KR20150003030A - Post metallocene compounds with phenanthroline backbone, catalyst compositions comprising the same, and method for preparing olefin polymers using the same - Google Patents
Post metallocene compounds with phenanthroline backbone, catalyst compositions comprising the same, and method for preparing olefin polymers using the same Download PDFInfo
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- KR20150003030A KR20150003030A KR1020130075869A KR20130075869A KR20150003030A KR 20150003030 A KR20150003030 A KR 20150003030A KR 1020130075869 A KR1020130075869 A KR 1020130075869A KR 20130075869 A KR20130075869 A KR 20130075869A KR 20150003030 A KR20150003030 A KR 20150003030A
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- group
- carbon atoms
- halogen
- formula
- substituted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims description 63
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 152
- 239000002904 solvent Substances 0.000 claims description 47
- 125000005843 halogen group Chemical group 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 239000003446 ligand Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- -1 cationic Lewis base Chemical class 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000007848 Bronsted acid Substances 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052795 boron group element Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000005353 silylalkyl group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims 6
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 239000010936 titanium Substances 0.000 claims 2
- IIYJCOKOQWJTHO-PKNBQFBNSA-N (e)-hexadec-5-ene Chemical compound CCCCCCCCCC\C=C\CCCC IIYJCOKOQWJTHO-PKNBQFBNSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 description 17
- 125000002524 organometallic group Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- GEJUFTHBORQCNQ-UHFFFAOYSA-N phenylalumane Chemical compound [AlH2]c1ccccc1 GEJUFTHBORQCNQ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 229960002163 hydrogen peroxide Drugs 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000012005 post-metallocene catalyst Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000003335 steric effect Effects 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 1
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NHOSADUTDSFMNF-UHFFFAOYSA-N CC1(CC=C(C=C1)C)[B] Chemical compound CC1(CC=C(C=C1)C)[B] NHOSADUTDSFMNF-UHFFFAOYSA-N 0.000 description 1
- UDIMWNNPXFTTCC-UHFFFAOYSA-N CCN(CC)CC.CN(C)C.[Al+3].[Al+3].[Al+3].[Al+3] Chemical compound CCN(CC)CC.CN(C)C.[Al+3].[Al+3].[Al+3].[Al+3] UDIMWNNPXFTTCC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
The present invention relates to a novel post metallocene ligand compound, an organometallic compound containing the ligand compound, a catalyst composition containing the organometallic compound, and a process for preparing an olefin polymer using the catalyst composition. More particularly, An organometallic compound which can exhibit high reactivity in the olefin polymerization reaction and can easily control the properties such as the chemical structure, molecular weight distribution and mechanical properties of the synthesized olefin polymer, a catalyst composition containing the same, To a process for producing a polymer.
In the early 1990s, DOW announced the use of [Me 2 Si (Me 4 C 5 ) N t Bu] TiCl 2 (Constrained-Geometry Catalyst, CGC) (US Pat. No. 5,064,802) (1) produce high molecular weight polymers with high activity even at high polymerization temperatures, (2) react with 1-hexene and It is also excellent in the copolymerization of α-olefins with large steric hindrance such as 1-octene. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.
One approach is to synthesize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges and olefin polymerization using the same. Representative metal compounds known until recently are listed below ( Chem. Rev. 2003 , 103 , 283).
The compounds listed above have been introduced with phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges, respectively, instead of the CGC structure of silicon bridges, In the case of the copolymerization, there were no excellent results in terms of activity or copolymerization performance in comparison with CGC.
Further, in another approach, a compound composed of an oxydol ligand instead of the amido ligand of the CGC was synthesized, and some polymerization using the compound was attempted. The examples are summarized as follows.
The compound (5) is reported by TJ Marks et al., And is characterized in that the Cp derivative and the oxydolidine are cross-linked by ortho-phenylene groups ( Organometallics 1997 , 16 , 5958). Compounds having the same cross-linking and polymerization using them have also been reported by Mu et al. ( Organometallics 2004 , 23 , 540). Also, Rothwell et al. ( Chem. Commun. 2003 , 1034) have reported that an indenyl ligand and an oxydol ligand are bridged by the same ortho-phenylene group. The compound (6) is reported by Whitby et al., And is characterized in that a cyclopentadienyl ligand and an oxydol ligand are bridged by three carbon atoms ( Organometallics 1999 , 18 , 348). These catalysts are synthesized from syndiotactic syndiotactic polystyrene polymerization. Similar compounds have also been reported by Hessen et al. ( Organometallics 1998 , 17 , 1652). (7) above is a compound represented by the feature that seems to be reported include Rau, high temperature and high pressure (210 ℃, 150 MPa) of ethylene and ethylene / 1-hexene copolymer in the active (J. Organomet. Chem. 2000, 608 , 71). Also, the synthesis of the catalyst (8) having similar structure and the high-temperature high-pressure polymerization using the same were patented by Sumitomo Co. (US Pat. No. 6,548,686).
