CN112778441B - Supported metallocene catalyst and preparation and application thereof - Google Patents
Supported metallocene catalyst and preparation and application thereof Download PDFInfo
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- CN112778441B CN112778441B CN201911064147.6A CN201911064147A CN112778441B CN 112778441 B CN112778441 B CN 112778441B CN 201911064147 A CN201911064147 A CN 201911064147A CN 112778441 B CN112778441 B CN 112778441B
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 92
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000000741 silica gel Substances 0.000 claims description 28
- 229910002027 silica gel Inorganic materials 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 7
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- -1 aluminum alkyl oxygen alkane Chemical class 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 59
- 239000000203 mixture Substances 0.000 description 48
- 229960002337 magnesium chloride Drugs 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 239000000843 powder Substances 0.000 description 17
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 14
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 13
- 150000003613 toluenes Chemical class 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 229910007926 ZrCl Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OEOUWMSQXZQDIP-UHFFFAOYSA-N CC[Al](CC)CC.CC1=CC=CC=C1 Chemical compound CC[Al](CC)CC.CC1=CC=CC=C1 OEOUWMSQXZQDIP-UHFFFAOYSA-N 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- RVVNCCSGNVEIAX-UHFFFAOYSA-N 2-tert-butylcyclopenta-1,3-diene;carbanide;hafnium(4+) Chemical compound [CH3-].[CH3-].[Hf+4].CC(C)(C)C1=[C-]CC=C1.CC(C)(C)C1=[C-]CC=C1 RVVNCCSGNVEIAX-UHFFFAOYSA-N 0.000 description 2
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 1
- XEEYVTMVFJEEEY-UHFFFAOYSA-L magnesium;dichloride;tetrahydrate Chemical compound O.O.O.O.[Mg+2].[Cl-].[Cl-] XEEYVTMVFJEEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The invention relates to a supported metallocene catalyst and preparation and application thereof, wherein the catalyst comprises a carrier and a reaction product of the following components supported on the carrier: (1) magnesium chloride; (2) an aluminum alkyl; (3) alkylaluminoxane; (4) a metallocene compound. The preparation method comprises the steps of preparing a magnesium chloride modified carrier in the presence of water, and then carrying out loading treatment of aluminum alkyl, aluminum alkyl oxygen alkane and metallocene compounds to obtain the loaded metallocene catalyst. The supported metallocene catalyst of the invention does not need to adopt alkyl aluminoxane when being applied to the subsequent polymerization process, thereby greatly reducing the production cost.
Description
Technical Field
The invention belongs to the field of metallocene catalysts, and particularly relates to a supported metallocene catalyst, and preparation and application thereof.
Background
Since the traditional Ziegler-Natta catalysts, the development and use of metallocene catalysts has been a major breakthrough in the field of olefin polymerization catalysts, and Kaminsky and Sinn et al in the 80 s (Angew.chem., 1980, 19, 390; adv. Organic. Chem.,1980, 18, 99) have found that metallocenes have extremely high catalytic activity under the action of high-efficiency co-catalyst Methylaluminoxane (MAO), leading to the development of metallocene catalysts in a rapidly evolving stage. The main problem of the industrialization of the homogeneous metallocene catalyst is that the MAO consumption is large, the production cost is high, the obtained polymer is amorphous and can not be used in the common slurry method or gas phase method industrial device, and the effective method for overcoming the problems is to carry out the loading treatment on the metallocene catalyst.
Common carriers are silica gel, magnesium chloride, clay, and the like. There has been considerable research on the loading of metallocene catalysts, such as Gregory G.Hlatky in chem.Rev.2000,100,1347-1376 and John R.Severn et al in chem.Rev.2005,105, 4073-4147.
At present, the industrial production mainly adopts silica gel as a carrier, and related patents are also numerous, such as PCT Int.Appl.99/21898; US 6,455,647; mol. Catalyst. A2002,188,123; PCT int.app1.2004/078804; CN101817892a; CN 101172988A; CN101817892a, the supported metallocene catalyst mainly consists of a carrier, aluminoxane and a metallocene compound, wherein the aluminoxane is used in a large amount and is expensive, and the cost of the catalyst is greatly affected.
In summary, there is a need to develop a novel loading method, which reduces the amount of aluminoxane used in the loading process, improves the catalytic performance of the catalyst and reduces its cost.
Disclosure of Invention
The inventor provides a supported metallocene catalyst through a great deal of experimental research, and the catalyst adopts part of alkyl aluminum to replace part of alkyl aluminoxane in preparation, so that the dosage of the alkyl aluminoxane in the supporting process is reduced, but the performance is maintained without being influenced.
It is an object of the present invention to provide a supported metallocene catalyst comprising a support and the reaction product of the following components supported on the support: (1) magnesium chloride; (2) an aluminum alkyl; (3) alkylaluminoxane; (4) a metallocene compound.
In a preferred embodiment, the support is selected from inorganic oxides, preferably silica gel.
