WO2014004396A1 - Heterocyclic organic compounds as electron donors for polyolefin catalysts - Google Patents
Heterocyclic organic compounds as electron donors for polyolefin catalysts Download PDFInfo
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- WO2014004396A1 WO2014004396A1 PCT/US2013/047391 US2013047391W WO2014004396A1 WO 2014004396 A1 WO2014004396 A1 WO 2014004396A1 US 2013047391 W US2013047391 W US 2013047391W WO 2014004396 A1 WO2014004396 A1 WO 2014004396A1
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- -1 Heterocyclic organic compounds Chemical class 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229920000098 polyolefin Polymers 0.000 title abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 claims abstract description 25
- 239000003426 co-catalyst Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 125000004429 atom Chemical group 0.000 claims description 25
- 125000005842 heteroatom Chemical group 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000003367 polycyclic group Chemical group 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 16
- 229920001155 polypropylene Polymers 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 description 17
- 239000002685 polymerization catalyst Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 7
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 4
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 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 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910010066 TiC14 Inorganic materials 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SNSYYBGUDOYAMB-UHFFFAOYSA-N ethyl 2-(oxolan-2-yl)acetate Chemical compound CCOC(=O)CC1CCCO1 SNSYYBGUDOYAMB-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OFBSTYYRPIFDPM-UHFFFAOYSA-N 2,2-di-2-furylpropane Chemical compound C=1C=COC=1C(C)(C)C1=CC=CO1 OFBSTYYRPIFDPM-UHFFFAOYSA-N 0.000 description 1
- GLBZUEUNJBRBHY-UHFFFAOYSA-N 2-(2-thiophen-2-ylpropan-2-yl)thiophene Chemical compound C=1C=CSC=1C(C)(C)C1=CC=CS1 GLBZUEUNJBRBHY-UHFFFAOYSA-N 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
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-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
- 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
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- PBTPREHATAFBEN-UHFFFAOYSA-N dipyrromethane Chemical compound C=1C=CNC=1CC1=CC=CN1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C08F4/42—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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—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
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
-
- 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
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
Definitions
- This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making such polymerization catalyst systems, and to polymerization processes to produce polyolefms, particularly polypropylene, which does not contain a phthalate derivative.
- Ziegler-Natta catalyst systems for polyolefin polymerization are well known in the art. Commonly, these systems are composed of a solid Ziegler-Natta catalyst component and a co- catalyst component, usually an organoaluminum compound. To increase the activity and sterospecificity of the catalyst system for the polymerization of a-olefins, electron donating compounds have been widely used (1) as an internal electron donor in the solid Ziegler-Natta catalyst component and/or (2) as an external electron donor to be used in conjunction with the solid Ziegler-Natta catalyst component and the co-catalyst component.
- an external electron donor which may or may not be in addition to the use of an internal electron donor.
- Acceptable external electron donors include organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc.
- Preferred external electron donors are organosilicon compounds containing Si-O-C and/or Si-N-C bonds, having silicon as the central atom.
- organosilicon compounds containing Si-O-C and/or Si-N-C bonds, having silicon as the central atom.
- Such compounds are described in U.S. Patent Nos. 4,472,524; 4,473,660; 4,560,671 ; 4,581,342; 4,657,882; 5, 106,807; 5,407,883; 5,684,173; 6,228,961 ; 6,362,124; 6,552,136; 6,689,849; 7,009,015; 7,244,794; 7,619,049; and 7,790,819, which are incorporated by reference herein.
- Common internal electron donor compounds include ethers, ketones, amines, alcohols, phenols, phosphines, and silanes. It is well known in the art that polymerization activity, as well as stereoregularity, molecular weight and molecular weight distribution of the resulting polymer, depend on the molecular structure of the internal electron donor employed. Therefore, in order to improve the polymerization process and the properties of the resulting polymer, there has been an effort and desire to develop various internal electron donors. Examples of such internal electron donor compounds and their use as a component of the catalyst system are described in U.S. Patent Nos.
- U.S. Patent No. 7,491,781 in particular teaches the use of an internal donor in a propylene polymerization catalyst component which does not contain a phthalate derivative.
- the resulted propylene polymerization catalyst has poorer hydrogen response and lower isotacticity than the catalyst containing a phthalate derivative.
- MFR melt flow rate
- This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making the polymerization catalyst systems, and to polymerization processes to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative.
- the present invention relates to a catalyst system for the polymerization or co-polymerization of alpha-olefins comprising a solid Ziegler- Natta type catalyst component, a co-catalyst component, and optionally an external electron donor component.
- the solid Ziegler-Natta type catalyst component comprises at least one heterocyclic organic compound of this invention.
- the heterocyclic organic compounds of the present invention that may be used as electron donors in polymerization catalyst systems are represented by Formula I:
- L is represented by Formula II: [Formula II] or is selected from the groups consisting of -OR 9 , -SR 9 , -OCOR 9 , -COOR 9 , -NH 2 , -NHR 9 , - NR 9 2, and PR 9 2 , wherein R 9 is a linear or branch Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 2 o cycloalkyl, C6-C 2 o aryl, C 7 -C 2 o alkylaryl or C 7 -C 20 arylalkyl group, optionally containing at least one heteroatom selected from the group consisting of B, Si and halogen atoms.
- R 9 is a linear or branch Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 2 o cycloalkyl, C6-C 2 o aryl, C 7 -C 2 o alkylaryl or C 7 -
- a and Al which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P.
- Q and Ql which may be identical or different, is a heteroatom selected from the group consisting of O, N, S, and P.
- R ⁇ R 4 , R 5 , and R 8 which may be identical or different, are each a hydrocarbon-based substituent to Q, A, Qi, and Ai, respectively.
- the subscripts p, q, i, and j, depending on the valence state of Q, A, Qj and Ai, are independently 0 or 1, which one of ordinary skill in the art having the benefit of this disclosure will recognize.
- the length and structure of R 1 , R 4 , R 5 , and R 8 are not generally limited. In preferred embodiments of the present invention, R 1 and R 5 are small groups such as hydrogen, methyl, or ethyl.
- R, R 2 , R 3 , R 6 , and R 7 which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R 2 , R 3 , R 6 , and R 7 , with the proviso that the resultant ring structure is a three to eight-membered ring.
- "Backbone chain length" in this context refers to the atoms that are in the direct linkage between the two atoms Q and A, Qi and Ai, or between the atom A and the group L.
- the associated backbone chain length is one and two atoms, respectively, referring to the carbon atoms that provide the direct linkage between the two atoms.
- the bridging group has the iso- structure, CH 3 CHCH 2 , then the associated backbone chain length is also two atoms.
- the backbone of the bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
- the backbone of the bridging group is selected from the group consisting of aliphatic radicals, with or without unsaturation.
- the bridging group may have one or more C1-C20 substituents (or side chains) extending off the backbone chain.
- the substituents may be branched or linear and may be saturated or unsaturated.
- the substituents may comprise aliphatic, alicyclic, and/or aromatic radicals.
