CN105263942B - 配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 - Google Patents
配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 Download PDFInfo
- Publication number
- CN105263942B CN105263942B CN201480032582.XA CN201480032582A CN105263942B CN 105263942 B CN105263942 B CN 105263942B CN 201480032582 A CN201480032582 A CN 201480032582A CN 105263942 B CN105263942 B CN 105263942B
- Authority
- CN
- China
- Prior art keywords
- olefin oligomerization
- chemical formula
- catalyst system
- alkyl
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 57
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 239000003446 ligand Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 claims description 35
- 239000004411 aluminium Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical class [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- -1 polyethylene Polymers 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 6
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Substances CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([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
- 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
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical group CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052787 antimony Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000037429 base substitution Effects 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229910000085 borane Inorganic materials 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
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine 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
- 239000012459 cleaning agent Substances 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
-
- 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
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- 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
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及配体化合物、用于烯烃低聚反应的催化剂体系,以及使用其的烯烃低聚方法。根据本发明的烯烃低聚反应催化剂体系具有优良的催化活性,并且显示出对1‑己烯或1‑辛烯的高选择性,从而能够更有效地制备α‑烯烃。
Description
技术领域
本发明涉及配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法。
背景技术
线性α-烯烃是用作共聚单体、清洁剂、润滑剂、增塑剂等的重要材料,在工业上被广泛使用,并且特别地,1-己烯和1-辛烯在制备线性低密度聚乙烯(LLDPE)时被大量用作控制聚乙烯的密度的共聚单体。
在现有的LLDPE制备方法中,乙烯与α-烯烃共聚单体(例如,1-己烯和1-辛烯)共聚,以便在聚合物骨架中形成分支以控制密度。
因此,问题在于在具有高共聚单体含量的LLPDE的制备中,共聚单体的成本占据了生产成本的大部分。已进行了多种尝试来解决这一问题。
并且,由于α-烯烃根据种类具有不同的应用领域或市场规模,所以用于选择性生产特定烯烃的技术在商业上非常重要,并且最近,已对用于通过选择性乙烯低聚反应来以高选择性制备1-己烯和1-辛烯的铬催化剂技术进行了很多研究。
现有的1-己烯或1-辛烯的商业制备方法包括壳牌化学(Shell Chemical)的SHOP法、雪佛龙菲利普斯(Chevron Philips)的齐格勒(Ziegler)法等,借此能够生产宽分布的C4-20α-烯烃。
作为用于乙烯三聚的催化剂,提出了使用通式(R1)(R2)X-Y-X(R3)(R4)的配体的基于铬的催化剂。其中,X是磷、砷或锑,Y是连接基团如-N(R5)-,并且R1、R2、R3和R4中至少之一具有极性取代基或给电子取代基。
此外,作为在催化条件下对1-己烯表现出催化活性的配体,对(邻-乙基苯基)2PN(Me)P(邻-乙基苯基)2已进行了研究,其在R1、R2、R3和R4中至少之一不具有极性取代基(Chem.Commun.,2002,858)。
然而,关于以上解释的现有技术的包含杂原子的配体,对于在制备1-辛烯或1-己烯时持续不断的多聚活性和高选择性具有持续的需求。
现有技术
非专利文献
1.Chem.Commun.,2002,858
发明详述
技术问题
本发明的目的是提供可以以高活性和选择性使烯烃低聚的新的配体化合物、包含其的用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法。
技术方案
本发明提供了由以下化学式1表示的配体化合物:
[化学式1]
在化学式1中,
R1和R2中的至少一个是C3-20支化烷基,包含选自N、O、F、S或P中的至少一个杂原子的C1-20线性或支化烃基,C6-40芳基,或者C3-30杂芳基,
R1和R2中的另一个是氢或者C1-20线性或支化烃基,
R3至R6独立地为C6-40芳基,并且m和n独立地为0至10的整数。
而且,本发明提供了用于烯烃低聚反应的催化剂体系,其包含所述配体化合物、过渡金属源和助催化剂。
而且,本发明还提供了用于烯烃低聚反应的方法,其包括在用于烯烃低聚反应的催化剂体系的存在下使烯烃多聚的步骤。
在下文中,将详细说明根据本发明的配体化合物、用于烯烃低聚反应的催化剂体系,以及用于烯烃低聚反应的方法。
根据本发明的一个实施方案,提供了由以下化学式1表示的配体化合物:
[化学式1]
在化学式1中,
R1和R2中的至少一个是C3-20支化烷基,包含选自N、O、F、S或P中的至少一个杂原子的C1-20线性或支化烃基,C6-40芳基,或者C3-30杂芳基,
R1和R2中的另一个是氢或者C1-20线性或支化烃基,
R3至R6独立地为C6-40芳基,并且m和n独立地为0至10的整数。
本发明人新合成了之前未知的配体化合物,经实验证实,如果适当地调节引入该配体化合物的取代基,那么可以很容易地控制过渡金属周围的电子/空间环境,因而能够使烯烃低聚反应具有高催化活性和选择性,从而完成本发明。
特别地,化学式1的配体化合物具有其中大体积烷基、芳基等与双膦胺基团相连的结构,并且其特征在于金属中心周围的空间变大,由此控制乙烯的插入,从而改善对1-己烯和1-辛烯的选择性。
在下文中,将对化学式1中的每个取代基进行详细说明。
芳基优选为C6-40芳香环,并且还包括被C1-10烷基取代的芳香环。芳基的具体实例包括芳香环基团如苯基、萘基、蒽基、吡啶基、二甲基苯胺基、苯甲氧基等,以及被C1-10烷基取代的芳香环,但不限于此。
而且,杂原子意指N、O、F、S或P,并且杂芳基意指包含至少一个杂原子的芳基。
而且,卤素基团意指氟(F)、氯(Cl)、溴(Br)和碘(I)。
其中,化学式1中R1和R2中的至少一个可为包含选自N、O、F、S或P中的至少一个杂原子的C1-20线性或支化烃基,C3-20支化烷基,C6-40芳基或者C3-30杂芳基。具体地,化学式1的配体化合物在R1和R2中的至少一个上被大体积烷基、芳基等取代,并且与在R1和R2处仅引入非大体积官能团例如氢、甲基、乙基等的化合物相比,这种化合物增加了金属中心周围的位阻,从而能够实现具有高催化活性和选择性的烯烃低聚反应。
在化学式1中,R1和R2中的至少一个可为包含选自N、O、F、S或P中的至少一个杂原子的C1-20线性或支化烃基,C3-10支化烷基,或者C6-20芳基。
而且,R1和R2中的另一个可为C1-10线性或支化烷基或者C6-20芳基。
而且,化学式1的配体化合物的代表性实例如下:
由化学式1表示的化合物包括所有可能的光学异构体。
同时,由化学式1表示的配体化合物可通过以下反应式1来合成,但不限于此。用于制备由化学式1表示的化合物的方法将在以下实施例中进行详细说明。
[反应式1]