In a preferred embodiment, the magnesium chloride is anhydrous magnesium chloride and/or hydrated magnesium chloride, preferably hydrated magnesium chloride, such as magnesium chloride hexahydrate, magnesium chloride tetrahydrate and magnesium chloride dihydrate.
Wherein, after the carrier loading aluminum chloride is dehydrated, a certain content of hydroxyl and crystallization water are added, and the carrier loading aluminum chloride can react with alkyl aluminum to generate alkyl aluminoxane, thereby reducing the dosage of the alkyl aluminoxane in the loading process and lowering the cost.
In a preferred embodiment, the alkyl aluminum is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, tripentylaluminum.
In a further preferred embodiment, the alkyl aluminum is selected from trimethylaluminum, triethylaluminum, triisobutylaluminum.
In a preferred embodiment, the alkylaluminoxane is according to formula (I) or formula (II):
in the formula (I) and the formula (II), R is selected from C 1 -C 12 A is selected from the group consisting of integers from 4 to 30.
In a further preferred embodiment, R is selected from C 1 -C 6 More preferably selected from methyl, ethyl or isobutyl; a is an integer from 4 to 10.
In a preferred embodiment, the metallocene compound is selected from compounds of formula (III) and/or formula (IV):
Cp* 2 MX n formula (III)
Cp* 2 ZMX n (IV)
In the formulae (III) and (IV), cp is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group, the substituents of which are selected from C 1 -C 20 Alkyl, alkoxy, silane, aralkoxy or halogen; z is a linking unit linking two metallocene rings selected from SiR 2 、CR* 2 、SiR* 2 SiR* 2 、CR* 2 CR* 2 、CR*＝CR*、CR* 2 SIR* 2 、GeR* 2 BR or BR 2 Wherein R is selected from hydrogen, alkyl having less than 20 carbon atoms, aryl, silyl, haloalkyl, or haloaryl; m is selected from transition metals of group 4 or group 5 of the periodic Table of the elements; x is the same or different and is selected from halogen, alkyl, alkoxy, acid radical or amino; n is an integer satisfying the valence of M.
Wherein when the metallocene compound is a non-bridged metallocene complex, the structure is shown as a formula (III), and when the metallocene compound is a bridged metallocene complex, the structure is shown as a formula (IV).
The use of a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group as described herein is to be interpreted as referring to the use of a substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl group, as described directly below: substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl groups, may also be described as cyclopentadienyl, indenyl, fluorenyl or substituted derivatives thereof.
In a further preferred embodiment, in formula (III) and formula (IV), cp is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group, preferably the substituents thereof are selected from hydrocarbyl groups; z is a linking unit linking two metallocene rings, preferably a dimethylsilyl bridge or an ethylbridge, wherein R is selected from alkyl groups having less than 20 carbon atoms; m is selected from zirconium; x is the same or different and is selected from chlorine; n is an integer satisfying the valence of M.
In a preferred embodiment, magnesium chloride is used in an amount of 1 to 100 parts, preferably 5 to 25 parts, based on 100 parts by weight of the carrier.
In a preferred embodiment, the total amount of alkylaluminum and alkylaluminoxane is 5 to 85 parts, preferably 25 to 70 parts, based on 100 parts by weight of carrier.
In a preferred embodiment, the weight ratio of alkylaluminum to alkylaluminoxane is (0.05-4): 1, preferably (0.5 to 1): 1.
the inventors have found through a large number of experiments that when the whole alkylaluminoxane is replaced by alkylaluminum, the catalyst activation is not obvious, and only when the alkylaluminoxane is partially replaced, the catalyst has the best catalytic effect, so that the dosage ratio of the alkylaluminoxane and the alkylaluminoxane needs to be strictly controlled.
In a preferred embodiment, the metallocene compound is used in an amount of 0.05 to 3 parts, preferably 0.1 to 2 parts, based on 100 parts by weight of the carrier, the weight of the metallocene compound being based on the weight of the metal element therein.
The second object of the present invention is to provide a method for preparing the supported metallocene catalyst according to one of the objects of the present invention, comprising the steps of:
step 1, mixing the carrier, the magnesium chloride and water, heating, stirring, drying and dehydrating to obtain a magnesium chloride modified carrier;
step 2, placing the magnesium chloride modified carrier in a solvent I in a protective atmosphere to form a suspension I, adding the aluminum alkyl into the suspension I, heating, stirring and performing post-treatment to obtain an intermediate product I;
step 3, placing the intermediate product I in a solvent II in a protective atmosphere to form a suspension II, adding the alkylaluminoxane into the suspension II, heating, stirring and performing post-treatment to obtain an intermediate product II;
and 4, placing the intermediate product II in a solvent III in protective atmosphere to form slurry, adding the metallocene compound into the slurry, heating, stirring and optionally carrying out aftertreatment to obtain the supported metallocene catalyst.
