KR20220106490A - Method for ethylene oligomerization - Google Patents
Method for ethylene oligomerization Download PDFInfo
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- KR20220106490A KR20220106490A KR1020210009462A KR20210009462A KR20220106490A KR 20220106490 A KR20220106490 A KR 20220106490A KR 1020210009462 A KR1020210009462 A KR 1020210009462A KR 20210009462 A KR20210009462 A KR 20210009462A KR 20220106490 A KR20220106490 A KR 20220106490A
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000005977 Ethylene Substances 0.000 title claims abstract description 94
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims description 62
- 125000000217 alkyl group Chemical group 0.000 claims description 47
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 27
- 239000004698 Polyethylene Substances 0.000 claims description 27
- 229920000573 polyethylene Polymers 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 125000003282 alkyl amino group Chemical group 0.000 claims description 19
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 17
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 16
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 15
- 125000001769 aryl amino group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 14
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 11
- 125000005104 aryl silyl group Chemical group 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 5
- 125000006313 (C5-C8) alkyl group Chemical group 0.000 claims description 4
- 125000006751 (C6-C60) aryloxy group Chemical class 0.000 claims description 4
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 20
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BPEMCEULJQTJMI-UHFFFAOYSA-N n-dichlorophosphanyl-n-ethylethanamine Chemical compound CCN(CC)P(Cl)Cl BPEMCEULJQTJMI-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000003828 azulenyl group 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
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005106 triarylsilyl group Chemical group 0.000 description 1
- QTKHQYWRGFZFHG-UHFFFAOYSA-N trioctylsilicon Chemical compound CCCCCCCC[Si](CCCCCCCC)CCCCCCCC QTKHQYWRGFZFHG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 에틸렌 올리고머화 방법에 관한 것으로, 상세하게는 특정한 크롬 화합물, 유기 알루미늄 화합물 및 특정 첨가제를 포함하는 에틸렌 올리고머화 방법에 관한 것이다.The present invention relates to a process for ethylene oligomerization, and more particularly, to a process for ethylene oligomerization comprising a specific chromium compound, an organoaluminum compound and a specific additive.
에틸렌 올리고머 중 1-헥센(1-hexene) 및 1-옥텐(1-octene)은 폴리에틸렌과 같은 폴리올레핀의 중합 시 공단량체로서 대량으로 사용되고 있는 물질로서, 균일계 메탈로센계 촉매를 사용한 폴리올레핀 생산이 증가함에 따라 이에 대한 수요가 꾸준히 증가하고 있다.Among ethylene oligomers, 1-hexene and 1-octene are materials used in large quantities as comonomers in the polymerization of polyolefins such as polyethylene, and polyolefin production using homogeneous metallocene catalysts is increasing. As a result, the demand for it is steadily increasing.
종래는 니켈 촉매를 근간으로 한 Shell Higher Olefin Process(SHOP)에서 에틸렌을 올리고머화함으로써, 탄소수 약 4개 내지 약 30개의 다양한 1-알켄(1-alkene)을 생성하고, 이로부터 1-헥센 및/또는 1-옥텐을 별도로 분리하여 얻을 수 있었다.Conventionally, by oligomerizing ethylene in the Shell Higher Olefin Process (SHOP) based on a nickel catalyst, various 1-alkenes having about 4 to about 30 carbon atoms are produced, and from this, 1-hexene and / Alternatively, 1-octene could be separately obtained.
이후 에틸렌 올리고머화 반응에서의 선택도를 높여, 1-헥센 또는 1-옥텐을 고수율로 생성할 수 있는 촉매 시스템이 개발되었다.Thereafter, a catalyst system capable of producing 1-hexene or 1-octene in high yield by increasing the selectivity in the ethylene oligomerization reaction was developed.
대표적인 예로, 미국특허 7511183B2 에서는 크롬 3가 화합물(CrCl3 또는 Cr(acac)3), 비스포스핀 리간드(bisphosphine ligand)인 (iPrN(PPh2)2) 및 메틸알루미녹산(methylaluminoxane, MAO)을 사용하여 1-옥텐 및 1-헥센을 선택적으로 생성할 수 있는 촉매 제조 방법이 보고되었다.As a representative example, US Patent 7511183B2 uses a chromium trivalent compound (CrCl 3 or Cr(acac) 3 ), a bisphosphine ligand (iPrN(PPh 2 ) 2 ) and methylaluminoxane (MAO). Thus, a method for preparing a catalyst capable of selectively producing 1-octene and 1-hexene has been reported.
그러나, 상기 촉매 시스템은 상업적으로 활용가능한 수준의 활성도를 구현하기 위해 고가의 MAO를 다량(Al/Cr = 300~500)으로 사용해야함은 물론 공정안정성을 심각하게 저해하는 폴리에틸렌(polyetylene, PE)이 다량 생성되는 문제점이 보고되었다(Organometallics, 27, 5712-5716).However, the catalyst system has to use a large amount of expensive MAO (Al/Cr = 300 to 500) to realize a commercially usable level of activity, as well as polyethylene (PE), which seriously inhibits process stability. A problem of mass production has been reported (Organometallics, 27, 5712-5716).
이러한 문제점을 개선하기 위하여 한국특허 10-2087994에서는 MAO를 사용하지 않으면서도 높은 촉매 활성을 발현함은 물론 폴리에틸렌 부산물의 생성을 줄일 수 있는 촉매 시스템을 보고하였으나, 경제성 있는 에틸렌 올리고머화 공정 상업화를 위해서는 촉매 활성 및 폴리에틸렌 부산물 생성 측면에 있어서 여전히 추가 개선이 필요하다.In order to improve this problem, Korean Patent No. 10-2087994 reported a catalyst system capable of reducing the production of polyethylene by-products as well as expressing high catalytic activity without using MAO. Further improvements are still needed in terms of activity and polyethylene by-product production.
즉, 높은 선택도로 1-헥센 및 1-옥텐을 제조할 수 있을 뿐만 아니라, 촉매 활성이 개선되고 공정 안정성을 저해하는 폴리에틸렌 생성량을 현저하게 감소시킬 수 있는 개선된 공정의 에틸렌 올리고머화 방법이 요구된다.That is, there is a need for an improved process for ethylene oligomerization that can produce 1-hexene and 1-octene with high selectivity, as well as improve catalytic activity and significantly reduce the amount of polyethylene produced that inhibits process stability. .
본 발명은 상기와 같은 종래기술들의 문제점을 해결하기 위한 것으로서, 높은 선택도로 1-헥센 및 1-옥텐을 제조할 수 있을 뿐만 아니라, 촉매 활성이 개선되고 공정 안정성을 저해하는 폴리에틸렌 생성량을 현저히 줄일 수 있는 에틸렌 올리고머화 방법을 제공한다.The present invention is intended to solve the problems of the prior art as described above, and not only can produce 1-hexene and 1-octene with high selectivity, but also improve catalytic activity and significantly reduce the amount of polyethylene produced that inhibits process stability. A method for ethylene oligomerization is provided.
본 발명은 향상된 촉매활성을 가지는 동시에 폴리에틸렌 생성을 억제하여 공정 안정성을 가지는 에틸렌 올리고머화 방법을 제공하는 것으로, 본 발명의 올리고머화 제조방법은,The present invention provides an ethylene oligomerization method having improved catalytic activity and process stability by suppressing polyethylene production, the oligomerization preparation method of the present invention comprising:
유기용매의 존재 하, 하기 화학식 1로 표시되는 크롬 화합물과 하기 화학식 2로 표시되는 유기 알루미늄 화합물을 반응시키는 단계; 및reacting the chromium compound represented by the following formula (1) with the organoaluminum compound represented by the following formula (2) in the presence of an organic solvent; and
상기 단계 반응물에 수소 및 에틸렌을 접촉시켜 에틸렌 올리고머를 제조하는 단계;를 포함한다.and contacting the reactants with hydrogen and ethylene to prepare an ethylene oligomer.
[화학식 1][Formula 1]
[화학식 2] [Formula 2]
Al(R11)(R12)(R13)Al(R 11 )(R 12 )(R 13 )
(상기 화학식 1 및 2에서,(In Formulas 1 and 2,
R은 C1-C60알킬 또는 C6-C60아릴이고; R is C1-C60 alkyl or C6-C60 aryl;
R1 내지 R4는 서로 독립적으로 C1-C60알킬 또는 C6-C60아릴이며; R 1 to R 4 are each independently C1-C60 alkyl or C6-C60 aryl;
X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트; 또는 에테르 및 아미노에서 선택되는 하나 이상을 포함하는 C1-C30하이드로카빌;이고; X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate; or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;
A는 보론 또는 알루미늄이고; A is boron or aluminum;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴, 불소가 치환된 C6-C60아릴옥시 또는 불소가 치환된 C6-C60알콕시이며;Y 1 to Y 4 are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;
R11 내지 R13은 서로 독립적으로 C1-C20알킬이며,R 11 to R 13 are each independently C1-C20 alkyl;
상기 R의 알킬 또는 아릴 및 R1 내지 R4의 알킬 또는 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노C1-C30알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있다.)Alkyl or aryl of R and alkyl or aryl of R 1 to R 4 are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)
바람직하게 본 발명의 일 실시예에 따른 에틸렌 올리고머를 제조하는 단계는 상기 단계 반응물에 수소를 주입한 후 에틸렌을 순차적으로 주입하는 것 일 수 있다.Preferably, the step of preparing the ethylene oligomer according to an embodiment of the present invention may be to sequentially inject ethylene after hydrogen is injected into the reactant in the step.
본 발명의 일 실시예에 따른 에틸렌과 수소의 몰비는 1: 0.001 내지 3.0일 수 있으며, 크롬 화합물과 하기 화학식 2로 표시되는 유기 알루미늄 화합물의 몰비는 1 : 10 내지 500일 수 있다.The molar ratio of ethylene and hydrogen according to an embodiment of the present invention may be 1: 0.001 to 3.0, and the molar ratio of the chromium compound to the organoaluminum compound represented by Formula 2 below may be 1: 10 to 500.
