CN115010838B - Olefin polymerization method and polyolefin obtained by same - Google Patents
Olefin polymerization method and polyolefin obtained by same Download PDFInfo
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- CN115010838B CN115010838B CN202110242673.8A CN202110242673A CN115010838B CN 115010838 B CN115010838 B CN 115010838B CN 202110242673 A CN202110242673 A CN 202110242673A CN 115010838 B CN115010838 B CN 115010838B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000005977 Ethylene Substances 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 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
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 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
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 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
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 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
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 76
- 229920000642 polymer Polymers 0.000 description 64
- 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 20
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000047 product Substances 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
- 238000002474 experimental method Methods 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 11
- 238000000113 differential scanning calorimetry Methods 0.000 description 11
- -1 cocatalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 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
- 238000002360 preparation method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 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
- 230000035484 reaction time Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 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
- 238000004458 analytical method Methods 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
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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
- 238000013459 approach Methods 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 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
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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)
- 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 optionally a comonomer in the presence of a catalyst composition, wherein the catalyst composition comprises a compound represented by formula (I) and an alkylaluminoxane, and the ethylene partial pressure is 1-100 atm when polymerizing, and the polymerization temperature is 120-220 ℃ to obtain polyolefin: In formula (I), R 1 is selected from hydrogen or alkyl of C 1～C10, R 2 is selected from aryl or substituted aryl, M is selected from group IVB elements, and X is selected from halogen, hydrocarbyl or hydrocarbyloxy. The method is carried out by adopting a special catalyst, and the method can realize high-efficiency catalytic polymerization at high temperature, namely, 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.
Description
Technical Field
The present invention relates to olefin polymerization catalysts, and more particularly to a process for polymerizing olefins and the polyolefin obtained thereby.
Background
Most comonomers have relatively high molecular weights and boiling points, which are not substantially suitable for use in the existing polymerization processes, both gas phase and slurry processes. For such comonomers, a process suitable for solution polymerization is generally required. Solution polymerization is a polymerization mode in which all reactants, including catalyst, cocatalyst, monomer and other auxiliaries, additives, can be dissolved or uniformly dispersed in a solvent system.
Since the polymer produced is also dissolved in the solvent, the high viscosity of the reaction system produced after dissolution of the polymer will have a significant impact on the heat transfer, mass transfer and transmission of the polymerization process, and may further affect the uniformity of the reaction. Reducing the viscosity of the polymerization system can be accomplished by reducing the solids content of the polymerization system, but this will greatly reduce the production efficiency. Another approach is to raise the polymerization temperature and, at the same solids content, lower the viscosity of the high temperature system.
For most catalysts, increasing the polymerization temperature over a range will decrease the polymerization activity, for example, most metallocene catalysts will have a sharp decrease in activity at polymerization temperatures above 100 degrees celsius. Therefore, it is an important and practical problem to realize efficient catalytic olefin polymerization at high temperatures as follows.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides an olefin polymerization method and polyolefin obtained by the method, wherein the method can realize system polymerization at high temperature by adopting a metallocene catalyst with a special structure, and the metallocene catalyst can still maintain high-efficiency olefin catalysis at high temperature.
It is an object of the present invention to provide a process for the polymerization of olefins 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 formula (I), R 1 is selected from hydrogen or alkyl of C 1～C10, each R 1 is the same or different, R 2 is selected from aryl or substituted aryl, each R 2 is the same or different, M is selected from group IVB elements, and X is selected from halogen, hydrocarbyl or hydrocarbyloxy, each X is the same or different.
The metallocene catalyst has high efficiency and broad spectrum of copolymerization, so that the metallocene catalyst can catalyze and obtain a plurality of new copolymers, and the copolymers have new compositions and structures compared with copolymers obtained by other catalysts, thereby possibly having new properties and further realizing the application of polyolefin materials in new fields. Most new polyolefin materials are copolymerized with simple olefins such as ethylene or propylene by selecting comonomers with proper structures, and the structural composition of the comonomers is diversified and special in functionality, so that the new compositions and performances of the polyolefin materials can be endowed. Meanwhile, the comonomer also generates a synergistic effect due to entering the polyolefin molecular chain, so that the quality of the polyolefin is greatly improved.