In a preferred embodiment, in step 1, the magnesium chloride is mixed with water, heated and stirred, then the carrier is added, stirred, dried and dehydrated to obtain the magnesium chloride modified carrier.
In a preferred embodiment, in step 1, water is added in an amount of 300 parts or more, preferably 500 to 1500 parts, based on 100 parts by weight of the carrier.
Wherein, the invention is carried out in the presence of water when the magnesium chloride is modified into a carrier, so that even if the magnesium chloride serving as a raw material is anhydrous magnesium chloride, magnesium chloride hydrate is formed in the system of the step 1.
In a preferred embodiment, in steps 1 to 4, the temperature is raised to 0 to 90 ℃, preferably 30 to 80 ℃, more preferably 30 to 60 ℃.
In a preferred embodiment, in steps 1 to 3, the stirring is carried out for 1 to 24 hours, preferably 3 to 8 hours, more preferably 3 to 6 hours.
In a further preferred embodiment, in step 4, the stirring is carried out for 0.5 to 24 hours, preferably for 1 to 2 hours.
In a preferred embodiment, in step 1, the dehydration is carried out in a protective atmosphere (< 5 ppmH) 2 O) is carried out.
In a further preferred embodiment, in step 1, the temperature of the dehydration is from 100 to 600 ℃, preferably from 100 to 450 ℃, more preferably from 100 to 250 ℃.
Wherein the temperature of the dehydration directly affects whether crystal water is present in the magnesium chloride or not, and if the dehydration temperature is too high, for example above 600 ℃, the magnesium chloride loses crystal water to form anhydrous magnesium chloride, then in step 2, the alkyl aluminum does not react to alkyl aluminoxane in the absence of crystal water. However, the temperature should not be too low, below 100 degrees, and the free water is too much to control. However, under the conditions of 100 to 600 ℃, preferably 100 to 450 ℃, more preferably 100 to 250 ℃, according to the present invention, the crystal water is not completely lost, but six crystal waters, four crystal waters, or two crystal waters may also be maintained.
In a preferred embodiment, in steps 2 to 4, the solvent one, solvent two and solvent three are each independently selected from at least one of toluene, benzene, xylene, hexane, heptane and cyclohexane, preferably toluene and/or cyclohexane, more preferably toluene.
In a preferred embodiment, in step 2, the suspension one has a weight concentration of 0.01 to 0.1g/mL, preferably 0.02 to 0.08g/mL.
In a preferred embodiment, in step 3, the suspension II has a weight concentration of 0.01 to 0.1g/mL, preferably 0.02 to 0.08g/mL.
In a preferred embodiment, in step 4, the slurry is present in a weight concentration of 0.01 to 0.1g/mL, preferably 0.02 to 0.08g/mL.
In a preferred embodiment, in steps 2 to 4, the post-treatment comprises washing with a solvent and drying.
In the step 4 of the present invention, if no post-treatment is performed, a slurry containing the supported metallocene catalyst is obtained, and the slurry can be directly used for polymerization reaction; if the post-treatment is carried out, a solid phase product of the supported metallocene catalyst is obtained.
In the present invention, the protective atmosphere is selected from nitrogen and/or inert gases, preferably from nitrogen and/or argon, more preferably nitrogen.
In the preparation process of the present invention, the carrier, the magnesium chloride, the alkylaluminoxane and the metallocene compound are selected in accordance with the definition in one of the objects of the present invention, and at the same time, the respective amounts are also used in accordance with the definition in one of the objects of the present invention.
The third object of the present invention is to provide a supported metallocene catalyst obtained by the second object of the present invention.
It is a fourth object of the present invention to provide the use of the supported metallocene catalyst according to one or three of the objects of the present invention in homo-or co-polymerization of olefins, in particular for homo-or co-polymerization of ethylene with other alpha-olefins, wherein the other alpha-olefins are selected from at least one of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
Meanwhile, the supported metallocene catalyst of the present invention can be applied to various polymerization methods, such as gas phase polymerization, slurry polymerization, etc.
The fifth object of the present invention is to provide an olefin polymerization system comprising one of the objects of the present invention or the fourth object of the present invention, a supported metallocene catalyst, an olefin monomer and optionally a solvent.
In a preferred embodiment, the olefin monomer is selected from ethylene and/or other alpha-olefins.
In a further preferred embodiment, the other alpha-olefin is selected from at least one of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
In a preferred embodiment, the solvent is selected from at least one of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons.
In a further preferred embodiment, the solvent is selected from at least one of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform and dichloroethane.
In a still further preferred embodiment, the solvent is selected from at least one of hexane, toluene and heptane.
In a preferred embodiment, the supported metallocene catalyst is present in the polymerization system at a concentration of 1X 10- 8 Mole/liter-1×10- 3 Moles/liter.
In a further preferred embodiment, the supported metallocene catalyst is present in the polymerization system in a concentration of 1X 10- 8 Mole/liter-1×10- 5 Moles/liter, the molar amount of the supported metallocene catalyst being based on the molar amount of the metallocene compound therein.