보다 우수한 촉매활성 및 에틸렌 올리고머의 선택도를 가지기 위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 화학식 1 및 2에서, R은 C1-C60알킬이며; R1 내지 R4는 서로 독립적으로 C6-C60아릴이며; X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C30하이드로카빌이고; A는 보론 또는 알루미늄이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴이며; R11 내지 R13은 서로 독립적으로 C1-C20알킬이며; 상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있다.Preferably, in Formulas 1 and 2 according to an embodiment of the present invention in terms of having better catalytic activity and selectivity of the ethylene oligomer, R is C1-C60 alkyl; R 1 to R 4 are each independently C6-C60 aryl; X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C30 hydrocarbyl including ether; A is boron or aluminum; Y 1 to Y 4 are each independently C6-C60 aryl substituted with fluorine; R 11 to R 13 are each independently C1-C20 alkyl; The alkyl of R and the aryl of R 1 to R 4 are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, mono C1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, triC6-C30 arylamino, monoalkylsilyl, diC1-C30alkylsilyl, triC1-C30alkylsilyl, monoC6-C30arylsilyl, diC6-C30aryl It may be further substituted with one or more selected from silyl and triC6-C30 arylsilyl.
본 발명의 일 실시예에 따른 화학식 1은 하기 화학식 3으로 표시될 수 있다.Formula 1 according to an embodiment of the present invention may be represented by Formula 3 below.
[화학식 3][Formula 3]
(상기 화학식 3에서,(In Formula 3,
R은 C1-C30알킬 또는 C6-C30아릴이고; R is C1-C30 alkyl or C6-C30 aryl;
X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C20하이드로카빌이고; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;
A는 보론 또는 알루미늄이고; A is boron or aluminum;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C30아릴, 불소가 치환된 C6-C30아릴옥시 또는 불소가 치환된 C6-C30알콕시이며;Y 1 to Y 4 are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy;
R21 내지 R32는 서로 독립적으로 C1-C20알킬이며,R 21 to R 32 are each independently C1-C20 alkyl,
상기 R의 알킬 또는 아릴은 C1-C20알킬, C6-C20아릴, C1-C20알콕시, 모노 C1-C20알킬아미노, 디C1-C20알킬아미노, 트리C1-C20알킬아미노, 모노C1-C20아릴아미노, 디C6-C20아릴아미노 및 트리C6-C20아릴아미노에서 선택되는 하나이상으로 더 치환될 수 있다.)Alkyl or aryl of R is C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, mono C1-C20 alkylamino, diC1-C20 alkylamino, triC1-C20 alkylamino, mono C1-C20 arylamino, It may be further substituted with one or more selected from diC6-C20 arylamino and triC6-C20 arylamino.)
보다 바람직하게 본 발명의 일 실시예에 따른 화학식 3에서, R은 C1-C20알킬이고; X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트이며; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C20아릴 또는 불소가 치환된 C6-C20아릴옥시일 수 있다.More preferably, in Formula 3 according to an embodiment of the present invention, R is C1-C20 alkyl; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate; A is boron; Y 1 to Y 4 may each independently represent fluorine-substituted C6-C20 aryl or fluorine-substituted C6-C20 aryloxy.
본 발명의 일 실시예에 따른 유기용매는 할로겐으로 치환 또는 비치환된 탄화수소일 수 있다.The organic solvent according to an embodiment of the present invention may be a hydrocarbon unsubstituted or substituted with a halogen.
본 발명의 일 실시예에 따른 올리고머를 제조하는 단계는 10 내지 80℃에서 10분 내지 2시간동안 수행될 수 있다.The step of preparing the oligomer according to an embodiment of the present invention may be performed at 10 to 80° C. for 10 minutes to 2 hours.
바람직하게 본 발명의 올리고머는 폴리에틸렌의 함량이 0.6중량%이하일 수 있다.Preferably, the content of polyethylene in the oligomer of the present invention may be 0.6% by weight or less.
본 발명의 에틸렌 올리고머화 제조방법은 높은 촉매활성 및 우수한 선택도로 1-헥센 및 1-옥텐을 제조할 수 있다.The method for preparing ethylene oligomerization of the present invention can produce 1-hexene and 1-octene with high catalytic activity and excellent selectivity.
나아가 본 발명의 에틸렌 올리고머화 방법은 수소 첨가제를 특정단계에서 주입함으로써 폴리에틸렌 생성량을 현저하게 감소시킬 수 있어 공정 안정성을 유지할 수 있어 매우 경제적이다.Furthermore, the ethylene oligomerization method of the present invention is very economical because the production of polyethylene can be significantly reduced by injecting a hydrogen additive in a specific step, thereby maintaining process stability.
또한 본 발명의 에틸렌 올리고머화 방법은 본 발명의 상기 화학식 1로 표시되는 크롬 화합물을 사용함으로써 종래의 비싼 메틸알루미녹산을 사용하지 않고도 에틸렌 올리고머화를 진행할 수 있어 매우 경제적이다.In addition, the ethylene oligomerization method of the present invention is very economical because ethylene oligomerization can be performed without using the conventional expensive methylaluminoxane by using the chromium compound represented by Formula 1 of the present invention.
도 1은 본 발명의 제조예 1에서 제조된 화학식 A의 13P NMR, 1H NMR, 19F NMR, EPR(Electron paramagnetic resonance) 결과를 나타낸 그래프이다.
도 2는 본 발명의 제조예 2에서 제조된 화학식 B의 13P NMR, 1H NMR, 19F NMR 결과를 나타낸 그래프이다.1 is a graph showing the results of 13 P NMR, 1 H NMR, 19 F NMR, and EPR (electron paramagnetic resonance) of Formula A prepared in Preparation Example 1 of the present invention.
2 is a graph showing the results of 13 P NMR, 1 H NMR, and 19 F NMR of Formula B prepared in Preparation Example 2 of the present invention.
이하, 본 발명에 대하여 보다 구체적으로 설명한다. 이 때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the technical field to which this invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. Descriptions of possible known functions and configurations will be omitted.
본 명세서에서 사용된 용어 "알킬"은 (탄소수가 특별히 한정되지 않은 경우) 탄소수 1 내지 60, 바람직하게 탄소수 1 내지 30, 일 양태에서 바람직하게 탄소수 1 내지 20, 일 양태에서 바람직하게 탄소수 1 내지 10, 일 양태에서 바람직하게 탄소수 1 내지 7을 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 7인 일 양태에서 바람직하게 탄소수 1 내지 5인 직쇄상 또는 분지상 알킬을 의미한다. 대표적인 포화 직쇄상 알킬은 -메틸, -에틸, -n-프로필, -n-부틸, -n-펜틸, -n-헥실, -n-헵틸, -n-옥틸, -n-노닐 과 -n-데실을 포함하고, 반면에 포화 분지상 알킬은 -이소프로필, -sec-부틸, -이소부틸, -tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다.As used herein, the term "alkyl" (when the number of carbon atoms is not particularly limited) has 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms in one embodiment, preferably 1 to 10 carbon atoms in one embodiment. , preferably in one aspect, refers to a saturated straight-chain or branched acyclic hydrocarbon having 1 to 7 carbon atoms. "Lower alkyl" means straight-chain or branched alkyl having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms in one aspect. Representative saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl, whereas saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5- Methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethyl Pentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 "C1-C10"와 같이 기재될 경우 이는 탄소수가 1 내지 10개임을 의미한다. 예를 들어, C1-C10알킬은 탄소 수가 1 내지 10인 알킬을 의미한다.When described as "C1-C10" in the present specification, it means that the number of carbon atoms is 1 to 10. For example, C 1 -C 10 alkyl means alkyl having 1 to 10 carbon atoms.
본 명세서에서 사용된 용어 "할로겐" 및 "할로"는 플루오린, 클로린, 브로민 또는 아이오딘을 의미한다.As used herein, the terms “halogen” and “halo” refer to fluorine, chlorine, bromine or iodine.
본 명세서에서 사용된 용어 "불소가 치환된 아릴", "불소가 치환된 아릴옥시" 또는 "불소가 치환된 알콕시"는 각각 하나 이상의 수소 원자가 불소 원자로 치환된 아릴, 아릴옥시 또는 알콕시 그룹을 의미한다. 예를 들어, 할로아릴은 -C6H4F, -C6H3F2, -C6HF4, 및 이와 유사한 것을 포함한다. 여기에서 아릴 및 할로겐은 위에서 정의된 것과 같으며, 알콕시는 하기에 정의된 바와 같다.As used herein, the terms "fluorine-substituted aryl", "fluorine-substituted aryloxy" or "fluorine-substituted alkoxy" refer to an aryl, aryloxy or alkoxy group in which one or more hydrogen atoms are each replaced by a fluorine atom . For example, haloaryl includes —C 6 H 4 F, —C 6 H 3 F 2 , —C 6 HF 4 , and the like. wherein aryl and halogen are as defined above and alkoxy is as defined below.
본 명세서에서 사용된 용어 "알콕시"는 -OCH3, -OCH2CH3, -O(CH2)2CH3, -O(CH2)3CH3, -O(CH2)4CH3, -O(CH2)5CH3, 및 이와 유사한 것을 포함하는 -O-(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.As used herein, the term "alkoxy" means -OCH 3 , -OCH 2 CH 3 , -O(CH 2 ) 2 CH 3 , -O(CH 2 ) 3 CH 3 , -O(CH 2 ) 4 CH 3 , -O-(alkyl), including -O(CH 2 ) 5 CH 3 , and the like, wherein alkyl is as defined above.
본 명세서에서 사용된 용어 "저급알콕시"는 -O-(저급알킬)을 의미하며, 여기에서 저급 알킬은 위에서 정의된 것과 같다.As used herein, the term "lower alkoxy" means -O- (lower alkyl), wherein lower alkyl is as defined above.
본 명세서에서 사용된 용어 "아릴"은 5 내지 10의 고리 원자를 함유하는 탄소고리 방향족 그룹을 의미한다. 대표적인 예는 페닐, 톨일(tolyl), 자이릴(xylyl), 나프틸, 테트라하이드로나프틸, 안트라세닐(anthracenyl), 플루오레닐(fluorenyl), 인데닐(indenyl), 아주레닐(azulenyl) 등을 포함하나 이에 한정되는 것은 아니다. 탄소고리 방향족 그룹은 선택적으로 치환될 수 있다.As used herein, the term "aryl" refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. including, but not limited to. Carbocyclic aromatic groups may be optionally substituted.
본 명세서에서 사용된 용어 "아릴옥시"는 RO-이며, R은 상기 정의된 아릴이다. "아릴티오"는 RS-이며, R은 상기 정의된 아릴이다.As used herein, the term “aryloxy” is RO—, and R is aryl as defined above. "Arylthio" is RS- and R is aryl as defined above.
