CN112654645A - 用于烯烃聚合的前体和催化剂组分 - Google Patents
用于烯烃聚合的前体和催化剂组分 Download PDFInfo
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- CN112654645A CN112654645A CN201980057415.3A CN201980057415A CN112654645A CN 112654645 A CN112654645 A CN 112654645A CN 201980057415 A CN201980057415 A CN 201980057415A CN 112654645 A CN112654645 A CN 112654645A
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- 239000003054 catalyst Substances 0.000 title claims description 22
- 239000002243 precursor Substances 0.000 title claims description 21
- 238000006116 polymerization reaction Methods 0.000 title claims description 12
- 150000001336 alkenes Chemical class 0.000 title claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 239000008247 solid mixture Substances 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- 239000000320 mechanical mixture Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- 239000011949 solid catalyst Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 22
- 238000005259 measurement Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 5
- 238000006062 fragmentation reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- -1 hydrocarbon radical Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- GXNXZJMAFGKLQI-UHFFFAOYSA-N (2-benzoyloxy-5-tert-butyl-3-methylphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC=1C(C)=CC(C(C)(C)C)=CC=1OC(=O)C1=CC=CC=C1 GXNXZJMAFGKLQI-UHFFFAOYSA-N 0.000 description 1
- ADJPHOXDUMMLMM-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(2-methylpentan-2-yl)silane Chemical compound CCCC(C)(C)[Si](OC)(OC)N1CCCCC1CC ADJPHOXDUMMLMM-UHFFFAOYSA-N 0.000 description 1
- PJSFQEVODHCOOF-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(3,3,3-trifluoropropyl)silane Chemical compound CCC1CCCCN1[Si](CCC(F)(F)F)(OC)OC PJSFQEVODHCOOF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 1
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NIOVJFCCEONHGJ-UHFFFAOYSA-N tert-butyl-(2-ethylpiperidin-1-yl)-dimethoxysilane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)(C)C NIOVJFCCEONHGJ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