在反应式1中,R1至R2如化学式1中所限定,A相同或不同并且独立地与化学式1中R3至R6的含义相同,并且X是卤素。
同时,根据另一个实施方案,提供的是用于烯烃低聚反应的催化剂体系,其包括根据一个实施方案的配体化合物、过渡金属源和助催化剂。
如本文中所用,术语“烯烃低聚反应”是指少量烯烃的聚合反应。在聚合3个烯烃时,其被称为三聚,在聚合4个烯烃时,其被称为四聚,并且少量烯烃聚合形成低分子量材料的过程通常称为多聚。特别地,在本发明中,涉及由乙烯选择性制备1-己烯和1-辛烯,它们是LLDPE的主要共聚单体。
选择性烯烃低聚反应与所用催化剂体系密切相关。用于烯烃低聚反应的催化剂体系包含起主催化剂作用的过渡金属源和助催化剂,其中,所述活性催化剂的结构可根据配体的化学结构发生变化,从而改变烯烃的选择性。
如上所述,由于根据一个实施方案的配体化合物具有其中大体积烷基、芳基等与双膦胺基团连接的结构,所以包含其的催化剂体系可容易地控制过渡金属周围的电子/空间环境,从而能够实现具有高催化活性和选择性的烯烃低聚反应。
过渡金属源起主催化剂的作用,并且优选地是选自以下的至少一种:乙酰丙酮铬(III)、三(四氢呋喃)三氯化铬、2-乙基己酸铬(III)和三(2,2,6,6-四甲基-3,5-庚二酮酸)铬(III)。
所述助催化剂是包含第13族金属的有机金属化合物,并且不受特别限制,只要其在过渡金属催化剂存在下可用于烯烃多聚反应即可。具体地,作为助催化剂,可使用选自由以下化学式2至4表示的化合物中的至少一种。
[化学式2]
-[Al(R7)-O]c-
在化学式2中,R7相同或不同,并且独立地为卤素基团、C1-20烃基或被卤素取代的C1-20烃基,并且c为2或更大的整数,
[化学式3]
D(R8)3
在化学式3中,
D是铝或硼,R8相同或不同并且独立地为氢、卤素、C1-20烃基或被卤素取代的C1-20烃基,
[化学式4]
[L-H]+[Q(E)4]-
在所述化学式5中,
L是中性路易斯碱,[L-H]+是布朗斯台德酸,Q是Br3+或Al3+,并且E独立地为被选自卤素、C1-20烃基、C1-20烷氧基和苯氧基中至少一个取代或者未被取代的C6-20芳基或C1-20烷基。
由化学式2表示的化合物的实例可包括:改性甲基铝氧烷(MMAO)、甲基铝氧烷(MAO)、乙基铝氧烷、异丁基铝氧烷、丁基铝氧烷等。
由化学式3表示的烷基金属化合物的实例可包括:三甲基铝、三乙基铝、三异丁基铝、三丙基铝、三丁基铝、二甲基氯化铝、二甲基异丁基铝、二甲基乙基铝、二乙基氯化铝、三异丙基铝、三仲丁基铝、三环戊基铝、三戊基铝、三异戊基铝、三己基铝、乙基二甲基铝、甲基二乙基铝、三苯基铝、三对甲苯基铝、二甲基铝甲醇盐、二甲基铝乙醇盐、三甲基硼、三乙基硼、三异丁基硼、三丙基硼、三丁基硼等。
由化学式4表示的化合物的实例可包括:三乙基铵四苯基硼、三丁基铵四苯基硼、三甲基铵四苯基硼、三丙基铵四苯基硼、三甲基铵四(对甲苯基)硼、三丙基铵四(对甲苯基)硼、三乙基铵四(邻,对-二甲苯基)硼、三甲基铵四(邻,对-二甲苯基)硼、三丁基铵四(对-三氟甲基苯基)硼、三甲基铵四(对-三氟甲基苯基)硼、三丁基铵四五氟苯基硼、N,N-二乙基苯铵四苯基硼、N,N-二乙基苯铵四苯基硼、N,N-二乙基苯铵四五氟苯基硼、二乙基铵四五氟苯基硼、三苯基磷四苯基硼、三甲基磷四苯基硼、三乙基铵四苯基铝、三丁基铵四苯基铝、三甲基铵四苯基铝、三丙基铵四苯基铝、三甲基铵四(对甲苯基)铝、三丙基铵四(对甲苯基)铝、三乙基铵四(邻,对-二甲基苯基)铝、三丁基铵四(对-三氟甲基苯基)铝、三甲基铵四(对-三氟甲基苯基)铝、三丁基铵四五氟苯基铝、N,N-二乙基苯铵四苯基铝、N,N-二乙基苯铵四苯基铝、N,N-二乙基苯铵四五氟苯基铝、二乙基铵四五氟苯基铝、三苯基磷四苯基铝、三甲基磷四苯基铝、三苯基碳四苯基硼、三苯基碳四苯基铝、三苯基碳四(对-三氟甲基苯基)硼、三苯基碳四五氟苯基硼等。
作为用于烯烃低聚反应的催化剂体系的助催化剂,可以优选使用铝氧烷,并且更优选地,可以使用甲基铝氧烷(MAO)。
用于烯烃低聚的催化剂体系的配体化合物∶过渡金属源∶助催化剂的摩尔比可为约1∶1∶1至约10∶1∶10,000,优选约1∶1∶100至约5∶1∶3,000,以增加对线性α-烯烃的选择性和多聚活性,但不限于此。
在包含由化学式1表示的配体化合物、过渡金属源和助催化剂的用于烯烃低聚反应的所述催化剂体系中,可在单体存在或不存在下,将这三种组分同时或以任意顺序依次添加到合适的溶剂中,并作为活性催化剂获得。活性溶剂可包括庚烷、甲苯、环己烷、甲基环己烷、1-己烯、乙醚、四氢呋喃、乙腈、二氯甲烷、氯仿、氯苯、甲醇、丙酮等,但不限于此。
同时,根据本发明的又一个实施方案,提供了用于烯烃低聚反应的方法,其包括在用于烯烃低聚反应的催化剂体系的存在下进行烯烃多聚的步骤。如果使用根据本发明的用于烯烃低聚反应的催化剂体系,可提供具有提高了活性和选择性的用于烯烃低聚反应的方法。所述烯烃可优选乙烯。
根据本发明的烯烃低聚反应可使用用于烯烃低聚反应的催化剂体系以及常用设备和接触技术,在惰性溶剂存在或不存在下作为以下反应来进行:均质液相反应;其中一部分或全部催化剂体系不溶解的淤浆反应;两相液-液反应;或者其中产物烯烃充当主要介质的本体相反应或气相反应,并且均质液相反应是优选的。