본 명세서에서 사용된 용어 "모노-알킬아미노"는 -NHCH3, -NHCH2CH3, -NH(CH2)2CH3, -NH(CH2)3CH3, -NH(CH2)4CH3, -NH(CH2)5CH3, 및 이와 유사한 것을 포함하는, -NH(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.As used herein, the term "mono-alkylamino" is -NHCH 3 , -NHCH 2 CH 3 , -NH(CH 2 ) 2 CH 3 , -NH(CH 2 ) 3 CH 3 , -NH(CH 2 ) 4 -NH(alkyl), including CH 3 , —NH(CH 2 ) 5 CH 3 , and the like, wherein alkyl is as defined above.
본 명세서에서 사용된 용어 "디-알킬아미노"는 -N(CH3)2, -N(CH2CH3)2, -N((CH2)2CH3)2, -N(CH3)(CH2CH3), 및 이와 유사한 것을 포함하는 -N(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.The term "di-alkylamino" as used herein means -N(CH 3 ) 2 , -N(CH 2 CH 3 ) 2 , -N((CH 2 ) 2 CH 3 ) 2 , -N(CH 3 ) -N(alkyl)(alkyl), including (CH 2 CH 3 ), and the like, wherein each alkyl independently of the other is alkyl as defined above.
본 명세서에서 사용된 용어 "모노-알킬실릴"는 -SiH2CH3, -SiH2CH3, - SiH2 (CH2)2CH3, -SiH2(CH2)3CH3, -SiH2(CH2)4CH3, -SiH2(CH2)5CH3, 및 이와 유사한 것을 포함하는, -SiH2(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.The term "mono-alkylsilyl" as used herein means -SiH 2 CH 3 , -SiH 2 CH 3 , -SiH 2 (CH 2 ) 2 CH 3 , -SiH 2 (CH 2 ) 3 CH 3 , -SiH 2 -SiH 2 (alkyl), including (CH 2 ) 4 CH 3 , —SiH 2 (CH 2 ) 5 CH 3 , and the like, wherein alkyl is as defined above.
본 명세서에서 사용된 용어 "디-알킬실릴"은 -SiH(CH3)2, -SiH(CH(CH3)2)(CH3), -SiH((CH2)2CH3)2, -SiH(CH3)(CH2CH3), 및 이와 유사한 것을 포함하는 -SiH(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, the term "di-alkylsilyl" means -SiH(CH 3 ) 2 , -SiH(CH(CH 3 ) 2 )(CH 3 ), -SiH((CH 2 ) 2 CH 3 ) 2 , - -SiH(alkyl)(alkyl), including SiH(CH 3 )(CH 2 CH 3 ), and the like, wherein each alkyl independently of the other is alkyl as defined above.
본 명세서에서 사용된 용어 "트리알킬실릴"은 -Si(CH3)3, -Si(CH2(CH3))3, -Si((CH2)2CH3)3, -Si(CH3)2(CH2CH3), 및 이와 유사한 것을 포함하는 -Si(알킬)(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, the term "trialkylsilyl" means -Si(CH 3 ) 3 , -Si(CH 2 (CH 3 )) 3 , -Si((CH 2 ) 2 CH 3 ) 3 , -Si(CH 3 ) ) 2 (CH 2 CH 3 ), and the like, —Si(alkyl)(alkyl)(alkyl), wherein each alkyl independently of the other is alkyl as defined above.
본 명세서에서 사용된 용어 "모노아릴실릴", "디아릴실릴" 및 "트리아릴실릴" 은 "모노알킬실릴", "디알킬실릴", 또는 "트리알킬실릴"에서 알킬 대신 아릴에 해당되는 치환기이다.As used herein, the terms "monoarylsilyl", "diarylsilyl" and "triarylsilyl" refer to a substituent corresponding to aryl instead of alkyl in "monoalkylsilyl", "dialkylsilyl", or "trialkylsilyl" to be.
이하, 본 발명의 실시예에 따른 에틸렌 올리고머화 방법을 상세히 설명한다.Hereinafter, an ethylene oligomerization method according to an embodiment of the present invention will be described in detail.
본 발명의 에틸렌 올리고머화 방법은,The ethylene oligomerization method of the present invention comprises:
유기용매의 존재 하, 하기 화학식 1로 표시되는 크롬 화합물과 하기 화학식 2로 표시되는 유기 알루미늄 화합물을 반응시키는 단계; 및reacting the chromium compound represented by the following formula (1) with the organoaluminum compound represented by the following formula (2) in the presence of an organic solvent; and
상기 단계 반응물에 수소 및 에틸렌을 접촉시켜 에틸렌 올리고머를 제조하는 단계를 포함한다.and contacting the reactants with hydrogen and ethylene to prepare an ethylene oligomer.
[화학식 1][Formula 1]
[화학식 2] [Formula 2]
Al(R11)(R12)(R13)Al(R 11 )(R 12 )(R 13 )
(상기 화학식 1 및 2에서,(In Formulas 1 and 2,
R은 C1-C60알킬 또는 C6-C60아릴이고; R is C1-C60 alkyl or C6-C60 aryl;
R1 내지 R4는 서로 독립적으로 C1-C60알킬 또는 C6-C60아릴이며; R 1 to R 4 are each independently C1-C60 alkyl or C6-C60 aryl;
X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트, 또는 에테르 및 아미노에서 선택되는 하나 이상을 포함하는 C1-C30하이드로카빌이고; X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate, or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;
A는 보론 또는 알루미늄이고; A is boron or aluminum;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴, 불소가 치환된 C6-C60아릴옥시 또는 불소가 치환된 C6-C60알콕시이며;Y 1 to Y 4 are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;
R11 내지 R13은 서로 독립적으로 C1-C20알킬이며,R 11 to R 13 are each independently C1-C20 alkyl;
상기 R의 알킬 또는 아릴 및 R1 내지 R4의 알킬 또는 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노C1-C30알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있다.)Alkyl or aryl of R and alkyl or aryl of R 1 to R 4 are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.)
본 발명의 에틸렌 올리고머화 방법은 상기 화학식 1로 표시되는 특정한 크롬 화합물을 사용함으로써 종래의 값비싼 메틸알루미녹산을 사용하지 않아도 높은 촉매 활성을 나타내어 에틸렌 올리고머화가 가능하다.In the ethylene oligomerization method of the present invention, ethylene oligomerization is possible by using a specific chromium compound represented by Formula 1, thereby exhibiting high catalytic activity without using conventional expensive methylaluminoxane.
나아가 본 발명의 에틸렌 올리고머화 방법은 상기 화학식 1로 표시되는 특정한 크롬 화합물을 사용함으로써 1-옥텐 및 1-헥센에 대한 선택도가 높고, 반응효율이 우수하여 매우 경제적이다.Furthermore, the ethylene oligomerization method of the present invention is very economical because of its high selectivity to 1-octene and 1-hexene and excellent reaction efficiency by using the specific chromium compound represented by Formula 1 above.
또한 본 발명의 에틸렌 올리고머화 방법은 수소 첨가제를 사용함으로써 촉매 활성이 저하시키기 않는 동시에 폴리올레핀 등의 부산물 생성을 획기적으로 억제시켜 공정안정성을 유지할 수 있다.In addition, the ethylene oligomerization method of the present invention can maintain process stability by dramatically suppressing the generation of by-products such as polyolefin without reducing catalyst activity by using a hydrogen additive.
본 발명의 일 실시예에 따른 에틸렌 올리고머화 방법에 있어서, 유기용매의 존재 하, 하기 화학식 1로 표시되는 크롬 화합물과 하기 화학식 2로 표시되는 유기 알루미늄 화합물을 반응시키는 단계 후에 수소 및 에틸렌을 순차적으로 주입함으로써 촉매 활성을 높이는 동시에 폴리에틸렌 등의 반응 부산물 생성을 획기적으로 저하시킬 수 있다.In the ethylene oligomerization method according to an embodiment of the present invention, in the presence of an organic solvent, hydrogen and ethylene are sequentially reacted with the chromium compound represented by the following formula (1) with the organoaluminum compound represented by the following formula (2) By injecting, it is possible to increase the catalytic activity and at the same time dramatically reduce the generation of reaction by-products such as polyethylene.
향상된 선택성 및 촉매활성을 가지기위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 에틸렌과 수소의 몰비는 1: 0.001 내지 3.0일 수 있다.Preferably in terms of having improved selectivity and catalytic activity, the molar ratio of ethylene and hydrogen according to an embodiment of the present invention may be 1: 0.001 to 3.0.
촉매 활성을 유지하면서도 에틸렌 올리고머화 방법의 부산물인 폴리에틸렌 등의 생성을 억제시키기 위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 에틸렌: 수소의 몰비는 1 : 0.01 내지 2.0, 보다 바람직하게 1 : 0.04 내지 0.32, 더욱 좋기로는 0.09 내지 0.19일 수 있다.In terms of suppressing the production of polyethylene, which is a by-product of the ethylene oligomerization method while maintaining catalytic activity, the molar ratio of ethylene: hydrogen according to an embodiment of the present invention is preferably 1: 0.01 to 2.0, more preferably 1: 0.04. to 0.32, more preferably 0.09 to 0.19.
본 발명의 일 실시예에 따른 본 발명의 일 실시예에 따른 크롬 화합물과 상기 화학식 2로 표시되는 유기 알루미늄 화합물의 몰비는 1 : 10 내지 500, 바람직하게 1: 100 내지 300, 보다 바람직하게 1 : 150 내지 250일 수 있다.The molar ratio of the chromium compound according to an embodiment of the present invention to the organoaluminum compound represented by Chemical Formula 2 according to an embodiment of the present invention is 1: 10 to 500, preferably 1: 100 to 300, more preferably 1: It may be 150 to 250.