- One or more of carbon atom or hydrogen atom of R 1 , R 4 , R 5 , R 8 , and bridging groups R, R 2 , R 3 , R 6 , and R 7 , including any substituents thereof, may be replaced with a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, with the proviso that O, N, S, and P can only be embedded in the ring structure or in the backbone atoms of R.
- two or more of said R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
- R group when the backbone of R group is a single carbon atom, either A or A] cannot be connected to a nitrogen atom to form a carbon nitrogen double bond.
- the present invention also relates to a composition containing a compound of the heterocyclic organic compound of the aforementioned formula.
- the present invention also relates to a method of polymerizing an alpha-olefin comprising polymerizing the alpha-olefin in the presence of the heterocyclic organic compound of the aforementioned formula.
- This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making such polymerization catalyst systems, and to polymerization processes to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative.
- heterocyclic organic compounds which are useful as electron donors in polymerization catalyst systems for the production of polyolefins, particularly polypropylene, are disclosed.
- These heterocyclic organic compounds may be used as either an internal electron donor or an external electron donor.
- these heterocyclic organic compounds are used as an internal electron donor.
- Polymerization catalyst systems employing the heterocyclic organic compounds of the present invention may have an internal electron donor, an external electron donor, or both an internal electron donor and an external electron donor.
- the heterocyclic organic compounds of the present invention may be used alone as a single constituent as the electron donor component of the catalyst system or may be used in combination with one or more other compounds as an electron donor component of the catalyst system. If more than one compound is used as the electron donor component, one or more of the constituents may be heterocyclic organic compounds of the present invention.
- heterocyclic organic compounds of the present invention that may be used as electron donors in polymerization catalyst systems are represented by Formula I:
- R 9 is a linear or branch Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 6 -C 2 o aryl, C7-C20 alkylaryl or C7-C20 arylalkyl group, optionally containing at least one heteroatom selected from the group consisting of B, Si and halogen atoms.
- a and Al which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P.
- Q and Ql which may be identical or different, is a heteroatom selected from the group consisting of O, N, S and P.
- R 1 , R 4 , R 5 , and R 8 which may be identical or different, are each a hydrocarbon-based substituent to Q, A, Q 1 ⁇ and Ai, respectively.
- the subscripts p, q, i, and j , depending on the valence state of Q, A, Qj, and Aj are independently 0 or 1, which one of ordinary skill in the art having the benefit of this disclosure will recognize.
- the length and structure of R 1 , R 4 , R 5 , and R 8 are not generally limited. In preferred embodiments of the present invention, R 1 and R 5 are small groups such as hydrogen, methyl, or ethyl.
- R, R 2 , R 3 , R 6 , and R 7 which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R 2 , R 3 , R 6 , and R 7 , with the proviso that the resulted ring structure is a three to eight-membered ring.
- "Backbone chain length" in this context refers to the atoms that are in the direct linkage between the two atoms Q and A, Qi and Ai, or between the atom A and the group L.
- the associated backbone chain length is one and two atoms, respectively, referring to the carbon atoms that provide the direct linkage between the two atoms.
- the bridging group has the iso- structure, CH3CHCH 2 , then the associated backbone chain length is also two atoms.
- the backbone of the bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
- the backbone of the bridging group is selected from the group consisting of aliphatic radicals, with or without unsaturation.
- the bridging group may have one or more C 1 -C20 substituents (or side chains) extending off the backbone chain.
- the substituents may be branched or linear and may be saturated or unsaturated.
- the substituents may comprise aliphatic, alicyclic, and/or aromatic radicals.
- One or more of carbon atom or hydrogen atom of R ⁇ R 4 , R 5 , R 8 , and bridging groups R, R 2 , R 3 , R 6 , and R 7 , including any substituents thereof, may be replaced with a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms with the proviso that O, N, S, and P can only be embedded in the ring structure or in the backbone atoms of R.
- two or more of said R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
- heterocyclic organic compounds of the Formula I include, but not are limited to:
- the heterocyclic organic compounds of the present invention may be used as a component in Ziegler-Natta type catalyst systems. Except for the inclusion of the heterocyclic organic compounds of the present invention, the Ziegler-Natta type catalyst systems, and methods for making such catalyst systems, which may be employed in accordance with the various embodiments of the present invention, are not generally limited.
- Typical, and acceptable, Ziegler-Natta type catalyst systems that may be used in accordance with the present invention comprise (a) a solid Ziegler-Natta type catalyst component, and (b) a co-catalyst component, and optionally (c) one or more external electron donors.
- At least one heterocyclic organic compound in accordance with the present invention is used as an electron donor in the Ziegler-Natta type catalyst system.
- these heterocyclic organic compounds may be used as either an internal electron donor or an external electron donor.
- these heterocyclic organic compounds are used as an internal electron donor.
- Preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium compound having at least a Ti-halogen bond and an internal electron donor compound supported on an anhydrous magnesium-dihalide support.
- Such preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium tetrahalide.
- a preferred titanium tetrahalide is TiCl 4 .
- Alkoxy halides may also be used.
- the acceptable additional internal electron donor compounds for the preparation of solid Ziegler-Natta type catalyst component (a) are not generally limited and include, but are not limited to, alkyl, aryl, and cycloalkyl esters of aromatic acids, in particular the alkyl esters of benzoic acid and phthalic acid and their derivatives. Examples of such compounds include ethyl benzoate, n-butyl benzoate, methyl-p-toluate, and methyl-p-methoxybenzoate and diisobutylphthalate.
- Other common internal electron donors, including alkyl or alkyl-aryl ethers, ketones, mono- or polyamines, aldehydes, and P-compounds, such as phosphines and phosphoramides, may also be used.
- Acceptable anhydrous magnesium dihalides forming the support of the solid Ziegler- Natta type catalyst component (a) are the magnesium dihalides in active form that are well known in the art. Such magnesium dihalides may be preactivated, may be activated in situ during the titanation, may be formed in-situ from a magnesium compound, which is capable of forming, magnesium dihalide when treated with a suitable halogen-containing transition metal compound, and then activated.
- Preferred magnesium dihalides are magnesium dichloride and magnesium dibromide.
- the water content of the dihalides is generally less than 1 % by weight.
- the solid Ziegler-Natta type catalyst component (a) may be made by various methods.
- One such method consists of co-grinding the magnesium dihalide and the internal electron donor compound until the product shows a surface area higher than 20 m 2 /g and thereafter reacting the ground product with the Ti compound.
- Other methods of preparing solid Ziegler-Natta type catalyst component (a) are disclosed in U.S. Patent Nos. 4,220,554; 4,294,721 ; 4,315,835; 4,330,649; 4,439,540; 4,816,433; and 4,978,648. These methods are incorporated herein by reference.
- the molar ratio between the magnesium dihalide and the halogenated titanium compound is between 1 and 500 and the molar ratio between said halogenated titanium compound and the internal electron donor is between 0.1 and 50.
- Preferred co-catalyst component (b) include aluminum alkyl compounds.
