.4.
The process of example 6 was repeated several times, and the yields of the polymers obtained each time were almost identical, with the same effect, and applicable to industrial popularization.
[ example 7 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 2, except that the following conditions were changed:
the amount of 1-hexene used was 0.6 ml, the reaction temperature was 120 ℃, and the obtained polymer was 0.59 g, number average molecular weight was 13700, molecular weight distribution was 3.1; the melting point of the polymer was 109.0 ℃ and the enthalpy of fusion was 6.21J/g as measured by differential scanning calorimetry.
The process of example 7 was repeated several times, and the yields of the polymers obtained each time were almost identical, the effects were the same, and it was applicable to industrial popularization.
[ example 8 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 7, except that the following conditions were changed:
the amount of 1-hexene used was 0.9 ml, giving a polymer of 0.84 g, number average molecular weight 10400, molecular weight distribution 3.4.
The melting point of the polymer was 102.9 ℃ and the enthalpy of fusion was 4.81 joules/gram as determined by differential scanning calorimetry.
The process of example 8 was repeated several times, and the yields of the polymers obtained each time were almost identical, the effects were the same, and it was applicable to industrial popularization.
[ example 9 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 7, except that the following conditions were changed:
the amount of 1-hexene used was 1.2 ml, giving a polymer of 1.00 g, number average molecular weight 9600, molecular weight distribution 2.8.
The melting point of the polymer was 85.5 ℃ and the enthalpy of fusion was 2.47J/g as measured by differential scanning calorimetry.
The process of example 9 was repeated several times, and the yields of the polymers obtained each time were almost identical, the effects were the same, and it was applicable to industrial popularization.
[ example 10 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 8 except that the following conditions were changed:
the amount of methylaluminoxane solution in toluene was 0.03 ml (containing 0.05 mmol of methylaluminoxane) to give 0.52 g of polymer having a number average molecular weight of 23000 and a molecular weight distribution of 2.3.
The melting point of the polymer was 98.3 ℃ and the enthalpy of fusion was 1.90J/g as measured by differential scanning calorimetry.
The process of example 10 was repeated several times, and the yields of the polymers obtained each time were almost identical, the effects were the same, and it was applicable to industrial popularization.
[ example 11 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 7 except that the following conditions were changed:
the reaction temperature was 140 ℃ to give a polymer of 0.67 g, number average molecular weight 8800 and molecular weight distribution 2.7.
The melting point of the polymer was 102.7 degrees celsius and the enthalpy of fusion was 3.48 joules/gram as measured by differential scanning calorimetry.
The process of example 11 was repeated several times, and the yields of the polymers obtained each time were almost identical and the effects were the same, and it was applicable to industrial popularization.
[ example 12 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 7, except that the following conditions were changed:
the reaction temperature was 160 ℃ to give 0.34 g of a polymer having a number average molecular weight of 10400 and a molecular weight distribution of 2.4.
The polymer has no melting point as measured by differential scanning calorimetry.
The procedure of example 12 was repeated a plurality of times, and the polymers obtained each time had almost the same yield and the same effect, and were applicable to industrial popularization.
[ example 13 ] copolymerization of ethylene with 1-hexene
The experimental procedure was the same as in example 10 except that the following conditions were changed:
the reaction temperature was 160 ℃ to give a polymer of 0.10 g, number average molecular weight 13700 and molecular weight distribution 2.29.
The melting point of the polymer was 93.5 ℃ and the enthalpy of fusion was 2.58J/g as measured by differential scanning calorimetry.
The process of example 13 was repeated several times, and the yields of the polymers obtained each time were almost identical and the effects were the same, and it was applicable to industrial popularization.
[ example 14 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 10 atm, and 0.1 ml of catalytic toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-t-butyl-fluorenyl) zirconium dichloride) was added to start timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. This gave 0.25 g of polymer having a number average molecular weight of 15600 and a molecular weight distribution of 2.2.
[ example 15 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. Vacuum pumping, charging ethylene, adding 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane), heating to 140 ℃, increasing the ethylene pressure to 10 standard atmospheric pressures, adding 0.1 ml of catalyst toluene solution (containing 0.1 μmol of diphenylmethylene (cyclopentadienyl) (fluorenyl) dibenzyl zirconium), and starting timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.36 g of polymer was obtained, with a number average molecular weight of 16200 and a molecular weight distribution of 2.1.
[ example 16 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 10 atm, 0.1 ml of catalyst toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium) was added, and the timer was started. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmosphere, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. This gave 0.32 g of polymer, had a number average molecular weight of 11600 and a molecular weight distribution of 2.3.
[ example 17 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 180 ℃ and the ethylene pressure was raised to 10 atm, 0.1 ml of catalytic toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added and the timer was started. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmosphere, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.19 g of polymer was obtained, with a number average molecular weight of 7700 and a molecular weight distribution of 2.1.
[ example 18 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) were added, the temperature was raised to 200 ℃ and the ethylene pressure was raised to 10 atm, 0.1 ml of catalyst toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added and the timer was started. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.13 g of polymer was obtained, having a number average molecular weight of 7300 and a molecular weight distribution of 2.0.
[ example 19 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 15 atm, 0.1 ml of catalytic toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added and the timer was started. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.35 g of polymer was obtained, having a number average molecular weight 17200 and a molecular weight distribution of 2.5.
[ example 20 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 20 atm, 0.1 ml of catalytic toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added and the timer was started. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. This gave 0.41 g of polymer having a number average molecular weight of 20100 and a molecular weight distribution of 2.2.
[ example 21 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 30 atm, and 0.1 ml of catalyst solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added to start timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.52 g of polymer was obtained, having a number average molecular weight of 26200 and a molecular weight distribution of 2.2.