一种固体混合物，包含以下的机械混合物(a)式MgCl2(R1OH)n的加合物的不同颗粒，其中R为C1‑C8烷基，优选乙基，并且n为0.2至6，具有范围从5至100μm的平均粒度(P50a)，(b)从0.2至5.0wt％的固体化合物的不同颗粒，含有超过50wt％的SiO2单元并且具有使得比例P50b/P50a在0.4至1.5范围内的平均粒度(P50b)。
Description
技术领域
本公开涉及齐格勒-纳塔催化剂组分前体及其制备方法。所述前体具有改善的流动性并用于制备用于烯烃聚合的ZN催化剂组分。
背景技术
齐格勒-纳塔催化剂组分可用于烯烃如丙烯的立体定向聚合。所述催化剂制备可涉及使用待与钛化合物和任选地与内部电子给体化合物反应的前体。
该前体可以包含式MgCl2(R1OH)n的加合物，其中R是C1-C8烷基，特别是乙基，并且n是2至6。它们的特定粒度为约5至约100μm。由于它们的固有性质，加合物颗粒可能经受内聚性问题，其在催化剂制备期间恶化流动性并降低前体颗粒的均匀分布。
为了解决这些问题，本领域中建议使用滑爽剂，例如硬脂酸酯或芥酸酰胺。然而，这些添加剂没有改善前体颗粒的流动性特征。美国专利申请公开第2015/0344667号建议用由导电材料如炭黑制成的纳米颗粒层涂布催化剂或载体颗粒。然而，该方法是繁重的，因为必须进行用于制备包含纳米颗粒的凝胶的额外的，单独的步骤。此外，额外层的存在可以防止催化活性金属和载体之间的必要相互作用。另外，包含使用水基纳米颗粒凝胶的程序可以随后使Ti基催化剂失活。
EP 1666505 A1描述了一种催化剂制备路线，其中最终的催化剂组分从包括几种成分的反应混合物中沉淀。当二氧化硅是成分之一时，所获得的催化剂显示出生产具有窄粒度分布的聚合物的能力。没有关于前体的流动性的描述或建议。
因此需要一种改善前体流动性而不损害其性能的简单方法。
令人惊奇地，已经发现，通过将MgCl2-ROH加合物颗粒与低量的具有特定组成的分离的无机颗粒机械混合，可以获得具有增强的流动性的前体。
发明内容
本公开的目的涉及ZN催化剂组分前体，其包含以下的机械混合物：(a)式MgCl2(R1OH)n的加合物的不同颗粒，其中R为C1-C8烷基，优选乙基，并且n为0.2至6，具有范围从5至100μm的平均粒度(P50a)；以及(b)从0.2至5.0wt％的固体化合物的不同颗粒，含有超过50wt％的SiO2单元并且具有使得比例P50b/P50a在0.4至1.5范围内的平均粒度(P50b)。
具体实施方式
术语机械混合表示加合物(a)的颗粒与固体化合物(b)的颗粒不同且分离。所述加合物(a)的颗粒和化合物(b)的颗粒通过机械混合彼此接触。
优选地，在本公开的前体中，固体化合物(b)具有范围为2至50μm，更优选10至40μm，特别是15至30μm的平均粒度(P50b)。
优选地，含有超过50wt％的SiO2单元的固体化合物(b)选自二氧化硅、硅酸盐和硅藻土。在硅酸盐中，特别优选的是层状硅酸盐如滑石。
二氧化硅可为亲水性二氧化硅(含有残余羟基)或其中OH基团已被SiOR替代的疏水性二氧化硅。
此外，优选使用硅藻土。其中，特别优选使用以商品名
出售的硅藻土。
以(P50a)表示的加合物(a)的平均粒度优选地范围为10μm至100μm，更优选地15μm至80μm，并且特别地15μm至60μm。
P50a和P50b的值在两种情况下都是指不包括聚集体的粉末样品。基本上不含聚集体的粉末样品可以通过根据实验部分中阐述的程序使粉末经受机械轧制或超声处理来获得。
优选地，比例P50b/P50a范围为0.60至1.50，更优选地0.75至1.50并且特别地0.8至1.3。
优选地，基于混合物(a)和(b)的总重量，固体化合物(b)的颗粒的量范围为0.5至5.0wt％，更优选地0.75至4.0wt％，特别地1.0至3.0wt％。
通过在与加合物不混溶的惰性烃的存在下混合醇和氯化镁，在搅拌条件下在加合物的熔融温度(100-130℃)下操作，可以适当地制备加合物。然后，将乳液快速骤冷，从而引起加合物以球形颗粒形式固化。例如在USP4,469,648、USP4,399,054、WO98/44009和WO02/051544中报道了用于制备这些球形加合物的代表性方法。另一种用于球化的可用方法是例如在USP 5,100,849和4,829,034中描述的喷雾冷却。
特别令人关注的是MgCl2(EtOH)m加合物，其中m为0.15至1.5并且粒度范围为10至100μm，其通过使具有较高醇含量的加合物经受在氮气流中在50至150℃的温度下进行的热脱醇过程直到醇含量降低至上述值而获得。在EP395083中描述了这种类型的方法。