본 발명의 에틸렌 올리고머화 방법은 본 발명의 상기 화학식 1로 표시되는 특정한 크롬 화합물과 상기 화학식 2와 보다 바람직한 조합으로 본 발명의 화학식 1 및 화학식 2에서, R은 C1-C60알킬이며; R1 내지 R4는 서로 독립적으로 C6-C60아릴이며; X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C30하이드로카빌이고; A는 보론 또는 알루미늄이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴, 불소가 치환된 C6-C60아릴옥시 또는 불소가 치환된 C6-C60알콕시이며; R11 내지 R13은 서로 독립적으로 C1-C20알킬이며, 상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있는 것일 수 있다.The ethylene oligomerization method of the present invention is a more preferred combination of a specific chromium compound represented by Chemical Formula 1 of the present invention and Chemical Formula 2, and in Chemical Formulas 1 and 2 of the present invention, R is C1-C60 alkyl; R 1 to R 4 are each independently C6-C60 aryl; X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C30 hydrocarbyl including ether; A is boron or aluminum; Y 1 to Y 4 are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy; R 11 to R 13 are each independently C1-C20 alkyl, wherein R alkyl and R 1 to R 4 aryl are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino; DiC1-C30alkylamino, triC1-C30alkylamino, monoC6-C30arylamino, diC6-C30arylamino, triC6-C30arylamino, monoalkylsilyl, diC1-C30alkylsilyl, triC1-C30 It may be one which may be further substituted with one or more selected from alkylsilyl, mono C6-C30 arylsilyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.
본 발명의 일 실시예에 따른 화학식 1 및 화학식 2의 보다 더 바람직한 조합으로는, 화학식 1 및 화학식 2에서 R은 C1-C30알킬이며; R1 내지 R4는 서로 독립적으로 C6-C30아릴이며; X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C20하이드로카빌이고; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C30아릴, 불소가 치환된 C6-C30아릴옥시 또는 불소가 치환된 C6-C30알콕시이며; R11 내지 R13은 서로 독립적으로 C1-C20알킬이며, 상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C20알킬, C6-C20아릴, C1-C20알콕시, 모노C1-C20알킬아미노, 디C1-C20알킬아미노, 트리C1-C20알킬아미노, 모노C6-C20아릴아미노, 디C6-C20아릴아미노, 트리C6-C20아릴아미노, 모노C1-C20알킬실릴, 디C1-C20알킬실릴, 트리C1-C20알킬실릴, 모노C6-C20아릴실릴, 디C6-C20아릴실릴 및 트리C6-C20아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있는 것일 수 있으며,In a more preferred combination of Formulas 1 and 2 according to an embodiment of the present invention, in Formulas 1 and 2, R is C1-C30 alkyl; R 1 to R 4 are each independently C6-C30 aryl; X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether; A is boron; Y 1 to Y 4 are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy; R 11 to R 13 are each independently C1-C20 alkyl, wherein the alkyl of R and the aryl of R 1 to R 4 are C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, monoC1-C20 alkylamino; diC1-C20alkylamino, triC1-C20alkylamino, monoC6-C20arylamino, diC6-C20arylamino, triC6-C20arylamino, monoC1-C20alkylsilyl, diC1-C20alkylsilyl, tri C1-C20 alkylsilyl, mono C6-C20 arylsilyl, diC6-C20 arylsilyl and triC6-C20 arylsilyl may be one that may be further substituted with one or more selected from,
더욱 좋기로는 R은 C1-C20알킬이며; R1 내지 R4는 서로 독립적으로 C6-C20아릴이며; X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트 또는 아세틸아세토네이트이고; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C20아릴, 불소가 치환된 C6-C20아릴옥시 또는 불소가 치환된 C6-C20알콕시이며; R11 내지 R13은 서로 독립적으로 C1-C10알킬이며, 상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C10알킬, C6-C12아릴, C1-C10알콕시, 모노C1-C10알킬아미노, 디C1-C10알킬아미노, 트리C1-C10알킬아미노, 모노C6-C12아릴아미노, 디C6-C12아릴아미노, 트리C6-C12아릴아미노, 모노C1-C10알킬실릴, 디C1-C10알킬실릴, 및 트리C1-C10알킬실릴에서 선택되는 하나이상으로 더 치환될 수 있는 것일 수 있으며, 보다 좋기로는 R은 C1-C10알킬이며; R1 내지 R4는 서로 독립적으로 C6-C12아릴이며; X1 및 X2는 각각 독립적으로 할로겐이고; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C12아릴이며; R11 내지 R13은 서로 독립적으로 C1-C7알킬이며, 상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C7알킬 및 트리C1-C7알킬실릴에서 선택되는 하나이상으로 더 치환될 수 있는 것일 수 있다.more preferably R is C1-C20 alkyl; R 1 to R 4 are each independently C6-C20 aryl; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate or acetylacetonate; A is boron; Y 1 to Y 4 are each independently fluorine-substituted C6-C20 aryl, fluorine-substituted C6-C20 aryloxy, or fluorine-substituted C6-C20 alkoxy; R 11 to R 13 are each independently C1-C10 alkyl, wherein the alkyl of R and the aryl of R 1 to R 4 are C1-C10 alkyl, C6-C12 aryl, C1-C10 alkoxy, monoC1-C10 alkylamino; diC1-C10 alkylamino, triC1-C10 alkylamino, monoC6-C12 arylamino, diC6-C12 arylamino, triC6-C12 arylamino, monoC1-C10 alkylsilyl, diC1-C10 alkylsilyl, and It may be one which may be further substituted with one or more selected from triC1-C10 alkylsilyl, more preferably R is C1-C10 alkyl; R 1 to R 4 are each independently C6-C12 aryl; X 1 and X 2 are each independently halogen; A is boron; Y 1 to Y 4 are each independently C6-C12 aryl substituted with fluorine; R 11 to R 13 are each independently C1-C7 alkyl, wherein the alkyl of R and the aryl of R 1 to R 4 may be further substituted with one or more selected from C1-C7 alkyl and triC1-C7 alkylsilyl it could be
촉매효율, 에틸렌 올리고머의 선택도 및 폴리올레핀 생성 억제 측면에서 보다 바람직하게 상기 화학식 1은 하기 화학식 3으로 표시될 수 있다.More preferably, in terms of catalyst efficiency, selectivity of ethylene oligomer, and inhibition of polyolefin production, Chemical Formula 1 may be represented by Chemical Formula 3 below.
[화학식 3][Formula 3]
(상기 화학식 3에서,(In Formula 3,
R은 C1-C30알킬 또는 C6-C30아릴이고; R is C1-C30 alkyl or C6-C30 aryl;
X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C20하이드로카빌이고; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;
A는 보론 또는 알루미늄이고; A is boron or aluminum;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C30아릴, 불소가 치환된 C6-C30아릴옥시 또는 불소가 치환된 C6-C30알콕시이며;Y 1 to Y 4 are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy;
R21 내지 R32는 서로 독립적으로 C1-C20알킬이며,R 21 to R 32 are each independently C1-C20 alkyl,
상기 R의 알킬 또는 아릴은 C1-C20알킬, C6-C20아릴, C1-C20알콕시, 모노 C1-C20알킬아미노, 디C1-C20알킬아미노, 트리C1-C20알킬아미노, 모노C1-C20아릴아미노, 디C6-C20아릴아미노 및 트리C6-C20아릴아미노에서 선택되는 하나이상으로 더 치환될 수 있다.)Alkyl or aryl of R is C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, mono C1-C20 alkylamino, diC1-C20 alkylamino, triC1-C20 alkylamino, mono C1-C20 arylamino, It may be further substituted with one or more selected from diC6-C20 arylamino and triC6-C20 arylamino.)
본 발명의 일 실시예에 따른 화학식 3으로 표시되는 크롬 화합물은 인(P)과 결합된 페닐(Ph)에 특정한 치환기인 트리알킬실릴기가 도입됨으로써 보다 향상된 촉매 활성 및 에틸렌 올리고머 선택도를 가진다.The chromium compound represented by Formula 3 according to an embodiment of the present invention has improved catalytic activity and ethylene oligomer selectivity by introducing a trialkylsilyl group, which is a specific substituent, to phenyl (Ph) bonded to phosphorus (P).
바람직하게 본 발명의 일 실시예에 따른 화학식 3에서 R은 C1-C20알킬이고; X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트이며; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C20아릴 또는 불소가 치환된 C6-C20아릴옥시일 수 있으며, 좋기로는 R은 C1-C10알킬이고; X1 및 X2는 각각 독립적으로 할로겐 또는 C1-C10알킬이며; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C12아릴일 수 있다.Preferably, in Formula 3 according to an embodiment of the present invention, R is C1-C20 alkyl; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate; A is boron; Y 1 to Y 4 may independently of each other be C6-C20 aryl substituted with fluorine or C6-C20 aryloxy substituted with fluorine, preferably R is C1-C10 alkyl; X 1 and X 2 are each independently halogen or C1-C10 alkyl; A is boron; Y 1 to Y 4 may be each independently fluorine-substituted C6-C12 aryl.
더욱 바람직하게 본 발명의 일 실시예에 따른 화학식 3에서 상기 화학식 3에서, R은 C1-C5알킬이고; X1 및 X2는 염소이고; A는 보론이고; Y1 내지 Y4는 (C6F5)4이고; R21 내지 R32는 서로 독립적으로 C5-C8알킬일 수 있다.More preferably, in Formula 3 in Formula 3 according to an embodiment of the present invention, R is C1-C5 alkyl; X 1 and X 2 are chlorine; A is boron; Y 1 to Y 4 are (C 6 F 5 ) 4 ; R 21 to R 32 may be each independently C5-C8 alkyl.
바람직하게 본 발명의 일 실시예에 따른 화학식 3은 하기 화학식 4로 표시될 수 있다.Preferably, Chemical Formula 3 according to an embodiment of the present invention may be represented by Chemical Formula 4 below.
[화학식 4][Formula 4]
(상기 화학식 4에서,(In Formula 4,
R은 C1-C20알킬 또는 C6-C20아릴이고; R is C1-C20 alkyl or C6-C20 aryl;
X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C20하이드로카빌이고; X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;
A는 보론 또는 알루미늄이고; A is boron or aluminum;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C20아릴, 불소가 치환된 C6-C20아릴옥시 또는 불소가 치환된 C6-C20알콕시이며;Y 1 to Y 4 are each independently fluorine-substituted C6-C20 aryl, fluorine-substituted C6-C20 aryloxy, or fluorine-substituted C6-C20 alkoxy;
Ra 내지 Rd는 서로 독립적으로 C1-C10알킬이며,R a to R d are each independently C1-C10 alkyl,
상기 R의 알킬 또는 아릴은 C1-C20알킬에서 선택되는 하나이상으로 더 치환될 수 있다.)Alkyl or aryl of R may be further substituted with one or more selected from C1-C20 alkyl.)