- Acceptable aluminum alkyl compounds include aluminum trialkyls, such as aluminum triethyl, aluminum triisobutyl, and aluminum triisopropyl.
- Other acceptable aluminum alkyl compounds include aluminum-dialkyl hydrides, such as aluminum-diethyl hydrides.
- Other acceptable co-catalyst component (b) include compounds containing two or more aluminum atoms linked to each other through hetero-atoms, such as:
- Acceptable external electron donor component (c) is organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc.
- Preferred component (c) is organosilicon compounds containing Si-O-C and/or Si-N-C bonds.
- organosilicon compounds are trimethylmethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, isobutyltriethoxysilane, vinyltrimethoxysilane, dicyclohexyldimethoxysilane, 3-tert-Butyl-2- isobutyl-2methoxy-[l,3,2]oxazasilolidine, 3-tert-Butyl-2-cyclopentyl-2-methoxy- [l ,3,2]oxazasilolidine, 2-Bicyclo[2.2.1]hept-5-en-2-yl-3-tert-butyl-2-methoxy- [l ,3,2]oxazasilolidine, 3-tert-Butyl-2,2-diethoxy-[l,3,2]oxazasil
- the olefin polymerization processes that may be used in accordance with the present invention are not generally limited.
- the catalyst components (a), (b) and (c), when employed, may be added to the polymerization reactor simultaneously or sequentially. It is preferred to mix components (b) and (c) first and then contact the resultant mixture with component (a) prior to the polymerization.
- the olefin monomer may be added prior to, with, or after the addition of the Ziegler- Natta type catalyst system to the polymerization reactor. It is preferred to add the olefin monomer after the addition of the Ziegler-Natta type catalyst system.
- the molecular weight of the polymers may be controlled in a known manner, preferably by using hydrogen.
- molecular weight may be suitably controlled with hydrogen when the polymerization is carried out at relatively low temperatures, e.g., from about 30 °C to about 105 °C. This control of molecular weight may be evidenced by a measurable positive change of the Melt Flow Rate.
- the polymerization reactions may be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which may be done either by batch or continuously.
- the polyolefin may be directly obtained from gas phase process, or obtained by isolation and recovery of solvent from the slurry process, according to conventionally known methods.
- polymerization conditions for production of polyolefins by the method of this invention such as the polymerization temperature, polymerization time, polymerization pressure, monomer concentration, etc.
- the polymerization temperature is generally from 40-90 °C and the polymerization pressure is generally 1 atmosphere or higher.
- the Ziegler-Natta type catalyst systems of the present invention may be precontacted with small quantities of olefin monomer, well known in the art as prepolymerization, in a hydrocarbon solvent at a temperature of 60 °C or lower for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst. If such a prepolymerization is done in liquid or gaseous monomer, the quantity of resultant polymer is generally up to 1000 times the catalyst weight.
- the Ziegler-Natta type catalyst systems of the present invention are useful in the polymerization of olefins, including but not limited to homopolymerization and copolymerization of alpha olefins.
- Ziegler-Natta type catalyst systems of the present invention may be employed in processes in which ethylene is polymerized, it is more desirable to employ the Ziegler-Natta type catalyst systems of the present invention in processes in which polypropylene or higher olefins are polymerized. Processes involving the homopolymerization or copolymerization of propylene are preferred.
- Xylene soluble components 5.0g of the polymer was added to 500ml of xylenes (bp: 137 ⁇ 140°C) and dissolved while maintaining the mixture at the boiling point over one hour. The mixture was cooled down to 5°C within 20 minutes in an ice-water bath. Thereafter the ice- water bath was replaced with a 20°C water bath and the mixture was equilibrated at 20°C for 30 minutes. The soluble matters were separated from insoluble matters by filtration. The soluble components were dried with heating, and the polymer thus obtained was determined as xylene soluble components (wt%).
- Molecular Weight (Mn and Mw) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of polymers are obtained by gel permeation chromatography on Waters GPCV 2000 system using Polymer Labs Plgel 10 um MIXED-B LS 300x7.5mm columns and 1,2,4-trichlorobenzene (TCB) as the mobile phase.
- the mobile phase is set at 1.0 ml/min, and temperature is set at 145 ° C. Polymer samples are heated at 150 C for two hours.
- the injection volume is 299 microliters. External standard calibration of polystyrene narrow standards is used to calculate the molecular weight.
- Diisopropyldimethoxysilane (P-donor) was purchased from Gelest, Inc. of Morrisville, PA, USA.
- a 250ml flask equipped with a stirrer and thoroughly purged with nitrogen was charged with 10 g of magnesium ethoxide and 100 ml of anhydrous toluene to form a suspension.
- To the suspension was injected 25 ml of TiC14 and was then heated up to a temperature of 90°C.
- 1.8g of 2,2-di(2-tetrahydrofuryl)propane was added thereto, followed by heating up to 110°C with agitation at that temperature for 2 hours.
- the product was washed twice with 100 ml of anhydrous toluene at 90°C, and 100 ml of fresh anhydrous toluene and 25 ml of TiC14 were added thereto for reacting with agitation at 110°C for two additional hours.
- the product was washed 8 times with 200 ml of anhydrous n-heptane at 90 °C and was dried under a reduced pressure to obtain a solid composition.
- a bench scale 2-liter reactor was used. The reactor was first preheated to at least 100 °C with a nitrogen purge to remove residual moisture and oxygen. The reactor was thereafter cooled to 50 °C. [0057] Under nitrogen, 1 liter dry heptane was introduced into the reactor. When reactor temperature was about 50°C, 4.3ml triethylaluminum (0.58M, in hexanes), 0.40ml cyclohexyl(dimethoxy)methylsilane (C-donor) (0.5 M in heptane), and then 30 mg of the solid catalyst component prepared above were added to the reactor. The pressure of the reactor was raised to 28.5 psig at 50°C by introducing nitrogen. 8 psi hydrogen in a 150cc vessel was flushed into the reactor with propylene.
- the reactor temperature was then raised to 70 °C.
- the total reactor pressure was raised to and controlled at 90 psig by continually introducing propylene into the reactor and the polymerization was allowed to proceed for 1 hour. After polymerization, the reactor was vented to reduce the pressure to 0 psig and the reactor temperature was cooled to 50 °C.
- Example 4 The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 1.7 g of 2,2'-dipyridylamine was used in place of 2,2-di(2- tetrahydrofuryl)propane.
- the present inventive catalyst systems can be used to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative. Furthermore, the present inventive catalyst systems also offer capabilities to produce polypropylene with acceptable isotacticity and high MFR.
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Abstract
Heterocyclic organic compounds are used as electron donors in conjunction with solid Ziegler- Natta type catalyst in processes in which polyolefins such as polypropylene are produced. The electron donors may be used in the preparation of solid catalyst system, thus serving as "internal electron donors", or they may be employed during or prior to polymerization with the co-catalyst as "external electron donors".