脱醇还可以通过使加合物与能够与醇基反应的化合物接触来化学地进行。
脱醇加合物的特征还在于由半径至多为1μm的孔引起的孔隙率(通过水银法测量)为0.15至2.5cm3/g，优选0.25至1.5cm3/g。
优选地，根据本公开，加合物颗粒(a)具有占优势的球形形状。特别地，它们的特征可在于球度因子高于0.60，优选高于0.70。使用在本申请的表征部分中描述的图像分析技术来计算球度因子。
包含加合物(a)的不同颗粒和固体化合物(b)的不同颗粒的干燥混合物的前体可以用几种共混方法制备，其中优选的方法包含在合适的设备中干燥共混两种固体。优选地，干混在室温下在氮气环境中进行0.2至20小时，优选0.5至15小时，更优选0.5至5小时的时间。
还可以通过搅拌颗粒(a)和(b)的液态烃浆液，然后除去液相，随后干燥颗粒来制备干燥前体。
从实施例可以看出，如此获得的前体显示出相对于原样的加合物颗粒(a)的降低的断裂和雪崩能量。该改善与比例P50b/P50a的使用是0.8或更高相结合是特别显著的。断裂能量和雪崩能量是与粉末流动性成反比的。这些性能的较低值表示较高的流动性。具有改善的流动性的前体允许在固体催化剂组分制备阶段更容易地转移和计量粉末。通常，相对于原样的加合物(a)的颗粒，前体显示出10％或更高，优选20％或更高，特别是高于30％的断裂能量改善百分比。此外，相对于原样的加合物(a)的颗粒，前体显示出25％或更高，优选50％或更高，特别是高于60％的雪崩能量改善百分比。断裂能量和雪崩能量改善百分比之和高于35％，优选高于60％，特别是高于80％。
如此获得的前体然后可用于制备固体催化剂组分。根据优选的方法，固体催化剂组分可以通过使式Ti(OR2)m-yXy的钛化合物与本公开的固体混合物反应来制备，其中m是钛的化合价，y是1至m的数，并且R2是C1-C10烷基。Ti化合物优选为TiCl4。与Ti化合物的反应可通过将固体混合物悬浮在冷TiCl4(约0℃)；将混合物加热至80-130℃并在该温度下保持0.5-2小时来进行。用TiCl4处理可以进行一次或多次。电子给体化合物优选在用TiCl4处理期间加入。球形催化剂组分的制备例如描述在欧洲专利申请EP-A-395083、EP-A-553805、EP-A-553806、EPA601525和WIPO专利申请公开第WO98/44009号中。
当根据该方法制备时，基于固体催化剂组分的总重量，固体催化剂组分可以包含8wt％至30wt％，更优选10wt％至25wt％的Mg。优选地，基于固体催化剂组分的总重量，Ti的量范围为0.1wt％至8wt％，更优选0.5wt％至5wt％，甚至更优选0.7wt％至3wt％。
在本公开的优选方面，如此获得的催化剂组分还包含电子给体化合物(内部给体)。优选地，其选自酯、醚、胺、硅烷、氨基甲酸酯和酮或其混合物。
内部给体优选选自以下各项组成的组：任选取代的芳族一元或多元羧酸的烷基和芳基酯，例如苯甲酸和邻苯二甲酸的酯，和选自丙二酸、戊二酸、马来酸和琥珀酸的脂族酸的酯。这种酯的具体实例是邻苯二甲酸正丁酯、邻苯二甲酸二异丁酯、邻苯二甲酸二正辛酯、苯甲酸乙酯和对乙氧基苯甲酸乙酯。此外，可以使用WO2010/078494和美国专利7,388,061中公开的二酯。在这一类中，特别优选的是2，4-戊二醇二苯甲酸酯衍生物和3-甲基-5-叔丁基邻苯二酚二苯甲酸酯。此外，内部给体可以选自二醇衍生物，所述二醇衍生物选自二氨基甲酸酯、单氨基甲酸酯单酯和单碳酸单酯。此外，还可以有利地使用下式的1，3二醚：
其中R、RI、RII、RIII、RIV和RV彼此相同或不同，是氢或具有1-18个碳原子的烃基，并且RVI和RVII彼此相同或不同，具有R-RV的相同含义，除了它们不能是氢；R-RVII基团中的一个或多个可以连接以形成环。特别优选其中RVI和RVII选自C1-C4烷基的1，3-二醚。
还可以使用上述给体的混合物。具体的混合物是由琥珀酸与1，3二醚的酯构成的那些，如WO2011/061134中所公开的。
当期望增加催化剂在聚合物链内分布烯烃共聚单体的能力时，例如在生产乙烯/α-烯烃共聚物的情况下，优选在单官能给体，特别是醚和酯中选择电子给体。优选的醚是C2-C20脂族醚，特别是优选具有3-5个碳原子的环醚，环醚例如四氢呋喃、二噁烷。优选的酯是脂族单羧酸的C1-C4烷基酯，例如乙酸乙酯和甲酸甲酯。四氢呋喃和乙酸乙酯是最优选的。
通常，固体催化剂组分中电子给体化合物的最终量可以范围为0.5wt％至40wt％，优选为1wt％至35wt％。
固体催化剂组分然后可以通过使它们与有机铝化合物反应而转化成用于烯烃聚合的催化剂。