바람직하게 본 발명의 일 실시예에 따른 화학식 4에서 R은 C1-C10알킬이고; X1 및 X2는 각각 독립적으로 할로겐, C1-C10알킬 또는 아세틸아세토네이트이고; A는 보론이고; Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C12아릴이며; Ra 내지 Rd는 서로 독립적으로 C1-C8알킬이며, 상기 R의 알킬 또는 아릴은 C1-C8알킬에서 선택되는 하나이상으로 더 치환될 수 있으며, 보다 바람직하게는 Ra 내지 Rd가 모두 동일하게 C1-C8알킬일 수 있다.Preferably, in Formula 4 according to an embodiment of the present invention, R is C1-C10 alkyl; X 1 and X 2 are each independently halogen, C1-C10 alkyl or acetylacetonate; A is boron; Y 1 to Y 4 are each independently C6-C12 aryl substituted with fluorine; R a to R d are each independently C1-C8 alkyl, and the alkyl or aryl of R may be further substituted with one or more selected from C1-C8 alkyl, more preferably all of R a to R d are the same It may be C1-C8 alkyl.
바람직하게 본 발명의 일 실시예에, 상기 화학식 4의 크롬 화합물은 R이 C1-C5알킬, Ra 내지 Rd는 C5-C8알킬일 수 있으며, 보다 바람직하게는 R이 분지쇄C3-C5알킬, Ra 내지 Rd는 C5-C8알킬일 수 있으며, 더욱 좋기로는 R이 이소프로필기, Ra 내지 Rd는 옥틸기(n-Octyl), [A(Y1)(Y2)(Y3)(Y4)]-이 [B(C6F5)4]-인 것일 수 있다. 이와 같은 구조적 예시의 크롬 화합물은 에틸렌 올리고머화 반응용 촉매 시스템에 적용 시 활성도 및 선택도를 더욱 현저하게 향상시키면서도 부산물인 고분자 폴리에틸렌 화합물의 생성량을 더욱 저감할 수 있다.Preferably, in an embodiment of the present invention, in the chromium compound of Formula 4, R may be C1-C5 alkyl, R a to R d may be C5-C8 alkyl, more preferably R is branched-chain C3-C5 alkyl , R a to R d may be C5-C8 alkyl, more preferably R is an isopropyl group, R a to R d are an octyl group (n-Octyl), [A(Y 1 )(Y 2 )( Y 3 )(Y 4 )] - may be [B(C 6 F 5 ) 4 ] - . When applied to a catalyst system for ethylene oligomerization reaction, the chromium compound of such a structural example can further significantly improve the activity and selectivity, while further reducing the amount of the by-product, a high molecular polyethylene compound.
본 발명의 일 실시예에 따른 에틸렌 올리고머화 방법에 있어서 유기 용매는 그 종류에 특별히 한정이 없으나, 할로겐으로 치환 또는 비치환된 탄화수소 용매일 수 있다. 구체적으로, 상기 탄화수소 용매로는 탄소수 4 내지 20의 지방족 탄화수소 용매, 탄소수 6 내지 20의 방향족 탄화수소 용매, 이들의 혼합물 등이 사용될 수 있다. 보다 구체적으로, 상기 할로겐으로 치환 또는 비치환된 탄화수소 용매로는 톨루엔, 자일렌, 클로로벤젠, 디클로로벤젠, 디클로로메테인, 메틸사이클로헥센, 사이클로헥센 등을 일례로 들 수 있으며, 바람직하게 디클로로메테인, 메틸사이클로헥센, 사이클로헥센일 수 있으며, 상기 예시한 용매를 사용할 경우 중합 활성이 높고 올리고머화 반응 후 생성물인 1-헥센 및 1-옥텐과 용매와의 분리가 보다 용이하다.In the ethylene oligomerization method according to an embodiment of the present invention, the organic solvent is not particularly limited in type, but may be a hydrocarbon solvent substituted or unsubstituted with halogen. Specifically, as the hydrocarbon solvent, an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms, an aromatic hydrocarbon solvent having 6 to 20 carbon atoms, a mixture thereof, and the like may be used. More specifically, examples of the hydrocarbon solvent substituted or unsubstituted with halogen include toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, methylcyclohexene, cyclohexene, and the like, preferably dichloromethane. , methylcyclohexene, or cyclohexene, and when the solvents exemplified above are used, the polymerization activity is high and the separation between the products 1-hexene and 1-octene and the solvent after the oligomerization reaction is easier.
본 발명의 일 실시예에 따른 올리고머를 제조하는 단계는 10 내지 80℃에서 10분 내지 2시간동안, 바람직하게 20 내지 80℃에서 10분 내지 1시간동안, 보다 바람직하게는 20 내지 60℃에서 20분 내지 50분동안 수행될 수 있다.The step of preparing the oligomer according to an embodiment of the present invention is performed at 10 to 80° C. for 10 minutes to 2 hours, preferably at 20 to 80° C. for 10 minutes to 1 hour, more preferably at 20 to 60° C. for 20 minutes. It can be carried out for minutes to 50 minutes.
본 발명의 일 실시예에 따른 올리고머는 폴리에틸렌의 함량이 0.6중량%이하, 바람직하게 0.5중량%이하, 보다 바람직하게는 0.4%미만일 수 있다.In the oligomer according to an embodiment of the present invention, the content of polyethylene may be 0.6% by weight or less, preferably 0.5% by weight or less, and more preferably less than 0.4%.
본 발명의 일 실시예에 따른 에틸렌 올리고머화 방법은 특정한 크롬 화합물과 수소 첨가제를 사용함으로써 높은 활성 및 선택도를 가지는 동시에 폴리에틸렌의 생성을 억제해 공정 안정성을 유지할 수 있다. The ethylene oligomerization method according to an embodiment of the present invention can maintain process stability by suppressing the production of polyethylene while having high activity and selectivity by using a specific chromium compound and a hydrogen additive.
이하 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 이들 실시예들은 예시적인 목적일 뿐 본 발명이 이들 실시예에 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.
[제조예 1][Production Example 1]
한국특허 10-2087994에 기재된 방법에 따라 하기 화학식 A로 표시되는 크롬 화합물을 제조하였다.According to the method described in Korean Patent No. 10-2087994, a chromium compound represented by the following formula (A) was prepared.
[화학식 A][Formula A]
도 1에 제조된 화학식 A의 13P NMR, 1H NMR, 19F NMR, EPR(Electron paramagnetic resonance) 결과를 나타낸 그래프를 나타내었으며, 이로부터 화학식 A가 제조되었음을 알 수 있다. A graph showing the results of 13 P NMR, 1 H NMR, 19 F NMR, and EPR (electron paramagnetic resonance) of Formula A prepared in FIG. 1 is shown, from which it can be seen that Formula A was prepared.
[제조예 2][Production Example 2]
제조예 1에서 n-butyl기를 n-octyl기로 치환한 화학식 B로 표시되는 크롬화합물을 제조하였다. In Preparation Example 1, a chromium compound represented by Formula B in which the n-butyl group was substituted with an n-octyl group was prepared.
<화학식 B><Formula B>
Cl-Si(n-Octyl)3 합성 : 아세틸클로라이드 (1.54 g, 19.6 mmol)을 CH2Cl2 (7 mL)에 용해한 용액을 트리옥틸실란 (4.83 g, 13.1 mmol) 및 FeCl3 (0.0549 g, 0.262 mmol)를 포함하는 CH2Cl2 (20 mL) 용액에 적하하였다. FeCl3가 녹아 들어가면서 발열과 함께 용액의 색이 노란색으로 바뀌는 것을 확인 후 상온에서 24 시간 동안 교반시켰다. 진공배관(vacuum line)을 이용하여 용매, 부산물 아세트알데히드와 비반응물인 아세틸클로라이드을 제거하였다. 잔여물을 헥산 (hexane, 10 mL)에 용해시킨 후 녹지 않는 갈색 고체(FeCl3)를 여과(Celite-aided filtration) 하여 제거하였다. 용매를 진공배관(vacuum line)을 이용하여 제거하여 연한 노란 오일(oil) 화합물을 수득하였다 (4.98 g, 98%). Cl-Si(n-Octyl) 3 Synthesis: A solution of acetyl chloride (1.54 g, 19.6 mmol) in CH 2 Cl 2 (7 mL) was dissolved in trioctylsilane (4.83 g, 13.1 mmol) and FeCl 3 (0.0549 g, 0.262 mmol) was added dropwise to a solution of CH 2 Cl 2 (20 mL). As FeCl 3 melted, it was confirmed that the color of the solution was changed to yellow with exotherm and stirred at room temperature for 24 hours. A solvent, by-product acetaldehyde and non-reactant acetyl chloride were removed using a vacuum line. After the residue was dissolved in hexane (hexane, 10 mL), an insoluble brown solid (FeCl 3 ) was removed by filtration (Celite-aided filtration). The solvent was removed using a vacuum line to obtain a pale yellow oil compound (4.98 g, 98%).
BrC6H4-p-Si(n-Octyl)3 합성 : 1,4-다이브로모벤젠 (3.31 g, 14.0 mmol)을 THF(35 mL)에 녹이고, -78 ℃에서 n-부틸리튬 (5 mL, 2.5 M 헥산 용액, 12.5 mmol)을 주입한 뒤 -78 ℃를 유지시키며 2 시간 동안 교반시켰다. Cl-Si(n-Octyl)3 (4.79 g, 11.9 mmol)을 THF (6 mL)에 용해시켜 주입하고, 온도를 상온으로 올려 3 시간 동안 반응시켰다. 진공배관(vacuum line)을 이용하여 용매를 제거하고, 헥산 (18 mL)에 원하는 산물을 용해시킨 후 불용성 흰색 고체(LiBr)를 여과(Celite-aided filtration) 하여 제거하였다. 여과된 액체를 진공배관(vacuum line)을 이용하여 용매를 제거하고, 다시 헥산 (18 mL)에 녹여 실리카겔 (short pad of silica gel, 6.22 g)을 통과시켰다. 용매를 진공배관(vacuum line)을 이용하여 제거한 뒤, 잔류물을 80 ℃에서 진공 증류하여 비반응물(1,4-다이브로모벤젠)을 제거하여 오일로 목적 화합물을 수득하였다 (5.71 g, 92%).BrC 6 H 4 -p-Si(n-Octyl) 3 Synthesis: 1,4-dibromobenzene (3.31 g, 14.0 mmol) was dissolved in THF (35 mL), and n-butyllithium (5 mL) at -78 ° C. , 2.5 M hexane solution, 12.5 mmol) was injected and stirred for 2 hours while maintaining -78 °C. Cl-Si(n-Octyl) 3 (4.79 g, 11.9 mmol) was dissolved in THF (6 mL) and injected, and the temperature was raised to room temperature and reacted for 3 hours. The solvent was removed using a vacuum line, the desired product was dissolved in hexane (18 mL), and the insoluble white solid (LiBr) was removed by filtration (Celite-aided filtration). After removing the solvent from the filtered liquid using a vacuum line, it was again dissolved in hexane (18 mL) and passed through a short pad of silica gel (6.22 g). After the solvent was removed using a vacuum line, the residue was vacuum distilled at 80 °C to remove the unreacted material (1,4-dibromobenzene) to obtain the target compound as an oil (5.71 g, 92%). ).