烯烃低聚反应可在不与催化剂化合物和活性剂反应的任何惰性溶剂中进行。合适的惰性溶剂可包括苯、甲苯、二甲苯、枯烯、庚烷、环己烷、甲基环己烷、甲基环戊烷、己烷、戊烷、丁烷、异丁烷等,但不限于此。其中,所述溶剂在使用前可用少量的烷基铝处理以除去少量充当催化剂毒物的水或空气。
所述烯烃低聚反应可在约5℃至约200℃,优选约30℃至约150℃的温度下进行。并且,所述烯烃低聚反应可在约1巴至约300巴,优选约2巴至约150巴的压力下进行。
根据本发明的一个实例,可以确认,由于使用由化学式1表示的配体化合物作为配体的催化剂体系使乙烯低聚,所以可选择性地合成1-己烯和1-辛烯。
有利效果
通过使用包含根据本发明的配体化合物的催化剂体系,与现有的催化剂体系相比可以以更高催化活性和选择性使乙烯低聚。
具体实施方式
在下文中,将通过参照以下实施例对本发明进行详细说明。然而,这些实施例仅用于举例说明本发明并且本发明的范围并不限于此。
<配体化合物的合成>
合成实施例
所有的反应都在氩气氛下使用Schlenk技术或手套箱进行。合成的化合物使用Varian 500MHz分光计通过1H(500MHz)和31P(202MHz)NMR谱进行分析。位移从TMS到低场以ppm来表示,以残留溶剂峰作为参考。用H3PO4水溶液校准磷探头。在氩气氛下,将胺(10mmol)和三乙胺(胺的3~10当量)溶解在二氯甲烷(80mL)中。当将烧瓶浸没在水浴中时,缓慢引入氯二苯基膦(20mmol)并且将混合物搅拌过夜。在真空下除去溶剂,然后引入另外的溶剂(二乙醚、四氢呋喃或己烷),充分搅拌混合物并且用无空气玻璃过滤器除去三乙基氯化铵盐。除去滤液中的溶剂以获得产物。用于制备每个实施例和比较实施例中使用的配体的起始胺示于下表1中。
【表1】
<乙烯低聚反应>
实施例1
在氩气氛下将Cr(acac)3(17.5mg,0.05mmol)和合成实施例1中制备的配体(0.1mmol)放入烧瓶中,添加甲苯(10mL)并搅拌混合物以制备5mM溶液。
准备600mL Parr反应器,在120℃下施加真空2小时,然后使温度降低至45℃,并且将内部替换为氩气。引入环己烷(270g)和2mL的MAO(10重量%甲苯溶液,Al/Cr=300)并将2mL的5mM溶液(10μmol)引入反应器中。将混合物在500rpm下搅拌2分钟,然后将调整为45巴的乙烯管线阀打开以用乙烯填充反应器内部,并将混合物在500rpm下搅拌15分钟。关闭乙烯管线阀,将温度调整为0℃,反应器用冰/丙酮浴冷却,然后缓慢排出未反应乙烯,并且放入0.5mL壬烷(GC内标准物)。之后,取出反应器中的2mL液体部分并用水淬灭,有机部分用PTFE注射过滤器过滤以制备GC样品。用GC分析GC样品。向剩余的反应溶液中添加400mL乙醇/HCl(10体积%),搅拌并过滤混合物以获得聚合物。将所得聚合物在65℃真空炉中干燥过夜。
实施例2
除了使用1ml(5μmol)的催化剂5mM溶液以外,通过与实施例1相同的方法进行反应。
实施例3
除了使用合成实施例2中制备的配体以外,通过与实施例1相同的方法进行反应。
实施例4
除了使用合成实施例2中制备的配体以外,通过与实施例2相同的方法进行反应。
实施例5
除了使用合成实施例3中制备的配体以外,通过与实施1相同的方法进行反应。
比较实施例1
在氩气氛下将Cr(acac)3(17.5mg,0.05mmol)和比较合成实施例1中制备的配体(0.1mmol)放入烧瓶中,添加甲苯(10mL)并搅拌混合物以制备5mM溶液。
准备600mL Parr反应器,在120℃下施加真空2小时,然后使温度降低至45℃并且将内部替换为氩气。然后,引入300g甲苯和2mL的MAO(10重量%甲苯溶液Al/Cr=300),并将2mL的5mM溶液(10μmol)引入反应器中。将混合物在500rpm下搅拌2分钟,然后将调整为45巴的乙烯管线阀打开以用乙烯填充反应器内部,并且将混合物在500rpm下搅拌30分钟。关闭乙烯管线阀,将温度调整为0℃,反应器用冰/丙酮浴冷却,然后缓慢排出未反应乙烯,并放入0.5mL壬烷(GC内标准物)。之后,取出反应器中的2mL液体部分并用水淬灭,有机部分用PTFE注射过滤器过滤以制备GC样品。用GC分析GC样品。向剩余的反应溶液中添加400mL乙醇/HCl(10体积%),搅拌并过滤混合物以获得聚合物。将所得聚合物在65℃真空炉中干燥过夜。
比较实施例2
除了使用比较合成实施例2中制备的配体并使用1ml(5μmol)的催化剂5mM溶液以外,通过与比较实施例1相同的方法进行反应。
比较实施例3
除了使用比较合成实施例3中制备的配体以外,通过与比较实施例1相同的方法进行反应。
实施例1至5和比较实施例1至3的结果示于下表2中。
【表2】
由表2的结果可以看出,与比较实施例相比,在实施例的情况下,表现出非常高的多聚活性,对1-己烯和1-辛烯的选择性显著改善,并且副产物固体PE的量少。
Claims (8)
1.选自如下的配体化合物:
2.一种用于烯烃低聚反应的催化剂体系,包含根据权利要求1所述的配体化合物、过渡金属源和助催化剂。
3.根据权利要求2所述的催化剂体系,其中所述过渡金属源为选自以下中的至少一种:乙酰丙酮铬(III)、三(四氢呋喃)三氯化铬、2-乙基己酸铬(III)和三(2,2,6,6-四甲基-3,5-庚二酮酸)铬(III)。
4.根据权利要求2所述的催化剂体系,其中所述助催化剂是选自由以下化学式2至4表示的化合物中的至少一种:
[化学式2]
-[Al(R7)-O]c-
在所述化学式2中,R7相同或不同并且独立地为卤素基团、C1-20烃基或被卤素取代的C1-20烃基,并且c是2或更大的整数,
[化学式3]
D(R8)3
在所述化学式3中,
D是铝或硼,R8相同或不同并且独立地为氢、卤素、C1-20烃基或被卤素取代的C1-20烃基,
[化学式4]
[L-H]+[Q(E)4]-
在所述化学式4中,
L是中性路易斯碱,[L-H]+是布朗斯台德酸,Q是B3+或Al3+,并且E独立地为被选自卤素、C1-20烃基、C1-20烷氧基和苯氧基中至少一个取代的或者未被取代的C6-20芳基或C1-20烷基。
5.一种用于烯烃低聚反应的方法,包括在根据权利要求2所述的用于烯烃低聚反应的催化剂体系存在下使烯烃多聚的步骤。
6.根据权利要求5所述的用于烯烃低聚反应的方法,其中所述烯烃是乙烯。
7.根据权利要求5所述的用于烯烃低聚反应的方法,其中多聚温度为5℃至200℃。
8.根据权利要求5所述的用于烯烃低聚反应的方法,其中多聚压力为1巴至300巴。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2013-0140873 | 2013-11-19 | ||
KR20130140873 | 2013-11-19 | ||
KR10-2014-0153906 | 2014-11-06 | ||
KR1020140153906A KR101657259B1 (ko) | 2013-11-19 | 2014-11-06 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
PCT/KR2014/010744 WO2015076520A1 (ko) | 2013-11-19 | 2014-11-10 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105263942A CN105263942A (zh) | 2016-01-20 |
CN105263942B true CN105263942B (zh) | 2017-08-18 |
Family
ID=53392689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480032582.XA Active CN105263942B (zh) | 2013-11-19 | 2014-11-10 | 配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9637509B2 (zh) |
EP (1) | EP2987797B1 (zh) |
JP (1) | JP6126741B2 (zh) |
KR (1) | KR101657259B1 (zh) |
CN (1) | CN105263942B (zh) |
WO (1) | WO2015076520A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101757369B1 (ko) | 2014-12-11 | 2017-07-12 | 주식회사 엘지화학 | 리간드 화합물, 유기크롬 화합물, 올레핀 올리고머화용 촉매 시스템, 및 이를 이용한 올레핀의 올리고머화 방법 |
KR101768194B1 (ko) | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
WO2016186282A1 (ko) | 2015-05-15 | 2016-11-24 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
KR101757370B1 (ko) | 2015-06-01 | 2017-07-12 | 주식회사 엘지화학 | 1-옥텐 조성물 |
KR102058142B1 (ko) | 2015-09-02 | 2019-12-20 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101761830B1 (ko) | 2015-10-21 | 2017-07-26 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101963009B1 (ko) * | 2016-12-15 | 2019-03-27 | 한화토탈 주식회사 | 에틸렌 올리고머화 방법 |