Recently, compounds such as the above compound (9) having a pyridyl-amide ligand deviating from the CGC structure have been reported by DOW (US 2004/0220050, J. Am. Chem. Soc . 2007 , 129 , 7831). This catalyst is capable of high-temperature polymerization and has multiple active sites, exhibiting activity against ethylene / octene copolymerization having a broad molecular weight distribution, and having stereoselectivity capable of producing isotactic polypropylene through a steric effect, It is widely used.
On the other hand, Mitsui Japan has developed a transition metal compound (Ti, Zr) having a basic skeleton of phenoxyimine, showing excellent activity and ability such as controlling various polypropylene as well as living polymerization, as well as polyethylene. This catalyst is characterized by the fact that cyclopentadiene ligands, which are important skeletons of conventional metallocene catalysts and CGCs, are not present in the catalyst structure. As a result, this catalyst began to receive its spotlight as a post-metallocene, ie, a next-generation catalyst outside the metallocene structure. This catalyst was named FI catalyst 10, and the activity and efficiency of the catalyst were investigated in detail as the various substituents were changed around the basic structure of the catalyst, and it has been quoted in numerous literatures at present ( J. Am. Chem. Soc . 2001, 123, 6847 and 2002 , 124, 3327).
Recently, LG Chem developed a catalyst (11, 12) having another bridge, that is, a ligand in which a phenyl group is introduced, in the CGC backbone ( Organometallics , 2006 , 25 , 5122 and 2008 , 27 , 3907). These catalysts have the same activity level, molecular weight, and 1-octene content as those of conventional CGC in the production of ethylene / 1-octene copolymer.
However, the post metallocene catalyst that can be actually applied to commercial processes is not well known, and accordingly, a post metallocene catalyst capable of realizing a higher polymerization performance and capable of providing an olefin polymer having excellent physical properties Catalyst studies are still needed.
The present invention is to provide a novel post metallocene ligand compound.
The present invention also provides an organometallic compound which can easily control the characteristics of the synthesized olefin polymer, such as the chemical structure, molecular weight distribution and mechanical properties, of the ligand compound and exhibits high reactivity in the olefin polymerization reaction .
The present invention also provides a catalyst composition comprising the organometallic compound.
The present invention also provides a process for preparing the catalyst composition.
The present invention also provides a process for preparing an olefin polymer using the catalyst composition.
The present invention provides a novel ligand compound represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 may be the same or different from each other and are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen group, a cycloalkyl group having 5 to 60 carbon atoms, Or an unsubstituted C6-C60 aryl group, a C5-C60 cyclic diene group substituted or unsubstituted with a halogen group, a C2-C20 alkenyl group substituted or unsubstituted with a halogen group, a substituted or unsubstituted C6- An alkylaryl group having 7 to 60 carbon atoms, and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group.
Wherein R 3 is selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms.
The present invention also provides an organometallic compound comprising the ligand compound.
The present invention also provides a catalyst composition comprising a cocatalyst comprising at least one selected from the group consisting of the organometallic compounds and the compounds represented by the following formulas (3) to (5).
(3)
[LH] + [Z (E ) 4] - or [L] + [Z (E ) 4] -
L is a neutral or cationic Lewis base, [LH] + or [L] + is a Bronsted acid, H is a hydrogen atom, Z is a Group 13 element, E is independently 1 Or more of the hydrogen atoms may be halogen, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is substituted or unsubstituted with hydrocarbyl, alkoxy or phenoxy having 1 to 20 carbon atoms.
[Chemical Formula 4]
D (R 4 ) 3
In Formula 4, D is aluminum or boron, R 4 is each independently halogen; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.
[Chemical Formula 5]
In Formula 5, R 5 , R 6 and R 7 are each hydrogen; A halogen group; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more.
The present invention also provides a process for producing the catalyst composition.