Description
HETEROCYCLIC ORGANIC COMPOUNDS AS ELECTRON DONORS FOR
POLYOLEFIN CATALYSTS
BACKGROUND
Field of the Invention
[oooi] This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making such polymerization catalyst systems, and to polymerization processes to produce polyolefms, particularly polypropylene, which does not contain a phthalate derivative.
Description of the Related Art
[0002] Ziegler-Natta catalyst systems for polyolefin polymerization are well known in the art. Commonly, these systems are composed of a solid Ziegler-Natta catalyst component and a co- catalyst component, usually an organoaluminum compound. To increase the activity and sterospecificity of the catalyst system for the polymerization of a-olefins, electron donating compounds have been widely used (1) as an internal electron donor in the solid Ziegler-Natta catalyst component and/or (2) as an external electron donor to be used in conjunction with the solid Ziegler-Natta catalyst component and the co-catalyst component.
[0003] In the utilization of Ziegler-Natta type catalysts for polymerizations involving propylene or other olefins for which isotacticity is a possibility, it may be desirable to utilize an external electron donor, which may or may not be in addition to the use of an internal electron donor. Acceptable external electron donors include organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc. Preferred external electron donors are organosilicon compounds containing Si-O-C and/or Si-N-C bonds, having silicon as the central atom. Such compounds are described in U.S. Patent Nos. 4,472,524; 4,473,660; 4,560,671 ; 4,581,342; 4,657,882; 5, 106,807; 5,407,883; 5,684,173; 6,228,961 ; 6,362,124; 6,552,136; 6,689,849; 7,009,015; 7,244,794; 7,619,049; and 7,790,819, which are incorporated by reference herein.
[0004] Common internal electron donor compounds, incorporated in the solid Ziegler-Natta catalyst component during preparation of such component, known in the prior art, include ethers, ketones, amines, alcohols, phenols, phosphines, and silanes. It is well known in the art that
polymerization activity, as well as stereoregularity, molecular weight and molecular weight distribution of the resulting polymer, depend on the molecular structure of the internal electron donor employed. Therefore, in order to improve the polymerization process and the properties of the resulting polymer, there has been an effort and desire to develop various internal electron donors. Examples of such internal electron donor compounds and their use as a component of the catalyst system are described in U.S. Patent Nos. 4, 107,414; 4, 186,107; 4,226,963; 4,347, 160; 4,382,019; 4,435,550; 4,465,782; 4,522,930; 4,530,912; 4,532,313; 4,560,671 ; 4,657,882; 5,208,302; 5,902,765; 5,948,872; 6,121,483; 6,436,864, 6,770,586; 7,022,640; 7,049,377; 7,202,314; 7,208,435; 7,223,712; 7,351,778; 7,371,802; 7,491,781 ; 7,544,748; 7,674,741 ; 7,674,943; 7,888,437; 7,888,438; 7,964,678; 8,003,558; and 8,003,559, which are incorporated by reference herein.
[0005] Most of commercial propylene polymerization catalysts currently used employ alkyl phthalate esters as an internal electron donor. However, certain environmental issues have been recently raised concerning the continued use of phthalate derivatives in human contact applications. As a result, the employment of a phthalate-free propylene polymerization catalyst is now necessary for the production of phthalate-free polypropylene to remedy these issues.
[0006] U.S. Patent No. 7,491,781 in particular teaches the use of an internal donor in a propylene polymerization catalyst component which does not contain a phthalate derivative. However the resulted propylene polymerization catalyst has poorer hydrogen response and lower isotacticity than the catalyst containing a phthalate derivative.
[0007] The polypropylene market also has an increasing demand in high melt flow rate (MFR) grade polypropylene to reduce cycle time and to achieve down-gauging while maintaining acceptable impact strength and stiffness. High MFR polypropylene is commonly achieved by adding peroxide to the polymer, but such obtained polypropylene usually has odor issues and the physical properties are sacrificed somehow. As such, production of reactor-grade high MFR polypropylene becomes necessary to avoid these issues.
[0008] There is a continuous need for developing catalyst systems that can be used to produce polyolefms, particularly polypropylene, which does not contain a phthalate derivative. Furthermore, the desirable catalyst systems should also offer capabilities to produce polypropylene with acceptable isotacticity and high MFR.
SUMMARY OF THE INVENTION
[0009] This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making the polymerization catalyst systems, and to polymerization processes to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative.
[ooio] In accordance with various aspects thereof, the present invention relates to a catalyst system for the polymerization or co-polymerization of alpha-olefins comprising a solid Ziegler- Natta type catalyst component, a co-catalyst component, and optionally an external electron donor component. The solid Ziegler-Natta type catalyst component comprises at least one heterocyclic organic compound of this invention. The heterocyclic organic compounds of the present invention that may be used as electron donors in polymerization catalyst systems are represented by Formula I:
L [Formula I]
wherein L is represented by Formula II:
[Formula II] or is selected from the groups consisting of -OR9, -SR9, -OCOR9, -COOR9, -NH2, -NHR9, - NR92, and PR9 2, wherein R9 is a linear or branch Ci-C20 alkyl, C2-C20 alkenyl, C3-C2o cycloalkyl, C6-C2o aryl, C7-C2o alkylaryl or C7-C20 arylalkyl group, optionally containing at least one heteroatom selected from the group consisting of B, Si and halogen atoms. A and Al, which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of
Si, N, B, and P. Q and Ql, which may be identical or different, is a heteroatom selected from the group consisting of O, N, S, and P.
[0011] R\ R4, R5, and R8, which may be identical or different, are each a hydrocarbon-based substituent to Q, A, Qi, and Ai, respectively. The subscripts p, q, i, and j, depending on the valence state of Q, A, Qj and Ai, are independently 0 or 1, which one of ordinary skill in the art having the benefit of this disclosure will recognize. The length and structure of R1, R4, R5, and R8 are not generally limited. In preferred embodiments of the present invention, R1 and R5 are small groups such as hydrogen, methyl, or ethyl.
[0012] Wherein R, R2, R3, R6, and R7, which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R2, R3, R6, and R7, with the proviso that the resultant ring structure is a three to eight-membered ring. "Backbone chain length" in this context refers to the atoms that are in the direct linkage between the two atoms Q and A, Qi and Ai, or between the atom A and the group L. For example, if -CH2- or -CH2-CH2- is the bridging group, then the associated backbone chain length is one and two atoms, respectively, referring to the carbon atoms that provide the direct linkage between the two atoms. Similarly, if the bridging group has the iso- structure, CH3CHCH2, then the associated backbone chain length is also two atoms.
[0013] The backbone of the bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals. Preferably, the backbone of the bridging group is selected from the group consisting of aliphatic radicals, with or without unsaturation. The bridging group may have one or more C1-C20 substituents (or side chains) extending off the backbone chain. The substituents may be branched or linear and may be saturated or unsaturated. Similarly, the substituents may comprise aliphatic, alicyclic, and/or aromatic radicals.