In a preferred embodiment, in formula (I), R 1 is selected from hydrogen or alkyl of C 1～C5 (e.g., C 1、C2、C3、C4 or C 5), each R 1 being the same or different; r 2 is selected from aryl, and each R 2 is the same or different; m is selected from Zr, ti or Hf; x is selected from halogen, alkyl of C 1～C10 (e.g., C 1、C2、C3、C4 or C 5) or aryl of C 6～C10 (e.g., C 6、C7、C8、C9 or C 10), each X being the same or different.
In a further preferred embodiment, in formula (I), R 1 is selected from hydrogen or tert-butyl, each R 1 being the same or different; r 2 is selected from phenyl, and each R 2 is 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 lower temperatures (e.g., 0-60 ℃ and even below 0 ℃). However, when the polymerization temperature is high (more than 100 ℃ C.), the polymerization activity is greatly lowered, which is widely known to researchers, so that general polymerization studies rarely use a polymerization temperature exceeding 100 ℃ C. Thus, the compound of formula (I) is not considered to be an effective polymerization catalyst at high temperatures, and the inventors have unexpectedly found that the use of the compound of formula (I) can be carried out at high temperatures, yet still have higher activity at high temperatures, and unexpected technical effects are obtained.
In a preferred embodiment, the alkylaluminoxane has a structure according to formula (II) or formula (III):
In the formula (II) and the formula (III), R is selected from alkyl of C 1-C12, and each R is the same or different; n is an integer from 4 to 30.
In a further preferred embodiment, in formula (II) and formula (III), R is selected from alkyl of C 1-C5, each R being 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 from 1 (50 to 20000), preferably from 1 (100 to 5000), more preferably from 1 (300 to 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 saturated alkanes of C 3～C18.
In a further preferred embodiment, the solvent is selected from toluene and/or saturated alkanes of C 5～C8, preferably toluene.
In a preferred embodiment, the ethylene partial pressure during polymerization is in the range of from 1 to 100 atmospheres, preferably from 5 to 50 atmospheres, more preferably from 5 to 30 atmospheres.
In a preferred embodiment, the polymerization temperature is 120 to 220 ℃, preferably 120 to 180 ℃, more preferably 120 to 160 ℃, e.g. 120 to 140 ℃ or 140 to 160 ℃. For example: 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃, and the above can be combined arbitrarily to form a polymerization temperature range.
As will be appreciated by those skilled in the art, the compounds of formula (I) should be reacted at temperatures below 100deg.C, which may result in a decrease in the catalytic activity of the catalyst. Thus, there has been no application to olefin polymerization at high temperatures using the 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 has the unexpected technical effect of significantly improving the yield, i.e., the yield of the polymer is significantly higher than that at conventional 100℃or less polymerization at the high temperatures described in the present invention.
Specifically, if polymerization is carried out at 70 to 100 ℃, the viscosity of the system is high when the polymerization is likely to reach 10%, and the reaction has to be stopped; however, if polymerized at high temperature, the degree of polymerization may be as high as 80%, and the productivity is very significantly improved.
In a preferred embodiment, the comonomer is selected from the group consisting of C 3～C10 olefins (or terminal olefins).
In a further preferred embodiment, the comonomer is selected from at least one of 1-butene, 1-hexene and 1-octene.
The second object of the present invention is to provide a polyolefin obtained by the olefin polymerization process according to one of the objects of the present invention.
In a preferred embodiment, the polyolefin has a number average molecular weight of up to 1 to 4 tens of thousands.
As will be generally recognized by 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 substantially with increasing reaction temperature, and the higher molecular weight polymer is not obtained. However, the inventors have found after a number of experiments that a polyolefin having a high molecular weight and a narrow molecular weight distribution can be obtained by polymerizing an olefin at a high temperature using the compound represented by the formula (I). Thus, unexpected technical effects are achieved by using the preparation method according to one of the objects of the present invention for the preparation of polymers.