The present invention also provides a process for preparing an olefin polymer using the catalyst composition.
According to the present invention, an organometallic compound capable of exhibiting high reactivity in the olefin polymerization reaction as well as easily controlling the characteristics of the synthesized olefin polymer such as chemical structure, molecular weight distribution and mechanical properties, a catalyst composition containing the same, A process for producing an olefin polymer using a catalyst composition can be provided.
Hereinafter, a novel ligand compound, an organometallic compound containing the same, a catalyst composition containing the organometallic compound, a method for preparing the catalyst composition, and a method for preparing an olefin polymer using the catalyst composition will be described in detail Will be described in detail.
According to one embodiment of the present invention, a ligand compound represented by the following formula (1) may be provided.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 may be the same or different from each other and are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen group, a cycloalkyl group having 5 to 60 carbon atoms, Or an unsubstituted C6-C60 aryl group, a C5-C60 cyclic diene group substituted or unsubstituted with a halogen group, a C2-C20 alkenyl group substituted or unsubstituted with a halogen group, a substituted or unsubstituted C6- An alkylaryl group having 7 to 60 carbon atoms, and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group.
Wherein R 3 is selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms.
The present inventors have newly synthesized an organometallic compound containing a ligand compound not previously known and can appropriately control the substituent introduced into the ligand compound to easily control the electronic and stereoscopic environment around the organic metal, It is possible to provide an organometallic catalyst which can exhibit high reactivity in the polymerization reaction of the olefin polymer and can easily control the characteristics of the synthesized olefin polymer such as chemical structure, molecular weight distribution and mechanical properties.
Particularly, the ligand compound of Formula 1 has a steric effect by including a rigid backbone phenanthroline, and since the phenanthroline has a high electron density The electron flow is very flexible, so that an electronic effect can be realized. Accordingly, the organometallic catalyst comprising the ligand compound of Formula 1 can react with the olefin monomer to form an olefin polymer more efficiently, and may exhibit improved stereoselectivity in polymerization of propylene.
Each of the substituents defined in Formula 1 will be described in detail as follows.
The halogen group means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group having 2 to 20 carbon atoms may include a straight chain or branched alkenyl group.
The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, and anisole. However, the aryl group is not limited thereto.
The alkylaryl group means an aryl group having at least one straight or branched alkyl group having 1 to 20 carbon atoms, and the arylalkyl group means a straight or branched alkyl group having at least one aryl group having 6 to 20 carbon atoms introduced thereto.
The aryloxy group means an aryl group having an oxygen atom introduced therein, that is, a functional group represented by '-O-Ar'.
The nitrile group may be a &
In addition,
R 1 and R 2 in Formula 1 are each independently hydrogen, an aryl group having 6 to 60 carbon atoms which is substituted or unsubstituted with a halogen group, or an alkylaryl group having 7 to 60 carbon atoms, which is substituted or unsubstituted with a halogen group.
Preferred examples of the ligand compound represented by the formula (1) include compounds represented by the following formulas (11) to (18).
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 15]
[Chemical Formula 16]
[Chemical Formula 17]
[Chemical Formula 18]
In the formulas (12) and (16), Ph is a phenyl group.
The compound represented by Formula 1 may be prepared by introducing an aldehyde or ketone using phenanthroline as a starting material, introducing a substituent through an imine condensation reaction, an amination reaction, and a CC coupling reaction to form a post metallocene type A catalyst without a pentadienyl ligand) -based ligand can be synthesized.
According to another embodiment of the present invention, an organometallic compound represented by the following general formula (2) may be provided.
(2)
In Formula 2, R 1 and R 2 may be the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen group, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms A cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 cyclic diene group substituted with a halogen group, a C2-C20 alkenyl group substituted or unsubstituted with a halogen group, a halogen A substituted or unsubstituted alkylaryl group having 7 to 60 carbon atoms, and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group.
Wherein R 3 is selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms.
The X 1 , X 2 and X 3 are each independently a halogen radical, an alkylamido group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an arylamido group having 6 to 60 carbon atoms, an alkyl group having 1 to 20 carbon atoms, An alkenyl group, an aryl group having 6 to 60 carbon atoms, an alkylaryl group having 7 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms.
The M may be a Group 3 to 12 metal or a lanthanide series metal.