[0014] One or more of carbon atom or hydrogen atom of R1, R4, R5, R8, and bridging groups R, R2, R3, R6, and R7, including any substituents thereof, may be replaced with a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, with the proviso that O, N, S, and P can only be embedded in the ring structure or in the backbone atoms of R.
[0015] In various embodiments of the present invention, two or more of said R, R1, R2, R3, R4, R5, R6, R7, or R8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
[0016] In various embodiments of the present invention, when the backbone of R group is a single carbon atom, either A or A] cannot be connected to a nitrogen atom to form a carbon nitrogen double bond.
[0017] In accordance with various aspects thereof, the present invention also relates to a composition containing a compound of the heterocyclic organic compound of the aforementioned formula. In accordance with various aspects thereof, the present invention also relates to a method of polymerizing an alpha-olefin comprising polymerizing the alpha-olefin in the presence of the heterocyclic organic compound of the aforementioned formula.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0018] This invention relates to heterocyclic organic compounds that may be employed as an electron donor for polymerization catalyst systems, to polymerization catalyst systems employing the heterocyclic organic compounds as an electron donor, to methods of making such polymerization catalyst systems, and to polymerization processes to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative.
[0019] In accordance with various embodiments, a class of heterocyclic organic compounds, which are useful as electron donors in polymerization catalyst systems for the production of polyolefins, particularly polypropylene, are disclosed. These heterocyclic organic compounds may be used as either an internal electron donor or an external electron donor. Preferably, these heterocyclic organic compounds are used as an internal electron donor. Polymerization catalyst systems employing the heterocyclic organic compounds of the present invention may have an internal electron donor, an external electron donor, or both an internal electron donor and an external electron donor.
[0020] The heterocyclic organic compounds of the present invention may be used alone as a single constituent as the electron donor component of the catalyst system or may be used in combination with one or more other compounds as an electron donor component of the catalyst system. If more than one compound is used as the electron donor component, one or more of the constituents may be heterocyclic organic compounds of the present invention.
[0021] The heterocyclic organic compounds of the present invention that may be used as electron donors in polymerization catalyst systems are represented by Formula I:
[Formula II]
or is selected from the groups consisting of -OR9, -SR9, -OCOR9, -COOR9, -NH2, - NHR9, - R92, and PR9 2, wherein R9 is a linear or branch Ci-C20 alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C6-C2o aryl, C7-C20 alkylaryl or C7-C20 arylalkyl group, optionally containing at least one heteroatom selected from the group consisting of B, Si and halogen atoms. A and Al, which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P. Q and Ql, which may be identical or different, is a heteroatom selected from the group consisting of O, N, S and P.
[0022] R1, R4, R5, and R8, which may be identical or different, are each a hydrocarbon-based substituent to Q, A, Q1 } and Ai, respectively. The subscripts p, q, i, and j , depending on the valence state of Q, A, Qj, and Aj are independently 0 or 1, which one of ordinary skill in the art having the benefit of this disclosure will recognize. The length and structure of R1, R4, R5, and R8 are not generally limited. In preferred embodiments of the present invention, R1 and R5 are small groups such as hydrogen, methyl, or ethyl.
[0023] R, R2, R3, R6, and R7, which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R2, R3, R6, and R7, with the proviso that the resulted ring structure is a three to eight-membered ring. "Backbone chain length" in this context refers to the atoms that are in the direct linkage between the two atoms Q and A, Qi and Ai, or between the atom A and the group L. For example, if -CH2- or ~CH2-CH2-
is the bridging group then the associated backbone chain length is one and two atoms, respectively, referring to the carbon atoms that provide the direct linkage between the two atoms. Similarly, if the bridging group has the iso- structure, CH3CHCH2, then the associated backbone chain length is also two atoms.
[0024] The backbone of the bridging group is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals. Preferably, the backbone of the bridging group is selected from the group consisting of aliphatic radicals, with or without unsaturation. The bridging group may have one or more C1-C20 substituents (or side chains) extending off the backbone chain. The substituents may be branched or linear and may be saturated or unsaturated. Similarly, the substituents may comprise aliphatic, alicyclic, and/or aromatic radicals.
[002S] One or more of carbon atom or hydrogen atom of R\ R4, R5, R8, and bridging groups R, R2, R3, R6, and R7, including any substituents thereof, may be replaced with a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms with the proviso that O, N, S, and P can only be embedded in the ring structure or in the backbone atoms of R.
[0026] In various embodiments of the present invention, two or more of said R, R1, R2, R3, R4, R5, R6, R7, or R8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
[0027] In various embodiments of the present invention, when the backbone of R group is a single carbon atom, either A or A] cannot be connected to a nitrogen atom to form a carbon nitrogen double bond.
[0028] Examples of suitable heterocyclic organic compounds of the Formula I include, but not are limited to:
[0029] The heterocyclic organic compounds of the present invention may be used as a component in Ziegler-Natta type catalyst systems. Except for the inclusion of the heterocyclic organic compounds of the present invention, the Ziegler-Natta type catalyst systems, and methods for making such catalyst systems, which may be employed in accordance with the various embodiments of the present invention, are not generally limited. Typical, and acceptable, Ziegler-Natta type catalyst systems that may be used in accordance with the present invention comprise (a) a solid Ziegler-Natta type catalyst component, and (b) a co-catalyst component, and optionally (c) one or more external electron donors. In accordance with the
various embodiments of the present invention, at least one heterocyclic organic compound in accordance with the present invention is used as an electron donor in the Ziegler-Natta type catalyst system. As previously disclosed herein, these heterocyclic organic compounds may be used as either an internal electron donor or an external electron donor. Preferably, these heterocyclic organic compounds are used as an internal electron donor.
[0030] Preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium compound having at least a Ti-halogen bond and an internal electron donor compound supported on an anhydrous magnesium-dihalide support. Such preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium tetrahalide. A preferred titanium tetrahalide is TiCl4. Alkoxy halides may also be used.
[0031] If the heterocyclic organic compounds of the present invention are used in combination with one or more other compounds as an internal electron donor component of the catalyst system, the acceptable additional internal electron donor compounds for the preparation of solid Ziegler-Natta type catalyst component (a) are not generally limited and include, but are not limited to, alkyl, aryl, and cycloalkyl esters of aromatic acids, in particular the alkyl esters of benzoic acid and phthalic acid and their derivatives. Examples of such compounds include ethyl benzoate, n-butyl benzoate, methyl-p-toluate, and methyl-p-methoxybenzoate and diisobutylphthalate. Other common internal electron donors, including alkyl or alkyl-aryl ethers, ketones, mono- or polyamines, aldehydes, and P-compounds, such as phosphines and phosphoramides, may also be used.
[0032] Acceptable anhydrous magnesium dihalides forming the support of the solid Ziegler- Natta type catalyst component (a) are the magnesium dihalides in active form that are well known in the art. Such magnesium dihalides may be preactivated, may be activated in situ during the titanation, may be formed in-situ from a magnesium compound, which is capable of forming, magnesium dihalide when treated with a suitable halogen-containing transition metal compound, and then activated. Preferred magnesium dihalides are magnesium dichloride and magnesium dibromide. The water content of the dihalides is generally less than 1 % by weight.