In particular, the catalyst still maintains higher reactivity at the high temperature of the application, and the high molecular weight polymer can still be obtained at the high temperature of 120-220 ℃. Compared with the prior art, the application can raise the initial temperature of the polymer whose molecular weight is reduced due to 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 about 1 ten thousand or more molecular weight polymers may not be obtained. However, in the polymerization system of the present application, a polymer having a molecular weight of about 1 ten thousand or more and even 1 ten thousand or more can be obtained at a polymerization temperature of 140℃or even 160℃and only when the molecular weight of the polymer is significantly reduced at a temperature exceeding 220 ℃.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give 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 is carried out by adopting a special catalyst, and the method can realize high-efficiency catalytic polymerization at high temperature, namely, 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) The method disclosed by the invention is carried out at a high temperature limit, but has very high repeatability, and the same method is adopted to repeatedly carry out a plurality of experiments, so that the effect is consistent, and the method can be suitable for industrial popularization.
Drawings
FIG. 1 shows the Gel Permeation Chromatography (GPC) curve of the polyolefin obtained in example 13;
FIG. 2 shows the Differential Scanning Calorimeter (DSC) curve of the polyolefin obtained in example 8;
FIG. 3 shows the Differential Scanning Calorimetric (DSC) profile of the polyolefin obtained in example 12.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are 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, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Preparation of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride:
a.500 ml three-port bottle, under the anhydrous and nitrogen atmosphere, 4.1 g of sodium methoxide, 50 ml of ethanol and 12.5 g of benzophenone are added, and the magnetic stirring is started. Cyclopentadiene (10 ml) was added thereto, and the reaction was stirred at room temperature for 120 hours. The orange solid was collected by filtration and after repeated washing with absolute 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-diphenylfulvene) are obtained;
b. Fully dried 250 ml three-port bottle, replaced three times by vacuum nitrogen, added with fluorene 2.89 g, added with 50ml dry deoxidized absolute ethyl ether, and started electromagnetic stirring. The solution was cooled to 0 ℃ with an ice bath. 7.3 ml of n-butyllithium (2.5 mol/L hexane solution of n-butyllithium) was slowly added dropwise using a syringe over a period of about 5 minutes. After the completion of the dropwise addition, the reaction mixture was naturally warmed to room temperature, and the reaction was continued with stirring for a total of 24 hours. 4.0 g of 6, 6-diphenylfulvene was added and the reaction stirred for a further 120 hours. The reaction was cooled to 0℃with an ice bath, and 20ml of water and then 10 ml of an aqueous ammonium chloride solution were added to the slow solution. The crude product is filtered off and washed in 150ml of boiling ethanol for 2 hours. The solid obtained was filtered while hot and dried in vacuo. 6.43 g of a product (fluorenyl cyclopentadienyl diphenylmethane) was obtained;
c. Fully dried 250 ml three-port bottle, replaced three times with vacuum nitrogen, added with 4.30 g of fluorenyl cyclopentadienyl diphenyl methane, added with 30ml of dry deoxidized absolute ethyl ether, and started electromagnetic stirring. The solution was cooled to 0 ℃ with an ice bath. 9.0 ml of n-butyllithium (2.5 mol/L hexane solution of n-butyllithium) was slowly added dropwise using a syringe over a period of about 8 minutes. After the completion of the dropwise addition, the reaction mixture was naturally warmed to room temperature, and the reaction was continued with stirring for a total of 24 hours. The reaction system was cooled to below-80 ℃ using liquid nitrogen plus acetone, 2.50 grams of zirconium tetrachloride solids were added and slowly warmed to room temperature with stirring. The reaction was carried out for 24 hours, all the solvent was removed in vacuo, extracted with dehydrated and deoxidized methylene chloride, and frozen for crystallization to give 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 preparation is similar 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) dibenzyl zirconium:
Fully dried 250 ml three-necked flask was replaced with vacuum nitrogen three times, 1113 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared above was added, 50ml of dry deoxygenated anhydrous diethyl ether was added, and electromagnetic stirring was turned on. The solution was cooled to 0 ℃ with an ice bath. 4.0ml of benzyl magnesium chloride (benzyl magnesium bromide 1.0 mol/l in diethyl ether) was slowly added dropwise using a syringe over a period of about 5 minutes. After the completion of the dropwise addition, the reaction mixture was naturally warmed to room temperature, and the reaction was continued with stirring for a total of 24 hours. All solvents were removed in vacuo, extracted with dry deoxygenated anhydrous dichloromethane and freeze crystallized to give 835 mg of (diphenylmethylene (cyclopentadienyl) (fluorenyl) dibenzyl zirconium) as a solid product.