The inventors of the present invention prepared an organometallic compound represented by the following formula (2) in which a metal of Group 3 to Group 12 or a lanthanide series metal was coordinately bonded using the compound represented by Formula 1 as a ligand, It has been confirmed through experiments that not only high reactivity can be exhibited when used as a catalyst but also properties such as chemical structure, molecular weight distribution and mechanical properties of the synthesized olefin polymer can be easily controlled.
In particular, as described above, the organometallic compound represented by Formula 2 may include phenanthroline as a backbone to achieve a steric effect and an electronic effect , The electronic and stereoscopic environment around the metal can be easily controlled, and ultimately, the structure and physical properties of the resulting olefin polymer can be easily controlled.
In the organometallic compound, M and N may be coordinately bonded, and '?' Means coordination bond.
The silyl group may include a silyl functional group introduced with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, Specific examples thereof include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) However, the present invention is not limited to these examples.
The alkylamido group refers to an amido group to which at least one linear or branched alkyl group having 1 to 20 carbon atoms is introduced. Specific examples thereof include a dimethylamido group and a diethylamido group, but are not limited thereto.
The arylamido group refers to an amido group having at least one aryl group having 6 to 20 carbon atoms introduced therein, and specifically includes, but is not limited to, a diphenylamido group.
On the other hand, Ti, Ti, Zr, and Hf, which are metals of Group 3 to Group 12 or a lanthanide series metal, may be specifically used, but the present invention is not limited thereto.
And R < 1 > and R < 2 & Each R 2 is preferably independently an aryl group having 6 to 60 carbon atoms or an alkylaryl group having 7 to 60 carbon atoms.
Preferred examples of the organometallic compound represented by the formula (2) include compounds represented by the following formulas (21) to (28).
[Chemical Formula 21]
[Chemical Formula 22]
(23)
≪ EMI ID =
(25)
(26)
(27)
(28)
In the above formulas (27) and (28), X 1 and X 2 are as defined in the above formula (2).
The compound represented by Formula 2 may be prepared by introducing an aldehyde or ketone using phenansroline as a starting material, introducing a substituent through an imine condensation reaction, an amination reaction, or a CC coupling reaction to obtain a ligand compound represented by Formula 1 Synthesized, and then reacting it with a metal source.
According to another embodiment of the present invention, there is provided a catalyst composition comprising a cocatalyst comprising at least one selected from the group consisting of the organometallic compound of the formula (2) and the compounds of the following formula (3) to (5).
(3)
[LH] + [Z (E ) 4] - or [L] + [Z (E ) 4] -
L is a neutral or cationic Lewis base, [LH] + or [L] + is a Bronsted acid, H is a hydrogen atom, Z is a Group 13 element, E is independently 1 Or more of the hydrogen atoms may be halogen, an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is substituted or unsubstituted with hydrocarbyl, alkoxy or phenoxy having 1 to 20 carbon atoms.
[Chemical Formula 4]
D (R 4 ) 3
In Formula 4, D is aluminum or boron, R 4 is each independently halogen; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.
[Chemical Formula 5]
In Formula 5, R 5 , R 6 and R 7 are each hydrogen; A halogen group; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more.
In the above formulas (3) and (4), "hydrocarbyl" is a monovalent functional group in which hydrogen atoms are removed from hydrocarbons, and may include ethyl, phenyl and the like.
The catalyst composition is in an activated state due to the reaction between the organometallic compound and the cocatalyst, and may be referred to as an activated catalyst composition. However, since it is well known in the art that the catalyst composition is present in an activated state, the term activated catalyst composition will not be used separately herein. The catalyst composition can be used for olefin mono-polymerization or copolymerization.
Meanwhile, the compound of Formula 3 may act as an activator and the compound of Formula 4 or 5 may serve as an alkylating agent.
More specifically, the compound of Formula 3 may have a role of activating the organometallic compound of Formula 2 and may include a non-coordinating anion that is compatible with the cations that are Bronsted acid. Preferred anions are relatively large in size and contain a single coordination complex containing a metalloid. Particularly, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, anion-containing salts containing coordination complex compounds containing a single boron atom are preferred.
When the compound of Formula 3 is included in the catalyst composition, the number of moles of the organometallic compound of Formula 2: moles of the compound of Formula 3 is 1: 1 to 1:25, preferably 1: 1 to 1: 10, and more preferably from 1: 2 to 1:15. When the molar ratio is less than 1: 1, the amount of the cocatalyst is relatively small, so that the activation of the metal compound is not completely performed, and the activity of the organometallic catalyst may not be sufficient. When the molar ratio is more than 1:25, The activity may be increased, but the use of unnecessarily cocatalyst may cause a problem of a large increase in production cost.