When the polymerization system is applied to polymerization, the polymerization temperature is-78 ℃ to 100 ℃, preferably 0 ℃ to 90 ℃; the polymerization pressure is 0.01 to 10.0MPa, preferably 0.01 to 2.0MPa.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the method, after the carrier-supported aluminum chloride is dehydrated, a certain content of hydroxyl and crystal water are added, so that the carrier-supported aluminum chloride can react with the alkyl aluminum to generate the alkyl aluminoxane, thereby reducing the dosage of the alkyl aluminoxane in the loading process and lowering the cost;
(2) The supported metallocene catalyst has very high ethylene polymerization catalytic activity;
(3) The supported metallocene catalyst has good catalytic ethylene and higher alpha-olefin copolymerization, and high copolymerization activity;
(4) The supported metallocene catalyst of the invention does not need to adopt alkyl aluminoxane when being applied to the subsequent polymerization process, thereby greatly reducing the production cost.
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.
Analytical characterization instruments used in the examples and comparative examples were as follows:
1. ICP (plasma emission Spectrometry) characterization-quantitative determination of the weight percent of metal in the supported catalyst. The instrument is a P1000 type ICP-AES plasma emission spectrometer manufactured by PE company in the United states.
2. Characterization of polymer molecular weight versus molecular weight distribution: the molecular weight and the distribution thereof are determined by Gel Permeation Chromatography (GPC), the instrument adopts Waters Alliance GPCV 2000, the solvent is 1,2, 4-trichlorobenzene, the sample concentration is lmg/mL, and the solvent flow rate is 1.0mL/min; the measured temperature was 150 ℃. Each sample was measured twice.
Examples and comparative examples (1, 3-BuMeCp) 2 ZrCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) zirconium dichloride]、(1,3-BuMeCp) 2 HfCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) hafnium dichloride]、(nBuCp) 2 ZrCl 2 Bis- (n-butylcyclopentadienyl) zirconium dichloride, dimethyl bis (T-butylcyclopentadienyl) hafnium (T-BuCp) 2 Hf(CH 3 ) 2 Purchased from carbofuran technology.
The starting materials not specifically described in the examples and comparative examples are commercially available or may be prepared by themselves according to the methods disclosed in the prior art.
Example 1
(1) To a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purging, 150mL of distilled water (H 2 O) 3.21 g of magnesium chloride hexahydrate (MgCl) were slowly added with stirring 2 ·6H 2 O), stirring at a constant temperature at 60 ℃ for 0.5 hours, adding 15 g of silica gel (model 948, grace company, america), continuously stirring at a constant temperature at 60 ℃ for 1 hour, heating and drying to obtain magnesium chloride-loaded silica gel with good fluidity, heating the magnesium chloride-loaded silica gel in a muffle furnace at a constant temperature of 180 ℃ for 4 hours under the protection of nitrogen, and cooling to obtain the magnesium chloride-loaded silica gel carrier. Is kept in a nitrogen atmosphere (< 5 ppmH) during the process 2 O)。
(2) Under the protection of nitrogen, 4.0 g of the obtained modified silica gel carrier is taken and added into a four-necked flask, 60 mL of dehydrated toluene is added, the mixture is dispersed into suspension, 10 mL of 1mmol/mL triethylaluminum toluene solution is added, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 mL of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) 3 g of the powder is taken, added into a four-neck flask under the protection of nitrogen, 60 ml of dehydrated toluene is added, dispersed into suspension, 11 ml of methylaluminoxane toluene solution (10% mass concentration) is added, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 ml of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(4) Under nitrogen protection, 2 g of the silica gel carrier obtained above was charged into a four-necked flask, and 20 ml of dehydrated toluene was added to prepare a slurry, which was dissolved in 20 ml of toluene to prepare 0.129 g (1, 3-BuMeCp) 2 ZrCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) zirconium dichloride]Is added dropwise into the reactor, reacts for 30 minutes at 30 ℃, is then washed with 20 ml of toluene, and is dried in vacuum to obtain the supported metallocene catalyst A. As characterized by ICP, in the catalyst A, the weight content of Zr is 0.49%, and the weight content of Al is 10.68%.
Example 2
Steps (1) - (3) repeat the procedure of example 1, except that step (4):
0.129 g of (1, 3-BuMeCp) from step (4) of example 1 2 ZrCl 2 Replaced by 0.156 g (1, 3-BuMeCp) 2 HfCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) hafnium dichloride]Obtaining the supported metallocene catalyst B. Characterized by ICP, the weight content of Hf in catalyst B was 0.94% and the weight content of Al was 9.91%.