[ example 22 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 1.2 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 160 ℃ and the ethylene pressure was raised to 30 atm, and 0.1 ml of a catalyst toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-t-butyl-fluorenyl) zirconium dichloride) was added to start timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.42 g of a polymer was obtained. The melting point of the polymer was 86.7 ℃ and the enthalpy of fusion was 1.33 joules/gram as determined by differential scanning calorimetry. Number average molecular weight 26200 and molecular weight distribution 2.4.
[ example 23 ] copolymerization of ethylene with 1-hexene
A fully dried 10mL polymerization reactor was evacuated, flushed with nitrogen and repeated three times. After evacuation, ethylene was charged, 5 ml of n-heptane, 1.2 ml of 1-hexene, 0.06 ml of methylaluminoxane toluene solution (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 ℃ and the ethylene pressure was raised to 30 atm, and 0.1 ml of catalytic toluene solution (containing 0.1. mu. mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-t-butyl-fluorenyl) zirconium dichloride) was added to start timing. After 30 minutes, the ethylene is closed, the pressure is reduced to 1 standard atmospheric pressure, the temperature is reduced to 80 ℃, and the vacuum is pumped for 8 hours. 0.50 g of a polymer was obtained. The melting point of the polymer was 88.5 degrees celsius and the enthalpy of fusion was 2.16 joules/gram as measured by differential scanning calorimetry. Number average molecular weight 37000, molecular weight distribution 2.4.
Comparative example 1
The procedure of example 1 was repeated except that: the polymerization temperature was 70 ℃.
When the reaction time reached 14 minutes, the system could not be stirred due to excessive viscosity. The pressure was reduced to 1 atmosphere and vacuum applied for 8 hours to give 0.13 g of polymer with a number average molecular weight of 15700 and a molecular weight distribution of 2.8.
The results of example 1 and comparative example 1 were analyzed to find that:
(1) the comparative example 1 was run at less than 120 degrees celsius to give only 0.13 grams of polymer, whereas example 1 gave 0.29 grams, with the yield of example 1 being significantly higher than comparative example 1;
(2) as can be seen from comparison with this comparative example 1, the molecular weight distribution of the polymer obtained in example 1 is significantly smaller than that of comparative example 1, and the analytical reason may be that the molecular weight distribution in comparative example 1 is too broad due to too large system viscosity;
(3) according to the knowledge of those skilled in the art, the average molecular weight of polyethylene decreases greatly with the increase of the reaction temperature, but in the present invention, the polymerization temperature of example 1 is significantly higher than that of comparative example 1, but the number average molecular weight of the polymer obtained in example 1 can still reach 12300, therefore, the molecular weight of the polymer obtained by polymerization at high temperature of example 1 does not decrease significantly, and the molecular weight distribution becomes smaller on the contrary.
Comparative example 2
The procedure of example 1 was repeated except that: diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was replaced with an equal amount of pentamethylcyclopentadienyl-2, 6-diisopropyl-phenoxy-titanium dichloride.
The polymerization did not yield a product, which was repeated several times, confirming that the catalyst was not active under these conditions.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. An olefin polymerization process comprising: reacting ethylene and optionally a comonomer in the presence of a catalyst composition to obtain a polyolefin, wherein the catalyst composition comprises a compound of formula (I):
in the formula (I), R 1 Selected from hydrogen or C 1 ～C 10 Alkyl of (a), each R 1 The same or different; r 2 Selected from aryl or substituted aryl, each R 2 The same or different; m is selected from group IVB elements; x is selected from halogen, hydrocarbyl or hydrocarbyloxy, each X being the same or different.
2. The process for the polymerization of olefins according to claim 1, characterized in that in formula (I), R 1 Selected from hydrogen or C 1 ～C 5 Alkyl of (a), each R 1 The same or different; r 2 Selected from aryl, each R 2 The same or different; m is selected from Zr, Ti or Hf, X is selected from halogen, C 1 ～C 10 Alkyl or C of 6 ～C 10 Each X is the same or different.
3. The process for the polymerization of olefins according to claim 2, characterized in that in formula (I), R 1 Selected from hydrogen or tert-butyl, each R 1 The same or different; r is 2 Selected from phenyl, each R 2 The same or different; m is selected from Zr; x is selected from chlorine atom, methyl, ethyl and nButyl or benzyl, each X being the same or different.
4. The method of claim 1, wherein the alkylaluminoxane has the structure of formula (II) or formula (III):
in the formulae (II) and (III), R is selected from C 1 -C 12 Is the same or different for each R, is preferably selected from C 1 -C 5 Each R is the same or different; n is an integer of 4 to 30, preferably an integer of 10 to 30.
5. The method of claim 4, wherein the alkylaluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
6. The method of claim 1, wherein the molar ratio of the compound of formula (I) to the alkylaluminoxane in the catalyst composition is 1 (50-20000), preferably 1 (100-5000).
7. The process for the polymerization of olefins according to claim 1, characterized in that the reaction is carried out in a solvent selected from toluene and/or C 3 ～C 18 Is a saturated alkane.
8. The method of olefin polymerization according to any one of claims 1 to 7,
the ethylene partial pressure during polymerization is from 1 to 100 atm, preferably from 5 to 50 atm; and/or
The polymerization temperature is 120-220 ℃, preferably 120-180 ℃.
9. The process for the polymerization of olefins according to claim 8Characterized in that the comonomer is selected from C 3 ～C 10 The olefin of (1).
10. Polyolefin obtainable by the olefin polymerization process according to any one of claims 1 to 9.
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