Specific examples of the compound of Formula 3 include triethylammoniumtetra (phenyl) boron, tributylammoniumtetra (phenyl) boron, trimethylammoniumtetra (phenyl) boron, tripropylammoniumtetra (phenyl) (P-tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl (Phenyl) boron, N, N-diethylamidinium tetra (phenyl) boron, N, N-diethylanilinium tetra (Pentafluorophenyl) boron, diethylammoniumtetra (pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, trimethylphosphonium tetra (phenyl) boron, triethylammonium Tetra (phenyl) aluminum, tributylammonium (P-tolyl) aluminum, trimethylammonium tetra (p-tolyl) aluminum, trimethylammonium tetra (phenyl) aluminum, trimethylammonium tetra Aluminum triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum, tributylammoniumtetra N, N-diethylaniliniumtetra (phenyl) aluminum, N, N-diethylaniliniumtetra (phenyl) aluminum, N, N-diethylaniliniumtetra (pentafluoro (Phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammoniumtetra (phenyl) aluminum, diethylammoniumtetra (pentafluorophenyl) aluminum, triphenylphosphonium tetra (Phenyl) boron, trimethylammoniumtetra (phenyl) boron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (p-tolyl) (O, p-dimethylphenyl) boron, tributylammoniumtetra (p-dimethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra ) Boron, N, N-diethylaniliniumtetra (pentafluorophenyl) boron, diethylammoniumtetra (pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, triphenylcarboniumtetra (p-tribromonomethylphenyl) boron, triphenylcarbonium tetra (pent And the like-fluorophenyl) boron, trityl tetra (pentafluorophenyl) boron, but the embodiment is not limited thereto.
When the compound of Formula 4 or 5 is contained in the catalyst composition, the number of moles of the organometallic compound of Formula 2: moles of the compound of Formula 4 or 5 is 1: 2 to 1: 5,000, 1:10 to 1: 1,000, more preferably 1:20 to 1: 500. More specifically, when one of the compounds represented by Formulas (4) and (5) is included, the ratio of the number of moles of the organometallic compound represented by Formula (2) to the compound represented by Formula (4) or (5) The ratio of the number of moles of the organometallic compound of formula (2) to the number of moles of the compound of formula (4) and (5) may be the same as above.
When the molar ratio is less than 1: 2, the amount of the alkylating agent is so small that the alkylation of the metal compound may not proceed completely. When the molar ratio exceeds 1: 5,000, alkylation of the metal compound occurs, The activation of the alkylated metal compound may not be completely due to side reactions between the activators of formula (3).
Specific examples of the compound of formula (4) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri- , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and preferably trimethylaluminum, triethylaluminum or triisobutylaluminum.
The alkylaluminoxane can be used without particular limitation, and specific examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and methylaluminoxane is preferably used. .
On the other hand, the catalyst composition contains the organic Metal compounds; And at least one selected from the group consisting of the compounds represented by Chemical Formulas 3 to 5; In addition, a solvent may be further included.
Solvents which are known to be usable for organometallic catalysts as the solvent can be used without any particular limitation and include, for example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene and benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The content of the solvent in the catalyst composition may be appropriately controlled depending on the characteristics of the catalyst composition used and the conditions of the production process of the olefin polymer to be used.
In addition, the organometallic compound and the promoter compound may be used in a fixed form to the carrier, and the carrier may be used without any particular limitation as long as it is known to be commonly used in the catalyst for producing an olefin polymer. For example, the carrier may be silica, alumina, magnesia, or a mixture thereof, and the carrier may be dried at high temperature, and these are usually Na 2 O, K 2 CO 3 , BaSO 4, and Mg NO 3 ) 2 or the like, carbonate, sulfate, nitrate components.
The catalyst composition of this embodiment may be prepared by reacting the organometallic compound of Formula 2 with at least one cocatalyst selected from the group consisting of the compounds of Formulas 3 to 5. For example, the catalyst composition may be prepared by reacting the organometallic compound of Formula 2 with the cocatalyst of Formula 3 or 5, or the organometallic compound of Formula 2 and the cocatalyst of Formula 4 or 5 And reacting the reactant with the cocatalyst of the compound of Formula 3 to form a catalyst composition.