Example 3
Steps (1) - (3) repeat the procedure of example 1, except that step (4):
0.129 g of (1, 3-BuMeCp) from step (4) of example 1 2 ZrCl 2 Replaced by 0.121 g of bis- (n-butylcyclopentadienyl) zirconium dichloride (nBuCp) 2 ZrCl 2 Obtaining the supported metallocene catalyst C. The ICP characterization shows that in the catalyst C, the weight content of Zr is 0.55%, and the weight content of Al is 9.22%.
Example 4
Steps (1) - (3) repeat the procedure of example 1, except that step (4):
0.129 g of (1, 3-BuMeCp) from step (4) of example 1 2 ZrCl 2 Replaced by 0.135 g of dimethyl bis (T-butylcyclopentadienyl) hafnium (T-BuCp) 2 Hf(CH 3 ) 2 Obtaining the supported metallocene catalyst D. Characterized by ICP, the weight content of Hf in catalyst D was 0.92% and the weight content of Al was 9.50%.
Example 5
(1) Step (1) of example 1 was repeated, except that: 3.21 g of magnesium chloride hexahydrate (MgCl) 2 ·6H 2 O) is replaced by 2.4 g of magnesium chloride hexahydrate (MgCl) 2 ·6H 2 O), the stirring temperature was replaced by 40 ℃ and the constant heating temperature in the muffle furnace was replaced by 150 ℃ from 180 ℃.
(2) Step (1) of example 1 was repeated, except that: 10 mL of 1mmol/mL triethylaluminum toluene solution was replaced with 10 mL of 1mmol/mL triisobutylaluminum toluene solution.
(3) Step (3) of example 1 was repeated.
(4) Step (4) of example 1 was repeated to obtain a supported metallocene catalyst E. As characterized by ICP, in the catalyst E, the weight content of Zr is 0.46%, and the weight content of Al is 10.33%.
Example 6
(1) To a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purging, 150mL of distilled water (H 2 O) 3.75 g of magnesium chloride hexahydrate (MgCl) are slowly added with stirring 2 ·6H 2 O), then stirring at a constant temperature of 30 ℃ for 1 hour, adding 15 g of silica gel (model 948, grace company, america), continuously stirring at a constant temperature of 30 ℃ for 2 hours, heating and drying to obtain magnesium chloride-loaded silica gel with good fluidity, heating the magnesium chloride-loaded silica gel in a muffle furnace at a constant temperature of 200 ℃ for 4 hours under the protection of nitrogen, and cooling to obtain the magnesium chloride-loaded silica gel carrier. Is kept in a nitrogen atmosphere (< 5 ppmH) during the process 2 O)。
(2) Under the protection of nitrogen, 4.0 g of the obtained modified silica gel carrier is taken and added into a four-necked flask, 40 mL of dehydrated toluene is added, the mixture is dispersed into suspension, 7 mL of 1mmol/mL triethylaluminum toluene solution is added, the temperature is raised to 40 ℃, the mixture is stirred and reacted for 6 hours, then the mixture is washed three times with 60 mL of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) 3 g of the powder is taken, added into a four-neck flask under the protection of nitrogen, 37.5 ml of dehydrated toluene is added, dispersed into suspension, 10 ml of methylaluminoxane toluene solution (10% mass concentration) is added, the temperature is raised to 40 ℃, the mixture is stirred and reacted for 6 hours, then the mixture is washed three times with 60 ml of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(4) Under nitrogen protection, 2 g of the silica gel carrier obtained above was put into a four-necked flask, 25 ml of dehydrated toluene was added to prepare a slurry, and 0.057 g (1, 3-BuMeCp) was dissolved in 20 ml of toluene 2 ZrCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) zirconium dichloride]Is added dropwise to the solution of (2)In the reactor, the reaction was carried out at 60℃for 60 minutes, followed by washing with 20 ml of toluene and vacuum drying, to obtain a supported metallocene catalyst F. As characterized by ICP, in the catalyst F, the weight content of Zr is 0.29%, and the weight content of Al is 9.68%.
Example 7
(1) To a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purging, 150mL of distilled water (H 2 O) 1.5 g of magnesium chloride hexahydrate (MgCl) were slowly added with stirring 2 ·6H 2 O), stirring at constant temperature for 20min at 80 ℃, adding 15 g of silica gel (model 948, grace company, america), continuously stirring at constant temperature for 40min at 80 ℃, heating and drying to obtain magnesium chloride-loaded silica gel with good fluidity, heating the magnesium chloride-loaded silica gel in a muffle furnace at constant temperature of 220 ℃ for 3 h under the protection of nitrogen, and cooling to obtain the magnesium chloride-loaded silica gel carrier. Is kept in a nitrogen atmosphere (< 5 ppmH) during the process 2 O)。
(2) Under the protection of nitrogen, 4.0 g of the obtained modified silica gel carrier is taken and added into a four-necked flask, 50mL of dehydrated toluene is added, the mixture is dispersed into suspension, 6.37 mL of 1mmol/mL triethylaluminum toluene solution is added, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 3 hours, then the mixture is washed three times with 60 mL of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) 3 g of the powder is taken and added into a four-neck flask under the protection of nitrogen, 150ml of dehydrated toluene is added, the mixture is dispersed into suspension, 6.1 ml of methylaluminoxane toluene solution (10% mass concentration) is added, the temperature is raised to 60 ℃, the mixture is stirred and reacted for 3 hours, then the mixture is washed three times with 60 ml of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(4) Under nitrogen protection, 2 g of the silica gel carrier obtained above was put into a four-necked flask, 40 ml of dehydrated toluene was added to prepare a slurry, and 0.028 g (1, 3-BuMeCp) of the slurry was dissolved in 20 ml of toluene 2 ZrCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) zirconium dichloride]Is added dropwise into the reactor, reacted at 80 ℃ for 40 minutes, then washed with 20 ml of toluene and dried in vacuum to obtain the supported metallocene catalyst G. Characterized by ICP, in catalyst G, the weight content of Zr was 0.19%, and the weight content of Al was 6.68%.