Preparation of diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium):
Fully dried 250 ml three-necked flask was replaced with vacuum nitrogen three times, 1113 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared above was added, 50 ml of dry deoxygenated anhydrous diethyl ether was added, 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 diethyl ether solution) was slowly added dropwise using a syringe over a period of about 5 minutes. After the completion of the dropwise addition, the reaction mixture was naturally warmed to room temperature, and the reaction was continued with stirring for a total of 24 hours. All solvents were removed in vacuo, extracted with dry deoxygenated anhydrous dichloromethane and freeze crystallized to give 717 mg of (diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium) as a solid product.
Example 1 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5ml of n-heptane, 0.18 ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane), the temperature was raised to 140℃and the ethylene pressure was increased to 10 standard atmospheres, 0.1 ml of catalyst toluene solution [ solution containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride prepared in example 1] was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.29 g of a polymer having a number average molecular weight of 12300 and a molecular weight distribution of 2.3 was obtained.
The procedure of example 1 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was 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 catalyst (containing 0.2. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added thereto for a reaction time of 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 polymer was found to have a melting point of 116.8 degrees celsius and a melting enthalpy of 72.9 joules/gram by differential scanning calorimetry.
The procedure of example 2 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was 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 was 0.36 ml and the reaction time was 21 minutes. 0.34 g of a polymer having a number average molecular weight of 9600 and a molecular weight distribution of 2.1 was obtained.
The polymer was found to have a melting point of 107.4 degrees celsius and a melting enthalpy of 22.9 joules/gram by differential scanning calorimetry.
The procedure of example 3 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was applicable to 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 catalyst (containing 0.3. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added; the reaction time was 24 minutes. 0.28 g of a polymer having a number average molecular weight of 10900 and a molecular weight distribution of 2.2 was obtained.
The procedure of example 4 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was applicable to 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 n-heptane dosage was 2.5 ml; ethylene pressure was 5.5 atmospheres gauge; 1-hexene was not added, and 0.18 ml of 1-octene was added; the reaction time was 30 minutes. 0.22 g of a polymer having a number average molecular weight 8300 and a molecular weight distribution of 2.5 was obtained.
The procedure of example 5 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was 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, and 0.07 g of a polymer having a number average molecular weight of 8700 and a molecular weight distribution of 2.4 was obtained.
The procedure of example 6 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was 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 dosage of 1-hexene is 0.6 ml, the reaction temperature is 120 ℃, 0.59 g of the obtained polymer has a number average molecular weight of 13700 and a molecular weight distribution of 3.1; the polymer was found to have a melting point of 109.0 degrees celsius and a melting enthalpy of 6.21 joules/gram by differential scanning calorimetry.
The procedure of example 7 was repeated a plurality of times, and the polymer products obtained each time were almost uniform in production and the same in effect, and thus, the method was suitable for 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, which gave 0.84 g of a polymer having a number average molecular weight of 10400 and a molecular weight distribution of 3.4.
The melting point of the polymer was measured by differential scanning calorimetry at 102.9 degrees celsius and the enthalpy of fusion at 4.81 joules/gram.
The procedure of example 8 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method 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 was 1.2 ml, which gave 1.00 g of a polymer having a number average molecular weight of 9600 and a molecular weight distribution of 2.8.
The polymer was found to have a melting point of 85.5 degrees celsius and a melting enthalpy of 2.47 joules/gram by differential scanning calorimetry.
The procedure of example 9 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method 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 methylaluminoxane solution in toluene was used in an amount of 0.03 ml (containing 0.05 mmol of methylaluminoxane) to obtain 0.52 g of a polymer having a number average molecular weight of 23000 and a molecular weight distribution of 2.3.
The polymer was found to have a melting point of 98.3 degrees celsius and a melting enthalpy of 1.90 joules/gram by differential scanning calorimetry.
The procedure of example 10 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method 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 degrees celsius, resulting in 0.67 grams of polymer having a number average molecular weight of 8800 and a molecular weight distribution of 2.7.
The polymer was found to have a melting point of 102.7 degrees celsius and a melting enthalpy of 3.48 joules/gram by differential scanning calorimetry.
The procedure of example 11 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method 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 was thermally detected by differential scanning calorimetry to have no melting point.
The procedure of example 12 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was 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 0.10 g of a polymer having a number average molecular weight of 13700 and a molecular weight distribution of 2.29.