More specifically, the catalyst composition comprises contacting the organometallic compound of Formula 2 with the compound of Formula 4 and / or the compound of Formula 5 to obtain a mixture; And adding the compound of Formula 3 to the mixture. The molar ratio of the organometallic compound of Formula 2 to the compound of Formula 4 and / or 5 or the compound of Formula 3 is as described above in the catalyst composition.
Alternatively, the catalyst composition may be prepared by bringing the organometallic compound of Formula 2 and the compound of Formula 5 or 3 into contact with each other. The molar ratio of the organometallic compound of Formula 2 to the compound of Formula 5 or 3 is as described above in the catalyst composition.
According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition.
As described above, the organometallic compound of Formula 2 can easily control the electronic and stereoscopic environment around the metal, thereby increasing the yield of the polymerization reaction and improving the chemical structure, molecular weight distribution, mechanical properties, etc. of the synthesized olefin polymer Can be easily controlled. In addition, the organometallic compound of Formula 2 has a relatively strong bond between atoms and a high intermolecular bond, so that the organometallic compound of Formula 2 has a high high-temperature activity (higher catalytic activity) than the former metallocene catalyst or post metallocene catalyst (a catalyst without a cyclopentadienyl ligand) Thereby allowing the olefin polymerization reaction to proceed at high efficiency over a higher temperature range than previous catalysts.
The polymerization reaction of the olefin monomer may be carried out at 90 ° C or higher, preferably 120 to 160 ° C. If the polymerization temperature is too low, the reactivity of the olefin monomer may not be high, so that the synthesis of the olefin polymer may be difficult. If the polymerization temperature is too high, the olefin monomer may be thermally decomposed.
The olefin monomer may be polymerized by a continuous polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process. Preferably, the olefin monomer may be subjected to a solution polymerization reaction in a single reactor.
The catalyst composition may be prepared by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane, Or a hydrocarbon solvent substituted with a chlorine atom, for example. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.
Examples of the olefin-based monomer polymerizable with the organometallic compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like. The diene olefin-based monomer or triene olefin-based monomer having two or more double bonds Can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and another comonomer, the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, It is preferably one or more comonomers.
In particular, in the process for preparing an olefin polymer according to the present invention, the catalyst composition has a steric hindrance such as ethylene and 1-octene at a reaction temperature not lower than the conventionally used reaction temperature, 90 ° C or higher, Copolymerization of a large monomer is also possible. By introducing various substituents into a tridentate ligand containing a hetero atom, it is possible to easily control the electronic and stereoscopic environment around the metal, ultimately controlling the structure and physical properties of the resulting olefin polymer This is possible.
Hereinafter, the polymerization process of the olefin polymer will be illustrated, but this is merely for the purpose of illustrating the present invention, and the scope of the present invention is not intended to be limited by the following description.
The reactor used in the process for producing a polymer according to one embodiment is preferably a continuously stirred reactor (CSTR) or a continuous flow reactor (PFR). It is preferable that two or more of the reactors are arranged in series or in parallel. It is also preferred that the process further comprises a separator for continuously separating the solvent and unreacted monomers from the reaction mixture.
When the process for producing a polymer according to the present invention is carried out by a continuous solution polymerization process, it can be composed of a catalytic process, a polymerization process, a solvent separation process, and a recovery process step, and more specifically, the following.
a) catalytic process
The catalyst composition according to the present invention can be injected by dissolving or diluting in an aliphatic or aromatic solvent having 5 to 12 carbon atoms which is unsubstituted or substituted with halogen suitable for the olefin polymerization process. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene Can be used. The solvent used herein is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum or the like, and it is also possible to use a large amount of a cocatalyst.
b) Polymerization process
The polymerization process proceeds on the reactor by introducing the catalyst composition comprising the organometallic compound of Formula 2 and the cocatalyst and one or more olefin monomers. In the case of solution phase and slurry polymerization, the solvent is injected onto the reactor. In the case of solution polymerization, a mixture of a solvent, a catalyst composition and a monomer is present in the reactor.
The molar ratio of the monomer to the solvent suitable for the reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of monomer to solvent is from 10: 1 to 1: 10,000, preferably from 5: 1 to 1: 100, and most preferably from 1: 1 to 1:20. When the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, and there is a problem in transferring the resulting polymer. When the molar ratio of the solvent is more than 1: 10,000, There is a problem such as an increase in equipment and an increase in energy cost due to the refining and recycling of the solvent.