[0033] The solid Ziegler-Natta type catalyst component (a) may be made by various methods. One such method consists of co-grinding the magnesium dihalide and the internal electron donor
compound until the product shows a surface area higher than 20 m2/g and thereafter reacting the ground product with the Ti compound. Other methods of preparing solid Ziegler-Natta type catalyst component (a) are disclosed in U.S. Patent Nos. 4,220,554; 4,294,721 ; 4,315,835; 4,330,649; 4,439,540; 4,816,433; and 4,978,648. These methods are incorporated herein by reference.
[0034] In a typical solid Ziegler-Natta type catalyst component (a), the molar ratio between the magnesium dihalide and the halogenated titanium compound is between 1 and 500 and the molar ratio between said halogenated titanium compound and the internal electron donor is between 0.1 and 50.
[0035] Preferred co-catalyst component (b) include aluminum alkyl compounds. Acceptable aluminum alkyl compounds include aluminum trialkyls, such as aluminum triethyl, aluminum triisobutyl, and aluminum triisopropyl. Other acceptable aluminum alkyl compounds include aluminum-dialkyl hydrides, such as aluminum-diethyl hydrides. Other acceptable co-catalyst component (b) include compounds containing two or more aluminum atoms linked to each other through hetero-atoms, such as:
(C2H5)2Al-0-Al(C2H5)2
(C2H5)2A1-N(C6H5)-A1(C2H5)2; and
(C2H5)2Al-0-S02-0-Al(C2H5)2.
[0036] Acceptable external electron donor component (c) is organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc. Preferred component (c) is organosilicon compounds containing Si-O-C and/or Si-N-C bonds. Special examples of such organosilicon compounds are trimethylmethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, isobutyltriethoxysilane, vinyltrimethoxysilane, dicyclohexyldimethoxysilane, 3-tert-Butyl-2- isobutyl-2methoxy-[l,3,2]oxazasilolidine, 3-tert-Butyl-2-cyclopentyl-2-methoxy- [l ,3,2]oxazasilolidine, 2-Bicyclo[2.2.1]hept-5-en-2-yl-3-tert-butyl-2-methoxy- [l ,3,2]oxazasilolidine, 3-tert-Butyl-2,2-diethoxy-[l,3,2]oxazasilolidine, 4,9-Di-tert-butyl-l,6-
dioxa-4,9-diaza-5-sila-spiro[4.4]nonane, bis(perhydroisoquinolino)dimethoxysilane, etc. Mixtures of organic electron donors may also be used. Finally, the heterocyclic organic compounds of the present invention may also be employed as an external electronic donor.
[0037] The olefin polymerization processes that may be used in accordance with the present invention are not generally limited. For example, the catalyst components (a), (b) and (c), when employed, may be added to the polymerization reactor simultaneously or sequentially. It is preferred to mix components (b) and (c) first and then contact the resultant mixture with component (a) prior to the polymerization.
[0038] The olefin monomer may be added prior to, with, or after the addition of the Ziegler- Natta type catalyst system to the polymerization reactor. It is preferred to add the olefin monomer after the addition of the Ziegler-Natta type catalyst system.
[0039] The molecular weight of the polymers may be controlled in a known manner, preferably by using hydrogen. With the catalysts produced according to the present invention, molecular weight may be suitably controlled with hydrogen when the polymerization is carried out at relatively low temperatures, e.g., from about 30 °C to about 105 °C. This control of molecular weight may be evidenced by a measurable positive change of the Melt Flow Rate.
[0040] The polymerization reactions may be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which may be done either by batch or continuously. The polyolefin may be directly obtained from gas phase process, or obtained by isolation and recovery of solvent from the slurry process, according to conventionally known methods.
[0041] There are no particular restrictions on the polymerization conditions for production of polyolefins by the method of this invention, such as the polymerization temperature, polymerization time, polymerization pressure, monomer concentration, etc. The polymerization temperature is generally from 40-90 °C and the polymerization pressure is generally 1 atmosphere or higher.
[0042] The Ziegler-Natta type catalyst systems of the present invention may be precontacted with small quantities of olefin monomer, well known in the art as prepolymerization, in a hydrocarbon solvent at a temperature of 60 °C or lower for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst. If such a prepolymerization is done in
liquid or gaseous monomer, the quantity of resultant polymer is generally up to 1000 times the catalyst weight.
[0043] The Ziegler-Natta type catalyst systems of the present invention are useful in the polymerization of olefins, including but not limited to homopolymerization and copolymerization of alpha olefins. Suitable a-olefins that may be used in a polymerization process in accordance with the present invention include olefins of the general formula CH2=CHR, where R is H or Cj.io straight or branched alkyl, such as ethylene, propylene, butene- 1, pentene-1, 4-methylpentene-l and octene-1. While the Ziegler-Natta type catalyst systems of the present invention may be employed in processes in which ethylene is polymerized, it is more desirable to employ the Ziegler-Natta type catalyst systems of the present invention in processes in which polypropylene or higher olefins are polymerized. Processes involving the homopolymerization or copolymerization of propylene are preferred.
EXAMPLES
[0044] In order to provide a better understanding of the foregoing discussion, the following non- limiting examples are offered. Although the examples may be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect.The activity values (AC) in TABLE 1 are based upon grams of polymer produced per gram of solid catalyst component used.
[0045] The following analytical methods are used to characterize the polymer.
[00 6] Xylene soluble components (XS): 5.0g of the polymer was added to 500ml of xylenes (bp: 137~140°C) and dissolved while maintaining the mixture at the boiling point over one hour. The mixture was cooled down to 5°C within 20 minutes in an ice-water bath. Thereafter the ice- water bath was replaced with a 20°C water bath and the mixture was equilibrated at 20°C for 30 minutes. The soluble matters were separated from insoluble matters by filtration. The soluble components were dried with heating, and the polymer thus obtained was determined as xylene soluble components (wt%).
[0047] Melt Flow Rate: ASTM D-1238, determined at 230 °C, under a load of 2.16 kg.
[0048] Molecular Weight (Mn and Mw): The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of polymers are obtained by gel permeation chromatography on Waters GPCV 2000 system using Polymer Labs
Plgel 10 um MIXED-B LS 300x7.5mm columns and 1,2,4-trichlorobenzene (TCB) as the mobile phase. The mobile phase is set at 1.0 ml/min, and temperature is set at 145°C. Polymer samples are heated at 150 C for two hours. The injection volume is 299 microliters. External standard calibration of polystyrene narrow standards is used to calculate the molecular weight.
[0049] Magnesium ethoxide (98%), anhydrous toluene (99.8%), TiCl4 (99.9%), anhydrous n- heptane (99%), 2,2-dipyridylamine (99%), diisobutyl phthalate (99%), cyclohexyl(dimethoxy)methylsilane (C-donor) (>99%) and triethylaluminum (93%) were all purchased from Sigma- Aldrich Co. of Milwaukee, WI, USA.