Example 8
(1) To a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purging, 150mL of distilled water (H 2 O) 0.75 g of magnesium chloride hexahydrate (MgCl) was slowly added with stirring 2 ·6H 2 O), stirring at constant temperature for 1h at 40 ℃, adding 15 g of silica gel (model 948, grace company, america), continuously stirring at constant temperature for 2h at 40 ℃, heating and drying to obtain magnesium chloride-loaded silica gel with good fluidity, heating the magnesium chloride-loaded silica gel in a muffle furnace at constant temperature of 230 ℃ for 3 h under the protection of nitrogen, and cooling to obtain the magnesium chloride-loaded silica gel carrier. Is kept in a nitrogen atmosphere (< 5 ppmH) during the process 2 O)。
(2) Under the protection of nitrogen, 4.0 g of the obtained modified silica gel carrier is taken and added into a four-necked flask, 200 mL of dehydrated toluene is added, the mixture is dispersed into suspension, 3.6 mL of 1mmol/mL triethylaluminum toluene solution is added, the temperature is raised to 40 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 mL of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) 3 g of the powder is taken, added into a four-neck flask under the protection of nitrogen, 50ml of dehydrated toluene is added, dispersed into suspension, 2.7 ml of methylaluminoxane toluene solution (10% mass concentration) is added, the temperature is raised to 40 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 ml of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(4) Under nitrogen protection, 2 g of the silica gel carrier obtained above was put into a four-necked flask, 100 ml of dehydrated toluene was added to prepare a slurry, and 0.06 g (1, 3-BuMeCp) of the slurry was dissolved in 20 ml of toluene 2 ZrCl 2 [ bis (1, 3-butylmethylcyclopentadienyl) dichlorideZirconium]Is added dropwise into the reactor, reacts for 1 hour at 50 ℃, is then washed with 20 ml of toluene, and is dried in vacuum to obtain the supported metallocene catalyst H. As characterized by ICP, in the catalyst H, the weight content of Zr is 0.31%, and the weight content of Al is 4.56%.
Comparative example 1
(1) 15 g of silica gel (model 948, grace Co., U.S.A.) was heated in a muffle furnace at 650℃for 8 hours under nitrogen protection, and cooled to obtain an activated silica gel carrier.
(2) Under the protection of nitrogen, 4.0 g of the obtained activated silica gel carrier is taken and added into a four-necked flask, 60 mL of dried toluene is added, the mixture is dispersed into suspension, 10 mL of 1mmol/mL triethylaluminum toluene solution is added, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 mL of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) The powder was taken out by taking 3 g, and added into a four-necked flask under the protection of nitrogen, 11 ml of methylaluminoxane solution (10% by mass concentration) was added, the temperature was raised to 50 ℃, the reaction was stirred for 4 hours, then the mixture was washed three times with 60 ml of x 3 toluene, then washed with hexane, and dried in vacuo to obtain a solid powder having good fluidity.
(4) The procedure of step (4) of example 1 was followed to obtain supported metallocene catalysts A to D1. As characterized by ICP, in the catalyst A-D1, the weight content of Zr was 0.51%, and the weight content of Al was 10.11%.
Comparative example 2
(1) To a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purge, 150mL of anhydrous tetrahydrofuran was added, 1.5 g of anhydrous magnesium chloride was slowly added under stirring, then stirred at a constant temperature for 0.5 hour at 60℃and 15 g of silica gel (model 948, grace, USA) was further added, stirring at a constant temperature for 1 hour at 60℃was continued, and the temperature was raised and dried to obtain a magnesium chloride-loaded silica gel having good fluidity, which was heated at a constant temperature for 4 hours at 650℃under nitrogen protection in a muffle furnace, and cooled to obtain a magnesium chloride-loaded silica gel carrier. Is maintained throughout the processIn a nitrogen atmosphere (< 5 ppmH) 2 O)。
(2) Under the protection of nitrogen, 4.0 g of the obtained modified silica gel carrier is taken and added into a four-necked flask, 60 ml of dried toluene is added, the mixture is dispersed into suspension, 21 ml of methylaluminoxane solution (10% mass concentration) is added, the temperature is raised to 50 ℃, the mixture is stirred and reacted for 4 hours, then the mixture is washed three times with 60 ml of x 3 toluene, then the mixture is washed with hexane, and the mixture is dried in vacuum, thus obtaining solid powder with good fluidity.