The solvent is -40 ° C using a heater or a freezer. To 150? Lt; / RTI > to the reactor, thereby initiating the polymerization reaction with the monomers and the catalyst composition. If the temperature of the solvent is -40? , The reaction temperature is also lowered due to a too low temperature of the solvent, which makes it difficult to control the temperature. , The temperature of the solvent is too high, and the heat of reaction due to the reaction is difficult to remove.
A high capacity pump may be used to pass the mixture of reactants without further pumping between the reactor arrangement, the pressure drop device, and the separator by raising the pressure to more than 50 bar to provide reactants (solvent, monomer, catalyst composition, etc.) .
Further, in the process for producing the olefin polymer, the internal pressure of the reactor may be from 1 bar to 300 bar, preferably from 10 to 200 bar, more preferably from 30 to 100 bar. If the internal pressure is less than 1 bar, the reaction rate is low and the productivity is low, and there is a problem due to vaporization of the used solvent. If the internal pressure exceeds 300 bar, the equipment cost such as the device cost due to the high pressure may be increased.
The polymer produced in the reactor is preferably maintained at a concentration of less than 20 wt% in the solvent and is preferably transferred to the first solvent separation process for solvent removal after a short residence time. The residence time in the reactor of the resulting polymer is from 1 minute to 10 hours, preferably from 3 minutes to 1 hour, more preferably from 5 minutes to 30 minutes. When the residence time is shorter than 3 minutes, there is a problem such as a decrease in productivity and a loss of catalyst due to a short residence time and an increase in manufacturing cost. There is a problem of increasing the equipment cost.
c) solvent separation process
A solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. For example, the polymer solution transferred from the reactor is heated to about 200? The pressure is lowered through the pressure drop device and the unreacted raw material and the solvent are vaporized in the first separator.
The pressure in the separator may be from 1 to 30 bar, preferably from 1 to 10 bar, more preferably from 3 to 8 bar, and the temperature in the separator may be in the range of 150 to 250 ° C, preferably 170 to 230 ° C, More preferably 180 ° C to 230 ° C.
If the pressure in the separator is less than 1 bar, the content of the polymer increases and there is a problem in transferring. If the pressure exceeds 30 bar, it may be difficult to separate the solvent used in the polymerization process. The temperature in the separator is 150? , The viscosity of the copolymer and the mixture thereof is increased and there is a problem in transferring the copolymer. , Discoloration due to carbonization of the polymer may occur due to denaturation at a high temperature.
The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. When the first stage solvent separation process is performed, a concentrated polymer solution of up to 65% can be obtained, which is transferred to the second separator by the transfer pump through the heater, and the separation process for the residual solvent is performed in the second separator. In order to prevent deformation of polymer due to high temperature while passing through a heater, a heat stabilizer is added and a reaction inhibitor is injected with a heat stabilizer together with a heat stabilizer to suppress the reaction of the polymer due to the residual activity of the active substance present in the polymer solution do. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and a granulated polymer can be obtained after passing through the cooling water and the cutter. In the second separation process, the gaseous solvent and other unreacted monomers can be sent to the recovery process for purification and reuse.
d) Recovery process
The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the unreacted raw material in the primary solvent separation process. However, the solvent recovered in the secondary solvent separation process contains a large amount of water acting as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply in the vacuum pump, It is preferable to be reused.
With respect to the method for producing an olefin polymer, except for the above-mentioned, apparatuses, apparatuses, synthesis methods, reaction conditions, and the like known to be usable for synthesizing an olefin polymer using a metallocene catalyst can be used without limitation.
Claims (16)
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a cycloalkyl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with a halogen atom, An alkyl group having 1 to 60 carbon atoms, an aryl group having 1 to 60 carbon atoms, a cyclodienylene group having 5 to 60 carbon atoms substituted or unsubstituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms substituted or unsubstituted with a halogen atom, An aryl group and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group,
R 3 is a group selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms.
Each of R 1 and R 2 is independently hydrogen, an aryl group having 6 to 60 carbon atoms which is substituted or unsubstituted with a halogen group, or an alkylaryl group having 7 to 60 carbon atoms, which is substituted or unsubstituted with a halogen group.
Wherein the ligand compound is a ligand compound represented by one of the following formulas (11) to (18):
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 15]
[Chemical Formula 16]
[Chemical Formula 17]
[Chemical Formula 18]
In the formulas (12) and (16), Ph is a phenyl group.