有机铝化合物优选选自烷基-Al化合物，特别选自三烷基铝化合物，例如三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝。还可以使用烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物，例如AlEt2Cl和Al2Et3Cl3，其可能与上述三烷基铝混合。该Al/Ti比高于1并且优选包含在50与2000之间。
该催化剂可以另外包含外部给体，该外部给体可以选自硅化合物、醚、酯、胺、杂环化合物并且特别是2，2，6，6-四甲基哌啶和酮。优选地，其选自式(R6)a(R7)bSi(OR8)c的硅化合物，其中a和b为0至2的整数，c为1至4的整数，且(a+b+c)的总和为4；R6、R7和R8是任选含有杂原子的具有1-18个碳原子的烷基、环烷基或芳基。特别优选的是硅化合物，其中a是1，b是1，c是2，R6和R7中的至少一个选自具有3-10个碳原子，任选地包含杂原子的支链烷基、环烷基或芳基基团，并且R8是C1-C10烷基基团，特别是甲基。这种优选的硅化合物的实例是甲基环己基二甲氧基硅烷(C给体)、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷(D给体)、二异丙基二甲氧基硅烷、(2-乙基哌啶基)叔丁基二甲氧基硅烷、(2-乙基哌啶基)叔己基二甲氧基硅烷、(3，3，3-三氟-正丙基)(2-乙基哌啶基)二甲氧基硅烷、甲基(3，3，3-三氟-正丙基)二甲氧基硅烷。此外，其中a为0，c为3，R7任选含有杂原子的支链烷基或环烷基且R8为甲基的硅化合物也是优选的。这种优选的硅化合物的实例是环己基三甲氧基硅烷、叔丁基三甲氧基硅烷和叔己基三甲氧基硅烷。
电子给体化合物(iii)的用量使得所述有机铝化合物与所述电子给体化合物(iii)的摩尔比为0.1至500，优选1至300，更优选3至100。
因此，本公开的另一个目的是用于烯烃CH2＝CHR的(共)聚合的方法，其中R是氢或具有1-12个碳原子的烃基，所述方法在催化剂的存在下进行，所述催化剂包含以下之间的反应产物：
(i)本公开的固体催化剂组分；
(ii)烷基铝化合物和，
(iii)任选的电子给体化合物(外部给体)。
聚合方法可以根据各种技术进行，例如使用惰性烃溶剂作为稀释剂的淤浆聚合，或使用液体单体(例如丙烯)作为反应介质的本体聚合。此外，可以在一个或多个流化床或机械搅拌床反应器中操作的气相中进行聚合方法。
聚合可以在20至120℃，优选40至80℃的温度下进行。当聚合在气相中进行时，操作压力为0.5至5Mpa，优选1至4MPa。在本体聚合中，操作压力可以为1至8Mpa，优选1.5至5MPa。
给出以下实施例以便更好地说明主题而不对其进行限制。
表征
平均粒度
通过基于单色激光的光学衍射原理的方法用“Malvern Instruments 2000”设备测定。平均尺寸以P50给出。也用该方法测定了P10和P90。
Malvem Mastersizer 2000粒度分析仪分为3个单元：
1)光学单元；用于测量尺寸在0,02至2000μ范围内的固体的光学核心单元，配备有两个激光束源：红色He/Ne激光器，功率5mw，波长633nm，蓝色(二极管)激光器，波长450nm。
2)采样单元；用于50-120ml体积的Hidro 2000S自动采样装置，其以内部容量、离心泵、搅拌器和具有40W功率输出的超声探头操作。
3)PC控制台；便携式LG Pentium系列，使用用于Windows 2000或NT的MalvemProfessional软件。数据加工方法使用Mie光学理论(样品的折射率＝1.596；正庚烷的折射率＝1.39)。
方法描述
对于本文所述的测量，正庚烷(加2g/l抗静电Span 80)用作分散剂。
向该计量池中装入分散剂，同时将泵/搅拌器速度设定为2205RPM。然后进行背景测量。然后通过使用用于固体或浆液的专用装载装置装载样品。此时，在进行PS测定之前，样品经历30秒的超声处理。此后，进行测量。
断裂能量和雪崩能量的测定
用旋转粉末分析仪(美国康涅狄格州纽镇汞科学院公司)进行测量。在2014年8月30日修订的用户手册中提供了具体的测量条件。
球度因子的测定
该测定用图像分析仪商业软件分析程序3.2进行，其描述了使用应用于由SEM照片构成的图像源的算法的颗粒的球形度，该SEM照片的尺寸基于催化剂颗粒的平均尺寸选择以包括统计上代表性数量的颗粒。对于具有70μm的平均粒度的催化剂样品，图片的尺寸是2.5x2.5mm。例如，对于具有约9μm的粒度的催化剂样品，图片的尺寸是150μm x 150μm。
起始MgCl2-EtOH颗粒(固体混合物的组分(a))
根据WO02/051544中描述的方法制备三批不同的微球MgCl2·2.8C2H5OH，其具有以下P50：
-批次A 28μm。
-批次B 34μm。
-批次C 20μm。
化合物(b)
使用以下化合物：
-
可从Sigma-Aldrich购得的硅藻土，P50为22μm；