ClP[C6H4-p-Si(n-Octyl)3]2 합성 : BrC6H4-p-Si(n-Octyl)3 (5.71 g, 10.9 mmol)을 THF (39 mL)에 녹이고, -78 ℃에서 n-부틸리튬 (4.36 mL, 2.5 M 헥산 용액, 10.9 mmol)을 주입한 뒤, -78 ℃를 유지시키며 1 시간 동안 교반시켰다. THF (9 mL)에 용해되어 있는 다이클로로(다이에틸아미노)포스핀 (0.949 g, 5.45 mmol)을 15분동안 주입하고, 온도를 5 ℃로 올려 온도를 유지하면서 2 시간 동안 반응시켰다. 메틸시클로헥산 (methylcyclohexane, 19 mL)을 주입한 뒤 상온에서 진공배관(vacuum line)을 이용하여 용매를 제거하고, 메틸시클로헥산 (31 mL)을 넣어 불용성 흰색 고체(LiBr 및 LiCl)를 여과(Celite-aided filtration) 하여 제거하였다. 용매를 제거한 후 PCl3 (4.12 g, 30.0 mmol)를 투입하고 70 ℃에서 2 시간 동안 반응시켰다. 80 ℃에서 진공 증류하여 비반응 물질인 PCl3와 부산물 다이클로로(다이에틸아미노)포스핀을 제거하고 노란 오일의 화합물을 수득하였다. 오일 화합물을 헥산 (23 mL)에 용해한 후 녹지 않는 부산물을 여과(Celite-aided filtration) 하여 제거하였다. 용매를 진공배관(vacuum line)을 통해 제거하여 노란 오일로 목적 화합물을 수득하였다 (5.18 g, 99%).ClP[C 6 H 4 -p-Si(n-Octyl) 3 ] 2 Synthesis: BrC 6 H 4 -p-Si(n-Octyl) 3 (5.71 g, 10.9 mmol) was dissolved in THF (39 mL), After injecting n-butyllithium (4.36 mL, 2.5 M hexane solution, 10.9 mmol) at -78 °C, the mixture was stirred at -78 °C for 1 hour. Dichloro(diethylamino)phosphine (0.949 g, 5.45 mmol) dissolved in THF (9 mL) was injected for 15 minutes, and the temperature was raised to 5° C. and reacted for 2 hours while maintaining the temperature. After injecting methylcyclohexane (19 mL), the solvent is removed using a vacuum line at room temperature, and methylcyclohexane (31 mL) is added and the insoluble white solids (LiBr and LiCl) are filtered (Celite). -aided filtration) to remove it. After removing the solvent, PCl 3 (4.12 g, 30.0 mmol) was added and reacted at 70° C. for 2 hours. By vacuum distillation at 80° C., PCl 3 as a non-reacting material and by-product dichloro(diethylamino)phosphine were removed to obtain a compound as a yellow oil. After dissolving the oil compound in hexane (23 mL), the insoluble by-product was removed by filtration (Celite-aided filtration). The solvent was removed through a vacuum line to give the title compound as a yellow oil (5.18 g, 99%).
i-PropylN[P(C6H4-p-Si(n-Octyl)3)2]2 합성 : i-PrNH2 (0.135 g, 2.28 mmol)를 CH2Cl2 (11 mL)에 용해한 용액을 ClP[C6H4-p-Si(n-Octyl)3]2 (4.79 g, 5.02 mmol) 및 Et3N (2.31 g, 22.8 mmol)를 포함하는 CH2Cl2 (19 mL) 용액에 적하하였다. 반응물을 상온에서 12 시간 교반시킨 후, 진공배관(vacuum line)으로 휘발성분을 제거하였다. 잔여물에 헥산 (40 mL)을 첨가한 후, 불용성 부산물인 (Et3NH)+Cl- 을 여과(Celite-aided filtration)하여 제거하였다. 여과된 액체는 hexane/Et3N (v/v, 50:1)로 전처리된 실리카겔(short pad of silica gel)을 통과시킨 후 진공배관(vacuum line)을 이용하여 용매를 제거하여 무색의 오일 형태의 결과물을 수득하였다 (4.26 g, 98%).i-PropylN[P(C 6 H 4 -p-Si(n-Octyl) 3 ) 2 ] 2 Synthesis: A solution of i-PrNH 2 (0.135 g, 2.28 mmol) in CH 2 Cl 2 (11 mL) was prepared ClP[C 6 H 4 -p-Si(n-Octyl) 3 ] 2 (4.79 g, 5.02 mmol) and Et 3 N (2.31 g, 22.8 mmol) containing CH 2 Cl 2 (19 mL) dropwise did. After the reaction was stirred at room temperature for 12 hours, volatiles were removed through a vacuum line. After adding hexane (40 mL) to the residue, an insoluble by-product (Et 3 NH) + Cl − was removed by filtration (Celite-aided filtration). The filtered liquid was passed through a short pad of silica gel pretreated with hexane/Et 3 N (v/v, 50:1), and the solvent was removed using a vacuum line to form a colorless oil. of (4.26 g, 98%).
[(i-PropylN[P(C6H4-p-Si(n-Octyl)3)2]2)-CrCl2]+[B(C6F5)4]- 합성 : CH2Cl2 (13 mL)에 i-PropylN[P(C6H4-p-Si(n-Octyl)3)2]2 (1.41 g, 0.742 mmol)을 용해시킨 용액을 CH2Cl2 (4.5 mL)에 [CrCl2(NCCH3)4]+[B(C6F5)4]- (0.715 g, 0.742 mmol)을 용해시켜 제조한 용액에 적하하였다. 반응물을 상온에서 2.5 시간 동안 교반한 후, 진공배관(vacuum line)으로 용매를 제거하여 점성의 녹색 오일을 수득하였다.[(i-PropylN[P(C 6 H 4 -p-Si(n-Octyl) 3 ) 2 ] 2 )-CrCl 2 ] + [B(C 6 F 5 ) 4 ] - Synthesis: CH 2 Cl 2 ( 13 mL) of i-PropylN[P(C 6 H 4 -p-Si(n-Octyl) 3 ) 2 ] 2 (1.41 g, 0.742 mmol) in CH 2 Cl 2 (4.5 mL) [ It was added dropwise to a solution prepared by dissolving CrCl 2 (NCCH 3 ) 4 ] + [B(C 6 F 5 ) 4 ] - (0.715 g, 0.742 mmol). After the reaction was stirred at room temperature for 2.5 hours, the solvent was removed through a vacuum line to obtain a viscous green oil.
도 2에 제조된 화학식 B의 13P NMR, 1H NMR, 19F NMR 결과를 나타낸 그래프를 나타내었으며, 이로부터 화학식 B가 제조되었음을 알 수 있다. A graph showing the 13 P NMR, 1 H NMR, and 19 F NMR results of Formula B prepared in FIG. 2 is shown, from which it can be seen that Formula B was prepared.
얻어진 오일을 메틸시클로헥산 (5 mL)에 녹인 뒤 진공배관(vacuum line)으로 용매를 제거하였다. 이 과정을 CH3CN과 CH3Cl2가 완전히 제거될 때까지 반복하여 점성의 녹색 오일 형태의 결과물을 수득하였다 (2 g, 100%). 이렇게 얻어진 결과물을 메틸시클로헥산 (23.4 mL)에 녹여 10 wt% 용액을 만들어 에틸렌 올리고머화에 사용하였다.The obtained oil was dissolved in methylcyclohexane (5 mL), and the solvent was removed through a vacuum line. This process was repeated until CH 3 CN and CH 3 Cl 2 were completely removed to obtain a result in the form of a viscous green oil (2 g, 100%). The resulting product was dissolved in methylcyclohexane (23.4 mL) to prepare a 10 wt% solution and used for ethylene oligomerization.
[제조예 3][Production Example 3]
제조예 1에서 n-butyl기를 를 n-hexyl기로 치환한 화학식 C로 표시되는 크롬화합물을 제조하였다. In Preparation Example 1, a chromium compound represented by Formula C in which the n-butyl group was substituted with an n-hexyl group was prepared.
<화학식 C><Formula C>
BrC6H4-p-Si(n-Hexyl)3 합성 : Cl-Si(n-Hexyl)3 (0.218 g, 0.682 mmol)를 사용하여 상기 C6H4-p-Si(n-Octyl)3 제조 방법에 기술한 동일 방법 및 조건에 의하여 합성하여 오일 화합물(C6H4-p-Si(n-Hexyl)3)을 수득하였다 (0.280 g, 94%).BrC 6 H 4 -p-Si(n-Hexyl) 3 Synthesis: Using Cl-Si(n-Hexyl) 3 (0.218 g, 0.682 mmol) above C 6 H 4 -p-Si(n-Octyl) 3 It was synthesized according to the same method and conditions described in the preparation method to obtain an oil compound (C 6 H 4 -p-Si(n-Hexyl) 3 ) (0.280 g, 94%).