[0050] 2,2'-Di(2-tetrahydrofuryl)propane [>96%(GC)], 2,2'-di(2-furyl)propane [>98.8% (GC)] and 2,2'-dipyrrolymethane [>97%(GQ] and ethyl Tetrahydrofuran-2-acetate [>98.0% (GC)] were purchased from TCI America.
[0051] Diisopropyldimethoxysilane (P-donor) was purchased from Gelest, Inc. of Morrisville, PA, USA.
[0052] Unless otherwise indicated, all reactions were conducted under an inert atmosphere.
Example 1
[0053] (A) The preparation of a solid catalyst component:
[0054] A 250ml flask equipped with a stirrer and thoroughly purged with nitrogen was charged with 10 g of magnesium ethoxide and 100 ml of anhydrous toluene to form a suspension. To the suspension was injected 25 ml of TiC14 and was then heated up to a temperature of 90°C. 1.8g of 2,2-di(2-tetrahydrofuryl)propane was added thereto, followed by heating up to 110°C with agitation at that temperature for 2 hours. After the completion of the reaction, the product was washed twice with 100 ml of anhydrous toluene at 90°C, and 100 ml of fresh anhydrous toluene and 25 ml of TiC14 were added thereto for reacting with agitation at 110°C for two additional hours. After the completion of the reaction, the product was washed 8 times with 200 ml of anhydrous n-heptane at 90 °C and was dried under a reduced pressure to obtain a solid composition.
[0055] (B) Polymerization:
[0056] A bench scale 2-liter reactor was used. The reactor was first preheated to at least 100 °C with a nitrogen purge to remove residual moisture and oxygen. The reactor was thereafter cooled to 50 °C.
[0057] Under nitrogen, 1 liter dry heptane was introduced into the reactor. When reactor temperature was about 50°C, 4.3ml triethylaluminum (0.58M, in hexanes), 0.40ml cyclohexyl(dimethoxy)methylsilane (C-donor) (0.5 M in heptane), and then 30 mg of the solid catalyst component prepared above were added to the reactor. The pressure of the reactor was raised to 28.5 psig at 50°C by introducing nitrogen. 8 psi hydrogen in a 150cc vessel was flushed into the reactor with propylene.
[0058] The reactor temperature was then raised to 70 °C. The total reactor pressure was raised to and controlled at 90 psig by continually introducing propylene into the reactor and the polymerization was allowed to proceed for 1 hour. After polymerization, the reactor was vented to reduce the pressure to 0 psig and the reactor temperature was cooled to 50 °C.
[0059] The reactor was then opened. 500 ml methanol was added to the reactor and the resulting mixture was stirred for 5 minutes then filtered to obtain the polymer product. The obtained polymer was vacuum dried at 80°C for 6 hours. The polymer was evaluated for melt flow rate (MFR), Xylene soluble (%XS), and molecular weight distribution (Mw/Mn). The activity of catalyst (AC) was also measured. The results are shown in TABLE 1.
Example 2
[0060] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 0.85g of 2,2-di(2-furyl)propane was used in place of 2,2-di(2- tetrahydrofuryl)propane.
[0061] Propylene polymerization was carried out in the same manner as described in Example 1. The results are shown in TABLE 1.
Example 3
[0062] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 1.03g of 2,2'-dipyrrolylmethane was used in place of 2,2-di(2- tetrahydrofuryl)propane.
[0063] Propylene polymerization was carried out in the same manner as described in Example 1 except that 8.6ml triethylaluminum (0.58M), 0.80ml cyclohexyl(dimethoxy)methylsilane (C- donor) (0.5 M in heptane), and then 60 mg of the solid catalyst component were added to the reactor instead. The results are shown in TABLE 1.
Example 4
[0064] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 1.7 g of 2,2'-dipyridylamine was used in place of 2,2-di(2- tetrahydrofuryl)propane.
[0065] Propylene polymerization was carried out in the same manner as described in Example 1. The results are shown in TABLE 1.
Example 5
[0066] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that magnesium ethoxide (6.0g) and 1.38g of 2,2-di(2-thiophenyl)propane [>98.0% (GC), prepared according to the procedure described in Journal of the American Chemical Society 1951, 73, 1377.] were used in place of lOg magnesium ethoxide and 1.8g of 2,2-di(2-tetrahydrofuryl)propane.
[0067] Propylene polymerization was carried out in the same manner as described in Example 1. The results are shown in TABLE 1.
Example 6
[0068] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 2.0g of ethyl tetrahydrofuran-2-acetate was used in place of 2,2-di(2- tetrahydrofuryl)propane.
[0069] Propylene polymerization was carried out in the same manner as described in Example 1 except that 0.4ml diisopropyldimethoxysilane (P-donor) (0.5 M in Heptane) was used in place of cyclohexyl(dimethoxy)methylsilane (C-donor). The results are shown in TABLE 1.
Comparative Example 1
[0070] The preparation of a solid catalyst component was carried out under the same conditions as Example 1 except that 2.7ml of diisobutyl phthalate was used in place of 2,2-di(2- tetrahydrofuryl)propane.
[0071] Propylene polymerization was carried out in the same manner as described in Example 1. The results are shown in TABLE 1.
Comparative Example 2
[0072] The solid catalyst component prepared in Comparative Example 1 was used here for the propylene polymerization which was carried out in the same manner as described in Example 1
except that 0.4ml diisopropyldimethoxysilane (P-donor) (0.5 M in Heptane) was used in place of cyclohexyl(dimethoxy)methylsilane (C-donor). The results are shown in TABLE 1.
TABLE 1
[0073] As shown from the above results, the present inventive catalyst systems can be used to produce polyolefins, particularly polypropylene, which does not contain a phthalate derivative. Furthermore, the present inventive catalyst systems also offer capabilities to produce polypropylene with acceptable isotacticity and high MFR.
[0074] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. Whenever a numerical range
with a lower limit and an upper limit is disclosed, any number falling within the range is specifically disclosed. Moreover, the indefinite articles "a" or "an", as used in the claims, are defined herein to mean one or more than one of the element that it introduces.
Claims
1. A solid catalyst component for the polymerization or co-polymerization of alpha-olefins comprising titanium, magnesium, halogen and at least one internal electron donor selected from heterocyclic organic compounds of:
wherein L is re resented by:
wherein R9 is selected from the group consisting of a linear or branch Ci-C2o alkyl, C2-C2o alkenyl, C3-C2o cycloalkyl, C6-C2o aryl, C7-C20 alkylaryl, and C7-C2o arylalkyl;
wherein A and Al, which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P;
wherein Q and Ql, which may be identical or different, is a heteroatom selected from the group consisting of O, N, S, and P;
4 5 8
wherein R1, R , R , and R , which may be identical or different, are aliphatic, alicyclic or aromatic groups;
wherein the subscripts p, q, i, and j are independently selected from 0 or 1 ;
wherein the bonds directly connected to Q, A, Qi, and Als are independently a single bond or a double bond;
wherein R, R2, R3, R6, and R7, which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R2, R3, R6, and R7, wherein the resultant ring structure is a three to eight-membered ring.