(2)
In Formula 2,
R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a cycloalkyl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with a halogen atom, An alkyl group having 1 to 60 carbon atoms, an aryl group having 1 to 60 carbon atoms, a cyclodienylene group having 5 to 60 carbon atoms substituted or unsubstituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms substituted or unsubstituted with a halogen atom, An aryl group and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group,
R 3 is a group selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms,
X 1 , X 2 and X 3 are each independently a halogen radical, an alkylamido group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an arylamido group having 6 to 60 carbon atoms, an alkyl group having 1 to 20 carbon atoms, An alkenyl group, an aryl group having 6 to 60 carbon atoms, an alkylaryl group having 7 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms,
M is a metal of group 3 to 12 or a lanthanide series metal.
Wherein M is titanium (Ti), zirconium (Zr), or hafnium (Hf).
The R < 1 & And R 2 are each independently an aryl group having 6 to 60 carbon atoms or an alkylaryl group having 7 to 60 carbon atoms.
Wherein the organometallic compound is represented by one kind selected from the group consisting of compounds represented by the following Chemical Formulas 21 to 28:
[Chemical Formula 21]
[Chemical Formula 22]
(23)
≪ EMI ID =
(25)
(26)
(27)
(28)
In the formulas (27) and (28), X 1 and X 2 each independently represents a halogen atom, an alkylamido group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an arylamido group having 6 to 60 carbon atoms, An alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkylaryl group having 7 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and an alkylidene radical having 1 to 20 carbon atoms do.
(3)
[LH] + [Z (E ) 4] - or [L] + [Z (E ) 4] -
In Formula 3,
L is a neutral or cationic Lewis base,
[LH] + or [L] + is a Bronsted acid,
H is a hydrogen atom,
Z is a Group 13 element,
E each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy,
[Chemical Formula 4]
D (R 4 ) 3
In Formula 4,
D is aluminum or boron,
R < 4 > are each independently selected from the group consisting of halogen; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 5]
In Formula 5,
R 5 , R 6 and R 7 are each hydrogen; A halogen group; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen; and a is an integer of 2 or more.
Wherein the number of moles of the organometallic compound of Formula 2: moles of the compound of Formula 3 is 1: 1 to 1:25.
Wherein the number of moles of the organometallic compound of Formula 2 is 1: 2 to 1: 5,000.
≪ / RTI > further comprising a solvent.
Wherein the organometallic compound and the cocatalyst compound are in a form fixed to a carrier.
(2)
In Formula 2,
R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a cycloalkyl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with a halogen atom, An alkyl group having 1 to 60 carbon atoms, an aryl group having 1 to 60 carbon atoms, a cyclodienylene group having 5 to 60 carbon atoms substituted or unsubstituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms substituted or unsubstituted with a halogen atom, An aryl group and an arylalkyl group having 7 to 60 carbon atoms substituted or unsubstituted with a halogen group,
R 3 is a group selected from the group consisting of deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms,
X 1 , X 2 and X 3 are each independently a halogen radical, an alkylamido group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an arylamido group having 6 to 60 carbon atoms, an alkyl group having 1 to 20 carbon atoms, An alkenyl group, an aryl group having 6 to 60 carbon atoms, an alkylaryl group having 7 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms,
M is a Group 3 to Group 12 metal or a lanthanide series metal,
(3)
[LH] + [Z (E ) 4] - or [L] + [Z (E ) 4] -
In Formula 3,
L is a neutral or cationic Lewis base,
[LH] + or [L] + is a Bronsted acid,
H is a hydrogen atom,
Z is a Group 13 element,
E each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein at least one hydrogen atom is substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy,
[Chemical Formula 4]
D (R 4 ) 3
In Formula 4,
D is aluminum or boron,
R < 4 > are each independently selected from the group consisting of halogen; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 5]
In Formula 5,
R 5 , R 6 and R 7 are each hydrogen; A halogen group; A hydrocarbyl group having 1 to 20 carbon atoms; Or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen; and a is an integer of 2 or more.
The olefin monomers may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Butadiene, 1,5-hexadecene, 1-hexadecene, 1-hexadecene, 1-hexadecene, Wherein the olefin polymer comprises at least one member selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
Wherein the step of polymerizing the olefin monomer is carried out at a polymerization temperature of at least 90 占 폚.
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