The polymer was found to have a melting point of 93.5 degrees celsius and a melting enthalpy of 2.58 joules/gram by differential scanning calorimetry.
The procedure of example 13 was repeated a plurality of times, and the polymer products obtained each time were almost uniform and the effect was the same, and the method was applicable to industrial popularization.
Example 14 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and 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 solution in toluene (containing 0.1 mmol of methylaluminoxane), the temperature was raised to 140℃and the ethylene pressure was increased to 10 standard atmospheres, 0.1 ml of catalyst solution in toluene (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride) was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.25 g of a polymer having a number average molecular weight of 15600 and a molecular weight distribution of 2.2 was obtained.
Example 15 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and 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 solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 degrees celsius, the ethylene pressure was increased to 10 standard atmospheric pressures, 0.1 ml of catalyst toluene solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) dibenzyl zirconium) was added, and the timing was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.36 g of a polymer having a number average molecular weight of 16200 and a molecular weight distribution of 2.1 was obtained.
EXAMPLE 16 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and 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 solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 degrees celsius, the ethylene pressure was raised to 10 standard atmospheric pressures, 0.1 ml of catalyst toluene solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) di-n-butylzirconium) was added, and the timing was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.32 g of a polymer having a number average molecular weight of 11600 and a molecular weight distribution of 2.3 was obtained.
Example 17 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5ml 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 degrees celsius, the ethylene pressure was raised to 10 standard atmospheric pressures, 0.1 ml of catalyst solution in toluene (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the timing was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.19 g of a polymer having a number average molecular weight of 7700 and a molecular weight distribution of 2.1 was obtained.
EXAMPLE 18 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5ml 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 200 degrees celsius, the ethylene pressure was raised to 10 standard atmospheric pressures, 0.1 ml of catalyst toluene solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the timing was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.13 g of a polymer having a number average molecular weight of 7300 and a molecular weight distribution of 2.0 was obtained.
Example 19 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and 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 solution in toluene (containing 0.1 mmol of methylaluminoxane), the temperature was raised to 140℃and the ethylene pressure was increased to 15 standard atmospheric pressure, 0.1 ml of catalyst solution in toluene (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.35 g of a polymer having a number average molecular weight 17200 and a molecular weight distribution of 2.5 was obtained.
Example 20 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and 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 solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 140 degrees celsius, the ethylene pressure was raised to 20 standard atmospheric pressure, 0.1 ml of catalyst solution in toluene (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.41 g of a polymer having a number average molecular weight 20100 and a molecular weight distribution of 2.2 was obtained.
Example 21 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5ml 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 degrees celsius, the ethylene pressure was increased to 30 standard atmospheric pressures, 0.1 ml of catalyst solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the timing was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.52 g of a polymer having a number average molecular weight of 26200 and a molecular weight distribution of 2.2 was obtained.
Example 22 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5ml of n-heptane, 1.2ml of 1-hexene, 0.06 ml of methylaluminoxane solution in toluene (containing 0.1 mmol of methylaluminoxane) was added, the temperature was raised to 160℃and the ethylene pressure was increased to 30 standard atmospheres, 0.1 ml of catalyst toluene solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride) was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.42 g of a polymer was obtained. The polymer was found to have a melting point of 86.7 degrees celsius and a melting enthalpy of 1.33 joules/gram by differential scanning calorimetry. Number average molecular weight 26200, molecular weight distribution was 2.4.
Example 23 copolymerization of ethylene with 1-hexene
The fully dried 10mL polymerization reactor was evacuated and flushed with nitrogen and repeated three times. Vacuum was applied, ethylene was charged, 5 ml of n-heptane, 1.2 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 degrees celsius, the ethylene pressure was increased to 30 standard atmospheres, 0.1 ml of catalyst toluene solution (containing 0.1. Mu. Mol of diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride) was added, and the time was started. After 30 minutes, the ethylene was turned off, depressurized to 1 standard atmosphere, cooled to 80 degrees celsius, and evacuated for 8 hours. 0.50 g of a polymer was obtained. The polymer was found to have a melting point of 88.5 degrees celsius and a melting enthalpy of 2.16 joules/gram by differential scanning calorimetry. Number average molecular weight 37000 and molecular weight distribution was 2.4.