2. The solid catalyst component of claim 1 , wherein R9 contains at least one heteroatom selected from the group consisting of B, Si, and halogen atoms.
3. The solid catalyst component of claim 1 , wherein the backbone of the bridging groups is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
4. The solid catalyst component of claim 1, wherein either A or Ai cannot be connected to a nitrogen atom to form a carbon nitrogen double bond when the backbone of R group is a single carbon atom.
5. The solid catalyst component of claim 1, wherein R1 and R5 is selected from the group consisting of hydrogen, methyl, and ethyl.
6. The solid catalyst component of claim 1, wherein R, R2, R3, R6, and R7 independently comprise Ci-C2o linear and/or branched substituents.
7. The solid catalyst component of claim 1, wherein two or more of said R, R1, R2, R3, R4, R5, R6, R7, and R8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
8. The solid catalyst component of claim 1, wherein at least one of a carbon atom or hydrogen atom of R may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the backbone of the bridging groups.
9. The solid catalyst component of claim 1, wherein at least one of a carbon atom or hydrogen atom of R1, R2, R3, R4, R5, R6 R7, and R8 may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the ring structure .
10. A catalyst system for the polymerization or co-polymerization of alpha-olefins comprising:
(1) a solid catalyst component for the polymerization or co-polymerization of alpha- olefin comprising titanium, magnesium, halogen and at least one internal electron donor selected from heterocyclic organic compounds of:
or is selected from the group consisting of -OR9, -SR9, -OCOR9, -COOR9, -NH2, -NHR9, -NR92, and PR9 2 :
wherein R9 is selected from the group consisting of a linear or branch Ci-C2o alkyl, C2-C20 alkenyl, C3-C2o cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl;
wherein A and Al, which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P;
wherein Q and Ql, which may be identical or different, is a heteroatom selected from the group consisting of O, N, S, and P;
wherein R1, R4, R5, and R8, which may be identical or different, are aliphatic, alicyclic or aromatic groups;
wherein the subscripts p, q, i, and j are independently selected from 0 or 1 ;
wherein the bonds directly connected to Q, A, Ql s and Al s are independently a single bond or a double bond;
wherein R, R2, R3, R6, and R7, which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R2, R3, R6, and R7, wherein the resultant ring structure is a three to eight-membered ring;
(2) a co-catalyst component.
1 1. The catalyst system of claim 10, further comprising one or more external electron donor components.
12. The catalyst system of claim 10, wherein R9 contains at least one heteroatom selected from the group consisting of B, Si, and halogen atoms.
13. The catalyst system of claim 10, wherein the backbone of the bridging groups is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
14. The catalyst system of claim 10, wherein either A or Ai cannot be connected to a nitrogen atom to form a carbon nitrogen double bond when the backbone of R group is a single carbon atom.
The catalyst system of claim 10, wherein R1 and R5 is selected from the group consisting of hydrogen, methyl, and ethyl.
16. The catalyst system of claim 10, wherein R, R2, R3, R6, and R7 independently comprise C1-C20 linear and/or branched substituents.
17. The catalyst system of claim 10, wherein two or more of said R, R1, R2, R3, R4, R5, R6, R7, and R8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
18. The catalyst system of claim 10, wherein at least one of a carbon atom or hydrogen atom of R may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the backbone of the bridging groups.
19. The catalyst system of claim 10, wherein at least one of a carbon atom or hydrogen atom of R1, R^, RJ, R\ RJ, R° R', and R° may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the ring structure .
20. A method for polymerizing alpha-olefins, comprising polymerizing alpha-olefins in the presence of:
(1) a solid catalyst component for the polymerization or co-polymerization of alpha-olefin comprising titanium, magnesium, halogen and at least one internal electron donor selected from heterocyclic organic compounds:
wherein L is represented by:
6 8.
or is selected from the group consisting of -OR9, -SR9, -OCOR9, -COOR9, -NH2,
wherein R9 is selected from the group consisting of a linear or branch C1-C20 alkyl, C2-C2o alkenyl, C3-C20 cycloalkyl, C6-C2o aryl, C7-C2o alkylaryl, and C7-C2o arylalkyl; wherein A and Al, which may be identical or different, is a carbon atom or a heteroatom selected from the group consisting of Si, N, B, and P; wherein Q and Ql, which may be identical or different, is a heteroatom selected from the group consisting of O, N, S, and P; wherein R1, R4, R5, and R8, which may be identical or different, are aliphatic, alicyclic or aromatic groups; wherein the subscripts p, q, i, and j are independently selected from 0 or 1 ; wherein the bonds directly connected to Q, A, Qi, and Als are independently a single bond or a double bond; wherein R, R2, R3, R6, and R7, which may be identical or different, are bridging groups with a backbone chain length being 1-6 atoms for R and 0-6 atoms for R2, R3, R6, and R7, wherein the resultant ring structure is a three to eight-membered ring. (2) a co-catalyst component.
21. The method of claim 20, further comprising one or more external electron donor components.
22. The method of claim 20, wherein R9 contains at least one heteroatom selected from the group consisting of B, Si, and halogen atoms.
23. The method of claim 20, wherein the backbone of the bridging groups is selected from the group consisting of aliphatic, alicyclic, and aromatic radicals.
24. The method of claim 20, wherein either A or Ai cannot be connected to a nitrogen atom to form a carbon nitrogen double bond when the backbone of R group is a single carbon atom.
25. The method of claim 20, wherein R1 and R5 is selected from the group consisting of hydrogen, methyl, and ethyl.
26. The method of claim 20, wherein R, R2, R3, R6, and R7 independently comprise C1-C20 linear and/or branched substituents.
27. The method of claim 20, wherein two or more of said R, R1, R2, R3, R4, R5, R6, R7, and R8 may be linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
28. The method of claim 20, wherein at least one of a carbon atom or hydrogen atom of R may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the backbone of the bridging groups.
29. The method of claim 20, wherein at least one of a carbon atom or hydrogen atom of R1, R , RJ, R\ RJ, R°, R', and R° may be replaced by a heteroatom selected from the group consisting of O, N, S, P, B, Si, and halogen atoms, wherein O, N, S, and P can only be embedded in the ring structure.
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CN104507986B (en) | 2018-01-16 |
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US10442874B2 (en) | 2019-10-15 |
US9951152B2 (en) | 2018-04-24 |
CN108299576A (en) | 2018-07-20 |
US8575283B1 (en) | 2013-11-05 |
CN104507986A (en) | 2015-04-08 |
EP2867265C0 (en) | 2023-06-07 |
US20180237552A1 (en) | 2018-08-23 |
JP2015521689A (en) | 2015-07-30 |
JP6062046B2 (en) | 2017-01-18 |
EP2867265B1 (en) | 2023-06-07 |
JP2019094514A (en) | 2019-06-20 |
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