(3) Supported metallocene catalysts A-D2 were obtained in the same manner as in step (4) of example 1. As characterized by ICP, in the catalysts A-D2, the weight content of Zr was 0.53%, and the weight content of Al was 10.39%.
Comparative example 3
The procedure of example 1 was repeated, except that the dehydration temperature in step (2) was different: heating at 650 ℃ for 4 hours. Catalysts A-D3 were obtained.
In this comparative example, although water was also added in the preparation of step (1), the temperature of the dehydration treatment of step (1) was too high, resulting in total loss of crystal water on magnesium chloride, and thus, the aluminum alkyl did not react to form alkylaluminoxane in the subsequent step (2).
Example 9 high pressure ethylene polymerization experiment
In a 1 liter stainless steel autoclave, replaced three times with nitrogen and ethylene each, then 500 ml of hexane solvent was added, 1 ml of 1 mol/liter Triethylaluminum (TEA) hexane solution and the required amount of 1-hexene were added with the addition of hexane, then 50 mg of the supported metallocene catalyst prepared in the above examples and comparative examples was added, and the temperature was raised to 85℃and the pressure was raised to and maintained at 1.1MPa for 1 hour. And after the polymerization reaction is finished, cooling, collecting polyethylene particle powder, and weighing. The specific polymerization results are shown in Table 1.
TABLE 1 polymerization results for Supported metallocene catalysts
Claims (25)
1. A supported metallocene catalyst comprising a support and a reaction product of: (1) magnesium chloride; (2) an aluminum alkyl; (3) alkylaluminoxane; (4) a metallocene compound; based on 100 parts by weight of the carrier, the magnesium chloride is used in an amount of 1-100 parts, the total amount of the aluminum alkyl and the alkyl aluminoxane is 5-85 parts, and the metallocene compound is used in an amount of 0.05-3 parts, wherein the weight of the metallocene compound is calculated by the weight of metal elements; the weight ratio of the alkyl aluminum to the alkyl aluminoxane is (0.05-4): 1, a step of;
the preparation method of the supported metallocene catalyst comprises the following steps: step 1, mixing the carrier, the magnesium chloride and water, heating, stirring, drying and dehydrating, wherein the dehydrating is performed in a protective atmosphere, and the dehydrating temperature is 100-600 ℃ to obtain a magnesium chloride modified carrier; step 2, placing the magnesium chloride modified carrier in a solvent I in a protective atmosphere to form a suspension I, adding the aluminum alkyl into the suspension I, heating, stirring and performing post-treatment to obtain an intermediate product I; step 3, placing the intermediate product I in a solvent II in a protective atmosphere to form a suspension II, adding the alkylaluminoxane into the suspension II, heating, stirring and performing post-treatment to obtain an intermediate product II; and 4, placing the intermediate product II in a solvent III in protective atmosphere to form slurry, adding the metallocene compound into the slurry, heating, stirring and optionally carrying out aftertreatment to obtain the supported metallocene catalyst.
2. The supported metallocene catalyst according to claim 1, wherein,
the support is selected from inorganic oxides; and/or
The alkyl aluminum is at least one selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, tricyclopentyl aluminum, tri-n-pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum and tripentyl aluminum.
3. The supported metallocene catalyst according to claim 2, characterized in that,
the carrier is silica gel; and/or
The alkyl aluminum is selected from trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.
4. The supported metallocene catalyst according to claim 1, wherein the alkylaluminoxane is represented by formula (I) or formula (II):
in the formula (I) and the formula (II), R is selected from C 1 -C 12 A is selected from the group consisting of integers from 4 to 30.
5. The supported metallocene catalyst according to claim 1, characterized in that the metallocene compound is selected from compounds of formula (III) and/or formula (IV):
Cp* 2 MX n formula (III)
Cp* 2 ZMX n (IV)
In the formulae (III) and (IV), cp is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group, the substituents of which are selected from C 1 -C 20 Alkyl, alkoxy, silane, aralkoxy or halogen; z is a linking unit linking two metallocene rings selected from SiR 2 、CR* 2 、SiR* 2 SiR* 2 、CR* 2 CR* 2 、CR*＝CR*、CR* 2 SIR* 2 、GeR* 2 BR or BR 2 Wherein R is selected from hydrogen, alkyl having less than 20 carbon atoms, aryl, silyl, haloalkyl, or haloaryl; m is selected from transition metals of group 4 or group 5 of the periodic Table of the elements; x is the same or different and is selected from halogen, alkyl, alkoxy, acid radical or amino; n is an integer satisfying the valence of M.