Comparative example 1
The procedure of example 1 was repeated, except that: the polymerization temperature was 70 degrees celsius.
When the reaction time reaches 14 minutes, the system cannot be stirred due to excessive viscosity. The pressure was reduced to 1 atm and the vacuum was applied for 8 hours to give 0.13 g of polymer having a number average molecular weight of 15700 and a molecular weight distribution of 2.8.
Analysis of the results of example 1 and comparative example 1 revealed that:
(1) This comparative example 1 was conducted at a temperature of less than 120 degrees celsius, yielding only 0.13 grams of polymer, whereas example 1 yielded 0.29 grams, with the yield of example 1 being significantly higher than comparative example 1;
(2) As can be seen from comparison with comparative example 1, the molecular weight distribution of the polymer obtained in example 1 is significantly smaller than that in comparative example 1, and the analysis may be that the molecular weight distribution in comparative example 1 is too broad due to too high viscosity of the system;
(3) As will be appreciated by those skilled in the art, the average molecular weight of polyethylene decreases greatly with increasing 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, so that the molecular weight of the polymer obtained by polymerization of example 1 at high temperature does not decrease significantly, and the molecular weight distribution becomes small instead.
Comparative example 2
The procedure of example 1 was repeated, except that: the diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was replaced with an equivalent amount of pentamethylcyclopentadienyl-2, 6-diisopropyl-phenoxy-titanium dichloride.
The polymerization did not give a product, and the catalyst was repeated several times to confirm that the catalyst was inactive under this condition.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art 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, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. A process for the polymerization of olefins comprising: reacting ethylene and optionally a comonomer in the presence of a catalyst composition having a polymerization temperature of 120-220 ℃ to obtain a polyolefin, wherein the catalyst composition consists of a compound represented by formula (I):
formula (I);
In formula (I), R 1 is selected from hydrogen or alkyl of C 1~C10, each R 1 being the same or different; r 2 is selected from aryl or substituted aryl, and each R 2 is the same or different; m is selected from group IVB elements; x is selected from halogen, alkyl or alkoxy, and each X is the same or different;
the structure of the alkyl aluminoxane is shown as a formula (II) or a formula (III):
Formula (II) formula (III)
In the formula (II) and the formula (III), R is selected from alkyl of C 1-C12, and each R is the same or different; n is an integer of 4 to 30.
2. The process for the polymerization of olefins according to claim 1, characterized in that in formula (I), R 1 is chosen from hydrogen or alkyl of C 1~C5, each R 1 being identical or different; r 2 is selected from aryl, and each R 2 is the same or different; m is selected from Zr, ti or Hf, X is selected from halogen, C 1~C10 alkyl or C 6~C10 aryl, and 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 is chosen from hydrogen or tert-butyl, each R 1 being identical or different; r 2 is selected from phenyl, and each R 2 is 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.
4. The olefin polymerization process according to claim 1, wherein the alkylaluminoxane has a structure represented by formula (II) or formula (III):
Formula (II) formula (III)
In the formula (II) and the formula (III), R is selected from alkyl of C 1-C5, and each R is the same or different; n is an integer of 10 to 30.
5. The olefin polymerization process of claim 1 wherein said alkylaluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
6. The process for polymerizing olefins according to claim 1, wherein the molar ratio of the compound represented by the formula (I) to the alkylaluminoxane in the catalyst composition is 1 (50 to 20000).
7. The process for polymerizing olefins according to claim 6, wherein the molar ratio of the compound represented by the formula (I) to the alkylaluminoxane in the catalyst composition is 1 (100 to 5000).
8. The olefin polymerization process according to claim 1, wherein the reaction is carried out in a solvent selected from toluene and/or saturated alkanes of C 3~C18.
9. The process for the polymerization of olefins according to claim 1 to 8, wherein,
The ethylene partial pressure is 1-100 atm during polymerization; and/or
The polymerization temperature is 120-180 ℃.
10. The process for the polymerization of olefins according to claim 9, wherein,
The ethylene partial pressure during polymerization is 5-50 atm.
11. The olefin polymerization process of claim 9 wherein said comonomer is selected from the group consisting of C 3~C10 olefins.
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| CN110922516A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Ethylene copolymer and preparation method thereof |
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