ClP[C6H4-p-Si(n-Hexyl)3]2 합성 : BrC6H4-p-Si(n-Hexyl)3 (0.197 g, 0.447 mmol)을 사용하여 상기 ClP[C6H4-p-Si(n-Octyl)3]2 제조 방법에 기술한 동일 방법 및 조건에 의하여 합성하여 오일인 목적 화합물을 수득하였다 (0.139 g, 79%).ClP[C 6 H 4 -p-Si(n-Hexyl) 3 ] 2 Synthesis: ClP[C 6 H above using BrC 6 H 4 -p-Si(n-Hexyl) 3 (0.197 g, 0.447 mmol) 4 -p-Si(n-Octyl) 3 ] 2 It was synthesized according to the same method and conditions described in the preparation method to obtain the target compound as an oil (0.139 g, 79%).
i-PropylN[P(C6H4-p-Si(n-Hexyl)3)2]2 합성 : ClP[C6H4-p-Si(n-Hexyl)3]2 (0.139 g, 0.177 mmol)을 사용하여 상기 i-PropylN[P(C6H4-p-Si(n-Octyl)3)2]2 제조 방법에 기술한 동일 방법 및 조건에 의하여 합성하여 오일인 목적 화합물을 수득하였다 (0.132 g, 76%).i-PropylN[P(C 6 H 4 -p-Si(n-Hexyl) 3 ) 2 ] 2 Synthesis: ClP[C 6 H 4 -p-Si(n-Hexyl) 3 ] 2 (0.139 g, 0.177 mmol ) using i-PropylN[P(C 6 H 4 -p-Si(n-Octyl) 3 ) 2 ] 2 was synthesized according to the same method and conditions described in the preparation method to obtain the target compound as an oil ( 0.132 g, 76%).
[(i-PropylN[P(C6H4-p-Si(n-Hexyl)3)2]2)-CrCl2]+[B(C6F5)4]- 합성 : i-PropylN[P(C6H4-p-Si(n-Hexyl)3)2]2 를 사용하여 상기 [(i-PropylN[P(C6H4-p-Si(n-Octyl)3)2]2)-CrCl2]+[B(C6F5)4]- 제조 방법에 기술한 동일 방법 및 조건에 의하여 합성하여 오일인 목적 화합물을 수득하였다 (0.0818 g, 90%).[(i-PropylN[P(C 6 H 4 -p-Si(n-Hexyl) 3 ) 2 ] 2 )-CrCl 2 ] + [B(C 6 F 5 ) 4 ] - Synthesis: i-PropylN[P (C 6 H 4 -p-Si(n-Hexyl) 3 ) 2 ] 2 above using [(i-PropylN[P(C 6 H 4 -p-Si(n-Octyl) 3 ) 2 ] 2 ) -CrCl 2 ] + [B(C 6 F 5 ) 4 ] - Synthesized by the same method and conditions described in the preparation method to obtain the target compound as an oil (0.0818 g, 90%).
[실시예 1] 에틸렌 올리고머화 반응[Example 1] Ethylene oligomerization reaction
40°C로 가열한 2L Auto-clave 반응기에 메틸시클로헥산 1L 및 화학식 A의 크롬 화합물(0.41 mg, 0.15 μmol)을 투입한 후, iBu3Al(30 μmol)를 메틸시클로헥산(methylcyclohexane, 1 mL)에 희석하여 상온에서 주사기를 사용하여 반응기 내로 주입하였다. 수소를 20 psig의 압력으로 주입 후, 에틸렌 가스를 500 psig의 압력으로 주입하였다. 반응기 내부 압력이 500psig를 유지하도록 에틸렌을 연속적으로 공급하면서 반응온도를 40°C로 유지한 상태에서 30분간 반응 진행 후, 에틸렌 가스를 배출하여 반응을 종료하였다. 생성된 물질의 가스크로마토그래피 분석(GC analysis)을 통해, 생성된 올리고머{1-octene (1-C8), 1-hexene (1-C6), methylcyclopentane + methylenecyclopentane (cy-C6), 및 C10이상의 올리고머 (> C10)}의 함량을 측정하여 생성물의 중량비를 계산하였다. 생성된 고체상의 폴리에틸렌은 상온에서 여과를 통하여 분리해 낸 후 중량을 측정하였으며, [생성된 PE 중량(g) / 생성물 총 중량(g)]의 식을 통해 폴리에틸렌의 중량%를 산출하였다.In a 2L auto-clave reactor heated to 40 °C, 1 L of methylcyclohexane and the chromium compound of Formula A (0.41 mg, 0.15 μmol) were added, and then iBu 3 Al (30 μmol) was added to methylcyclohexane (methylcyclohexane, 1 mL). ) and injected into the reactor using a syringe at room temperature. After hydrogen was injected at a pressure of 20 psig, ethylene gas was injected at a pressure of 500 psig. After the reaction proceeded for 30 minutes while maintaining the reaction temperature at 40 °C while continuously supplying ethylene so that the internal pressure of the reactor was maintained at 500 psig, the reaction was terminated by discharging ethylene gas. Through gas chromatography analysis (GC analysis) of the produced material, the produced oligomers {1-octene (1-C8), 1-hexene (1-C6), methylcyclopentane + methylenecyclopentane (cy-C6), and C10 or higher oligomers (> C10)} was measured to calculate the weight ratio of the product. The resulting solid polyethylene was separated through filtration at room temperature, and then the weight was measured, and the weight % of polyethylene was calculated through the formula [weight of PE produced (g) / total weight of product (g)].
[실시예 2] 에틸렌 올리고머화 반응[Example 2] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 40 psig로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 40 psig.
[실시예 3] 에틸렌 올리고머화 반응[Example 3] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 60 psig 로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 60 psig.
[실시예 4] 에틸렌 올리고머화 반응[Example 4] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 80 psig 로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 80 psig.
[실시예 5] 에틸렌 올리고머화 반응[Example 5] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 100 psig 로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 100 psig.
[실시예 6] 에틸렌 올리고머화 반응[Example 6] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 120 psig 로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 120 psig.
[실시예 7] 에틸렌 올리고머화 반응[Example 7] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소 주입 압력을 250 psig 로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the hydrogen injection pressure was adjusted to 250 psig.
[비교예 1] 에틸렌 올리고머화 반응[Comparative Example 1] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 수소를 주입하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, an ethylene oligomerization reaction was performed in the same manner as in Example 1, except that hydrogen was not injected.
(mol/mol)H 2 /C 2
(mol/mol)
(kg/g-Cr/hr)Activity
(kg/g-Cr/hr)
(wt%)1-C8
(wt%)
(wt%)1-C6
(wt%)
(wt%)Cy-C6
(wt%)
(wt%)C10+
(wt%)
(wt%)PE
(wt%)
표 1에 나타낸 바와 같이, 에틸렌 올리고머화 반응에서 수소를 주입한 실시예 1 내지 실시예 7의 경우가 수소를 주입하지 않은 비교예 1과 대비하여 폴리에틸렌(PE) 생성량이 크게 감소하는 것을 볼 수 있으며, 수소 주입량을 증가시킬수록 폴리에틸렌 생성 억제 효과가 증가하는 것을 알 수 있다.As shown in Table 1, in the case of Examples 1 to 7 in which hydrogen was injected in the ethylene oligomerization reaction, compared to Comparative Example 1 in which hydrogen was not injected, it can be seen that the amount of polyethylene (PE) production is greatly reduced, , it can be seen that as the amount of hydrogen injected increases, the effect of inhibiting polyethylene production increases.
또한, 실시예 1 내지 실시예 7에 나타낸 바와 같이, 수소 주입량을 증가시킬수록 촉매 활성도 증가하였으며, H2/C2 몰비가 0.19인 실시예 4은 수소를 주입하지 않은 비교예 1과 대비 촉매 활성이 약 60%가 증가하는 놀라운 결과를 보였다. In addition, as shown in Examples 1 to 7, as the amount of hydrogen injected increased, the catalytic activity also increased, and Example 4, in which the H 2 /C 2 molar ratio was 0.19, had catalytic activity compared to Comparative Example 1 in which hydrogen was not injected. It showed surprising results with an increase of about 60%.
[실시예 8] 에틸렌 올리고머화 반응[Example 8] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 화학식 B의 크롬 화합물을 사용하고, 수소 주입 압력을 40 psig로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was carried out in the same manner as in Example 1, except that the chromium compound of Formula B was used and the hydrogen injection pressure was adjusted to 40 psig.
[실시예 9] 에틸렌 올리고머화 반응[Example 9] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 화학식 B의 크롬 화합물을 사용하고, 수소 주입 압력을 80 psig로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the chromium compound of Formula B was used and the hydrogen injection pressure was adjusted to 80 psig.
[실시예 10] 에틸렌 올리고머화 반응[Example 10] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 화학식 B의 크롬 화합물을 사용하고, 수소 주입 압력을 250 psig로 조정한 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was carried out in the same manner as in Example 1, except that the chromium compound of Formula B was used and the hydrogen injection pressure was adjusted to 250 psig.
[비교예 2] 에틸렌 올리고머화 반응[Comparative Example 2] Ethylene oligomerization reaction
상기 실시예 1의 [에틸렌 올리고머화] 단계에서, 화학식 B의 크롬 화합물을 사용하고, 수소를 주입하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 에틸렌 올리고머화 반응을 진행하였다.In the [ethylene oligomerization] step of Example 1, the ethylene oligomerization reaction was performed in the same manner as in Example 1, except that the chromium compound of Formula B was used and hydrogen was not injected.
(mol/mol)H 2 /C 2
(mol/mol)
(kg/g-Cr/hr)Activity
(kg/g-Cr/hr)
(wt%)1-C8
(wt%)
(wt%)1-C6
(wt%)
(wt%)Cy-C6
(wt%)
(wt%)C10+
(wt%)
(wt%)PE
(wt%)
표 2에 나타낸 바와 같이, 에틸렌 올리고머화 반응에서 수소 주입량을 증가시킬수록 폴리에틸렌 생성 억제 효과가 증가하는 것을 알 수 있다. H2/C2 몰비가 0.19인 실시예 9는 수소를 주입하지 않은 비교예 2 대비 촉매 활성이 4배 가까이 증가하는 결과를 보였다. As shown in Table 2, it can be seen that as the amount of hydrogen injected in the ethylene oligomerization reaction increases, the effect of inhibiting polyethylene production increases. Example 9, in which the H 2 /C 2 molar ratio was 0.19, showed a result of nearly four-fold increase in catalytic activity compared to Comparative Example 2 in which hydrogen was not injected.