-Silica S5631，具有0.9μm平均颗粒(可从Fluka购得)；
-Gasil AB 200DF由PQ公司商业化。其是具有8μm的P50尺寸的无定形二氧化硅；
-Gasil AB 735由PQ公司商业化。其是具有24μm的P50尺寸的无定形二氧化硅；
-Silica H30由Wacker Chemie AG商业化。其具有22μm的P50尺寸；
-Silica T30由Wacker Chemie AG商业化。其具有23μm的P50尺寸；
-Silica T40由Wacker Chemie AG商业化。其具有33μm的P50尺寸；
实施例
实施例1-2和对比例1
通过干混批次A的固体加合物与表1中报道的特定量的
制备一系列的三种混合物。共混如下进行。将100克固体催化剂组分引入到1L玻璃瓶中，然后还加入表1中报道的量的
通过在60rpm下滚动瓶子1小时来混合固体。对所得混合物进行能量断裂和雪崩能量测定，结果报道在表1中。
实施例3-6和对比例2-7
如实施例1-2中所述制备混合物，不同之处在于使用表1中报道的化合物(b)。对所得混合物进行能量断裂和雪崩能量测定，结果记录在表1中。
实施例7-13和对比例C8-C10
如实施例1-2中所述制备混合物，区别在于使用加合物(a)的实施例批次B代替批次A，并且使用表1中报道的SiO2基单元化合物代替
使所得混合物经受能量断裂和雪崩能量测定，并且结果报道于表1中。
实施例14-24和对比例C11
如实施例1-2中所述制备混合物，区别在于使用加合物(a)的批次C代替批次A，并且使用表1中报道的SiO2基单元化合物代替
使所得混合物经受能量断裂和雪崩能量测定，并且结果报道于表1中。
表1
Claims (15)
1.一种齐格勒-纳塔催化剂组分前体，其包含以下的机械混合物(a)式MgCl2(R1OH)n的加合物的不同颗粒，其中R是C1-C8烷基，并且n是从0.2至6，具有范围从5至100μm的平均粒度(P50a)，以及基于(a)和(b)的总量，(b)从0.2至5.0wt％的固体化合物的不同颗粒，含有超过50wt％的SiO2单元并且具有使得比例P50b/P50a在0.4至1.5范围内的平均粒度(P50b)。
2.根据权利要求1所述的混合物，其中含有大于50wt％SiO2单元的固体化合物(b)选自二氧化硅、硅酸盐和硅藻土及其混合物。
3.根据权利要求2所述的混合物，其中含有大于50wt％SiO2单元的固体化合物(b)选自二氧化硅。
4.根据权利要求1所述的混合物，其中以(P50a)表示的加合物(a)的平均粒度范围为10至100μm。
5.根据权利要求4所述的混合物，其中以(P50a)表示的加合物(a)的平均粒度范围为15至80μm。
6.根据权利要求1所述的混合物，其中比例P50b/P50a范围为0.60至1.50。
7.根据权利要求6所述的混合物，其中所述P50b/P50a范围为0.75至1.50。
8.根据权利要求1所述的混合物，其中基于(a+b+c)的总和，固体化合物(b)的颗粒的量范围为0.5至5.0％。
9.根据权利要求8所述的混合物，其中基于(a+b+c)的总和，固体化合物(b)的颗粒的量范围为0.75至4.0％。
10.根据权利要求9所述的混合物，其中基于(a+b+c)的总和，固体化合物(b)的颗粒的量范围为1.0至3.0％。
11.根据权利要求1所述的混合物，其中所述固体化合物(b)的粒度范围为2至50μm。
12.根据权利要求11所述的催化剂混合物，其中所述固体化合物(b)的粒度范围为10至40μm。
13.一种用于烯烃聚合的固体催化剂组分，其通过使式Ti(OR2)m-yXy的钛化合物与根据权利要求1的固体混合物反应而获得，其中m是钛的化合价，y是1至m的数，R2是C1-C10烷基。
14.根据权利要求13所述的固体催化剂组分，进一步包含选自酯、醚、胺、硅烷、氨基甲酸酯和酮或其混合物的内部给体。
15.一种用于烯烃CH2＝CHR的(共)聚合的催化剂体系，其中R是氢或具有1-12个碳原子的烃基，所述催化剂体系包含通过使以下物质接触而获得的产物：
(i)根据权利要求13所述的固体催化剂组分；
(ii)烷基铝化合物和，
(iii)任选地外部电子给体化合物。
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| PCT/EP2019/074766 WO2020069847A1 (en) | 2018-10-01 | 2019-09-17 | Precursors and catalyst components for the polymerization of olefins |
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