6. The supported metallocene catalyst according to claim 1 to 5, characterized in that,
based on 100 parts by weight of the carrier, the dosage of the magnesium chloride is 5-25 parts; and/or
The total amount of the alkylaluminum and the alkylaluminoxane is 25 to 70 parts based on 100 parts by weight of the carrier; and/or
The metallocene compound is used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the carrier, the weight of the metallocene compound being based on the weight of the metal element therein; and/or
The weight ratio of the alkyl aluminum to the alkyl aluminoxane is (0.5-1): 1.
7. the method for preparing a supported metallocene catalyst according to any one of claims 1 to 6, comprising the steps of:
step 1, mixing the carrier, the magnesium chloride and water, heating, stirring, drying and dehydrating to obtain a magnesium chloride modified carrier; the dehydration is carried out in a protective atmosphere, and the temperature of the dehydration is 100-600 ℃;
step 2, placing the magnesium chloride modified carrier in a solvent I in a protective atmosphere to form a suspension I, adding the aluminum alkyl into the suspension I, heating, stirring and performing post-treatment to obtain an intermediate product I;
step 3, placing the intermediate product I in a solvent II in a protective atmosphere to form a suspension II, adding the alkylaluminoxane into the suspension II, heating, stirring and performing post-treatment to obtain an intermediate product II;
and 4, placing the intermediate product II in a solvent III in protective atmosphere to form slurry, adding the metallocene compound into the slurry, heating, stirring and optionally carrying out aftertreatment to obtain the supported metallocene catalyst.
8. The method according to claim 7, wherein in step 1, water is added in an amount of 300 parts or more based on 100 parts by weight of the carrier.
9. The method of claim 8, wherein in step 1, water is added in an amount of 500 to 1500 parts by weight based on 100 parts by weight of the carrier.
10. The method according to claim 7, wherein,
in the steps 1 to 4, the temperature is raised to 0 to 90 ℃; and/or
In the step 1 to the step 3, stirring is carried out for 1 to 24 hours; and/or
In step 4, the stirring is carried out for 0.5-24 hours.
11. The method according to claim 10, wherein,
in the steps 1 to 4, the temperature is raised to 30 to 80 ℃.
12. The method according to claim 10, wherein,
in the step 1 to the step 3, the stirring is carried out for 3 to 8 hours; and/or
In step 4, the stirring is carried out for 1-2 hours.
13. The process according to any one of claims 7 to 11, wherein the dehydration is carried out in a protective atmosphere at a temperature of 100 to 450 ℃.
14. The method according to claim 13, wherein the dehydration is performed under a protective atmosphere, and the temperature of the dehydration is 100 to 250 ℃.
15. The method of claim 13, wherein the process comprises,
in the step 2, the weight concentration of the suspension I is 0.01-0.1 g/mL; and/or
In the step 3, the weight concentration of the second suspension is 0.01-0.1 g/mL; and/or
In step 4, the weight concentration of the slurry is 0.01-0.1 g/mL.
16. The method according to claim 15, wherein,
in the step 2, the weight concentration of the suspension I is 0.02-0.08 g/mL; and/or
In the step 3, the weight concentration of the second suspension is 0.02-0.08 g/mL; and/or
In step 4, the weight concentration of the slurry is 0.02-0.08 g/mL.
17. A supported metallocene catalyst obtainable by the process according to any one of claims 7 to 16.
18. Use of a supported metallocene catalyst according to one of claims 1 to 6 or a supported metallocene catalyst according to claim 17 in olefin homo-or co-polymerization.
19. The use according to claim 18 for ethylene homo-polymerization or copolymerization of ethylene with other alpha-olefins, wherein the other alpha-olefins are selected from at least one of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
20. An olefin polymerization system comprising the supported metallocene catalyst of any one of claims 1 to 6 or the supported metallocene catalyst of claim 17, together with an olefin monomer and optionally a solvent.
21. The olefin polymerization system of claim 20 wherein said olefin monomer is selected from ethylene and/or other alpha-olefins selected from at least one of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
22. The olefin polymerization system of claim 20 wherein said solvent is selected from at least one of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons.
23. The olefin polymerization system of claim 22 wherein said solvent is selected from at least one of hexane, toluene and heptane.
24. The olefin polymerization system of claim 20 wherein in said polymerization system the supported metallocene catalyst has a concentration of 1 x 10 －8 Molar/liter-1×10 －3 Moles/liter.
25. The olefin polymerization system of claim 24 wherein in said polymerization system said supported metallocene catalyst has a concentration of 1 x 10 －8 Molar/liter-1×10 －5 Moles/liter.
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| CN101817892A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Method for preparing magnesium chloride loaded metallocene catalyst |
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| CN101423575A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst component and preparation method thereof and use |
| CN101817892A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Method for preparing magnesium chloride loaded metallocene catalyst |
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