특히 화학식 B로 표시되는 크롬화합물을 사용한 실시예 8 내지 10의 경우, 화학식 A로 표시되는 크롬화합물을 사용한 실시예 1 내지 7에 비해 촉매활성이 더욱 증가하였으며, 폴리에틸렌 부산물의 생성량이 50% 이상 감소하였다. In particular, in the case of Examples 8 to 10 using the chromium compound represented by Formula B, the catalytic activity was further increased compared to Examples 1 to 7 using the chromium compound represented by Formula A, and the amount of polyethylene by-product was reduced by more than 50%. did.
따라서 본 발명의 에틸렌 올리고머화 반응은 특정한 크롬 화합물과 수소 첨가제를 포함하여 높은 촉매 활성과 선택도를 가지는 동시에 폴리에틸렌 생성이 저하됨으로써 매우 효율적이고 경제적인 방법임을 알 수 있다.Therefore, it can be seen that the ethylene oligomerization reaction of the present invention is a very efficient and economical method by including a specific chromium compound and a hydrogen additive, while having high catalytic activity and selectivity, and at the same time reducing polyethylene production.
이상에서 살펴본 바와 같이 본 발명의 실시예에 대해 상세히 기술되었지만, 본 발명이 속하는 기술분야에 있어서 통상의 지식을 가진 사람이라면, 첨부된 청구범위에 정의된 본 발명의 정신 및 범위를 벗어나지 않으면서 본 발명을 여러 가지로 변형하여 실시할 수 있을 것이다. 따라서 본 발명의 앞으로의 실시예들의 변경은 본 발명의 기술을 벗어날 수 없을 것이다.Although the embodiments of the present invention have been described in detail as described above, those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention as defined in the appended claims The invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the technology of the present invention.
Claims (10)
상기 단계 반응물에 수소 및 에틸렌을 접촉시켜 에틸렌 올리고머를 제조하는 단계;를 포함하는 에틸렌 올리고머화 방법.
[화학식 1]
[화학식 2]
Al(R11)(R12)(R13)
상기 화학식 1 및 2에서,
R은 C1-C60알킬 또는 C6-C60아릴이고;
R1 내지 R4는 서로 독립적으로 C1-C60알킬 또는 C6-C60아릴이며;
X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트, 또는 에테르 및 아미노에서 선택되는 하나 이상을 포함하는 C1-C30하이드로카빌이고;
A는 보론 또는 알루미늄이고;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴, 불소가 치환된 C6-C60아릴옥시 또는 불소가 치환된 C6-C60알콕시이며;
R11 내지 R13은 서로 독립적으로 C1-C20알킬이며,
상기 R의 알킬 또는 아릴 및 R1 내지 R4의 알킬 또는 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노C1-C30알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있다.reacting the chromium complex represented by the following formula (1) with the organoaluminum compound represented by the following formula (2) in the presence of an organic solvent; and
Ethylene oligomerization method comprising a; contacting the reactants with hydrogen and ethylene to prepare an ethylene oligomer.
[Formula 1]
[Formula 2]
Al(R 11 )(R 12 )(R 13 )
In Formulas 1 and 2,
R is C1-C60 alkyl or C6-C60 aryl;
R 1 to R 4 are each independently C1-C60 alkyl or C6-C60 aryl;
X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate, or C1-C30 hydrocarbyl comprising at least one selected from ether and amino;
A is boron or aluminum;
Y 1 to Y 4 are each independently fluorine-substituted C6-C60 aryl, fluorine-substituted C6-C60 aryloxy, or fluorine-substituted C6-C60 alkoxy;
R 11 to R 13 are each independently C1-C20 alkyl;
Alkyl or aryl of R and alkyl or aryl of R 1 to R 4 are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, monoC1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 Alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, tri C6-C30 arylamino, mono C1-C30 alkylsilyl, diC1-C30 alkylsilyl, triC1-C30 alkylsilyl, mono C6-C30 aryl It may be further substituted with one or more selected from silyl, diC6-C30 arylsilyl and triC6-C30 arylsilyl.
상기 에틸렌과 수소의 몰비는 1: 0.001 내지 3.0인 에틸렌 올리고머화 방법.2. The method of claim 1
The molar ratio of ethylene and hydrogen is 1: 0.001 to 3.0 ethylene oligomerization method.
상기 크롬 착물과 하기 화학식 2로 표시되는 유기 알루미늄 화합물의 몰비는 1 : 10 내지 500인 에틸렌 올리고머화 방법.The method of claim 1,
The molar ratio of the chromium complex to the organoaluminum compound represented by the following formula (2) is 1: 10 to 500 ethylene oligomerization method.
상기 화학식 1 및 2에서, R은 C1-C60알킬이며;
R1 내지 R4는 서로 독립적으로 C6-C60아릴이며;
X1 및 X2는 각각 독립적으로 할로겐, C1-C30알킬, C1-C30알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C30하이드로카빌이고;
A는 보론 또는 알루미늄이고;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C60아릴이며;
R11 내지 R13은 서로 독립적으로 C1-C20알킬이며,
상기 R의 알킬 및 R1 내지 R4의 아릴은 C1-C30알킬, C6-C30아릴, C1-C30알콕시, 모노C1-C30알킬아미노, 디C1-C30알킬아미노, 트리C1-C30알킬아미노, 모노C6-C30아릴아미노, 디C6-C30아릴아미노, 트리C6-C30아릴아미노, 모노알킬실릴, 디C1-C30알킬실릴, 트리C1-C30알킬실릴, 모노C6-C30아릴실릴, 디C6-C30아릴실릴 및 트리C6-C30아릴실릴에서 선택되는 하나이상으로 더 치환될 수 있는 에틸렌 올리고머화 방법.The method of claim 1,
In Formulas 1 and 2, R is C1-C60 alkyl;
R 1 to R 4 are each independently C6-C60 aryl;
X 1 and X 2 are each independently halogen, C1-C30 alkyl, C1-C30 alkylcarboxylate, acetylacetonate or C1-C30 hydrocarbyl including ether;
A is boron or aluminum;
Y 1 to Y 4 are each independently C6-C60 aryl substituted with fluorine;
R 11 to R 13 are each independently C1-C20 alkyl;
The alkyl of R and the aryl of R 1 to R 4 are C1-C30 alkyl, C6-C30 aryl, C1-C30 alkoxy, mono C1-C30 alkylamino, diC1-C30 alkylamino, triC1-C30 alkylamino, mono C6-C30 arylamino, diC6-C30 arylamino, triC6-C30 arylamino, monoalkylsilyl, diC1-C30alkylsilyl, triC1-C30alkylsilyl, monoC6-C30arylsilyl, diC6-C30aryl Ethylene oligomerization method which may be further substituted with one or more selected from silyl and triC6-C30 arylsilyl.
상기 화학식 1은 하기 화학식 3으로 표시되는 에틸렌 올리고머화 방법.
[화학식 3]
상기 화학식 3에서,
R은 C1-C30알킬 또는 C6-C30아릴이고;
X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트 또는 에테르를 포함하는 C1-C20하이드로카빌이고;
A는 보론 또는 알루미늄이고;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C30아릴, 불소가 치환된 C6-C30아릴옥시 또는 불소가 치환된 C6-C30알콕시이며;
R21 내지 R32는 서로 독립적으로 C1-C20알킬이며,
상기 R의 알킬 또는 아릴은 C1-C20알킬, C6-C20아릴, C1-C20알콕시, 모노 C1-C20알킬아미노, 디C1-C20알킬아미노, 트리C1-C20알킬아미노, 모노C1-C20아릴아미노, 디C6-C20아릴아미노 및 트리C6-C20아릴아미노에서 선택되는 하나이상으로 더 치환될 수 있다.The method of claim 1,
Formula 1 is an ethylene oligomerization method represented by Formula 3 below.
[Formula 3]
In Formula 3,
R is C1-C30 alkyl or C6-C30 aryl;
X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate or C1-C20 hydrocarbyl including ether;
A is boron or aluminum;
Y 1 to Y 4 are each independently fluorine-substituted C6-C30 aryl, fluorine-substituted C6-C30 aryloxy, or fluorine-substituted C6-C30 alkoxy;
R 21 to R 32 are each independently C1-C20 alkyl,
Alkyl or aryl of R is C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxy, mono C1-C20 alkylamino, diC1-C20 alkylamino, triC1-C20 alkylamino, mono C1-C20 arylamino, It may be further substituted with one or more selected from diC6-C20 arylamino and triC6-C20 arylamino.
상기 화학식 3에서,
R은 C1-C20알킬이고;
X1 및 X2는 각각 독립적으로 할로겐, C1-C20알킬, C1-C20알킬카복실레이트, 아세틸아세토네이트이며;
A는 보론이고;
Y1 내지 Y4는 서로 독립적으로 불소가 치환된 C6-C20아릴 또는 불소가 치환된 C6-C20아릴옥시인 에틸렌 올리고머화 방법.6. The method of claim 5,
In Formula 3,
R is C 1 -C 20 alkyl;
X 1 and X 2 are each independently halogen, C1-C20 alkyl, C1-C20 alkylcarboxylate, acetylacetonate;
A is boron;
Y 1 to Y 4 are each independently fluorine-substituted C6-C20 aryl or fluorine-substituted C6-C20 aryloxy;
상기 화학식 3에서,
R은 C1-C5알킬이고;
X1 및 X2는 염소이고;
A는 보론이고;
Y1 내지 Y4는 (C6F5)4이고;
R21 내지 R32는 서로 독립적으로 C5-C8알킬인 에틸렌 올리고머화 방법.6. The method of claim 5,
In Formula 3,
R is C1-C5 alkyl;
X 1 and X 2 are chlorine;
A is boron;
Y 1 to Y 4 are (C 6 F 5 ) 4 ;
R 21 to R 32 are each independently C5-C8 alkyl.
상기 유기용매는 할로겐으로 치환 또는 비치환된 탄화수소인 에틸렌 올리고머화 방법.The method of claim 1,
The organic solvent is a halogen-substituted or unsubstituted hydrocarbon ethylene oligomerization method.
상기 올리고머를 제조하는 단계는 10 내지 80℃에서 10분 내지 2시간동안 수행되는 에틸렌 올리고머화 방법.The method of claim 1,
The step of preparing the oligomer is an ethylene oligomerization method performed at 10 to 80° C. for 10 minutes to 2 hours.
상기 올리고머는 폴리에틸렌의 함량이 0.6중량%이하인 에틸렌 올리고머화 방법.The method of claim 1,
The oligomer is an ethylene oligomerization method in which the content of polyethylene is 0.6% by weight or less.
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