CN109134538B (zh) * | 2018-09-25 | 2021-05-14 | 万华化学集团股份有限公司 | 碘膦氧配体及其制备方法和络合物、包括该络合物的催化剂体系和用途 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102307662A (zh) * | 2009-02-16 | 2012-01-04 | Sasol技术股份有限公司 | 在活化的低聚催化剂存在下烯属化合物的低聚 |
CN103270006A (zh) * | 2010-12-29 | 2013-08-28 | 切弗朗菲利浦化学公司 | 烯烃低聚反应催化剂以及制备和使用其的方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1578531B9 (en) | 2002-12-20 | 2011-02-02 | Sasol Technology (PTY) Limited | Tetramerization of olefins |
MXPA05006658A (es) | 2002-12-20 | 2005-11-17 | Sasol Tech Pty Ltd | Tetramerizacion-polimerizacion en tandem de olefinas. |
ES2372474T3 (es) * | 2004-06-18 | 2012-01-20 | Sasol Technology (Pty) Ltd | Oligomerización en presencia tanto de un catalizador de tetramerización como de un catalizador de oligomerización adicional. |
US7259123B2 (en) | 2005-04-08 | 2007-08-21 | Shell Oil Company | Catalytic trimerization and tetramerization of olefinic monomers |
WO2007057458A1 (en) | 2005-11-21 | 2007-05-24 | Shell Internationale Research Maatschappij B.V. | Catalytic process for the oligomerization of olefinic monomers |
CN104353493A (zh) * | 2006-02-03 | 2015-02-18 | 英力士销售(英国)有限公司 | 过渡金属催化剂 |
WO2008004986A1 (en) * | 2006-07-05 | 2008-01-10 | National University Of Singapore | Catalyst system for oligomerization of olefins |
EP2490990B1 (en) | 2009-10-19 | 2013-12-04 | Sasol Technology (Proprietary) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
CA2701252C (en) | 2010-04-20 | 2017-01-03 | Nova Chemicals Corporation | Polymer mitigation |
KR101471156B1 (ko) * | 2011-06-14 | 2014-12-10 | 주식회사 엘지화학 | 선택적 에틸렌 올리고머화 촉매계 |
CA2747501C (en) * | 2011-07-26 | 2018-01-23 | Nova Chemicals Corporation | "bulk" ethylene oligomerization |
WO2013168102A1 (en) * | 2012-05-09 | 2013-11-14 | Sasol Technology (Proprietary) Limited | Tetramerisation of ethylene |
BR112014024524B1 (pt) * | 2012-05-09 | 2020-04-22 | Sasol Tech Pty Ltd | tetramerização de etileno |
MY164153A (en) | 2012-05-09 | 2017-11-30 | Sasol Tech (Proprietary) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
KR101676835B1 (ko) * | 2013-11-18 | 2016-11-17 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
-
2014
- 2014-11-06 KR KR1020140153906A patent/KR101657259B1/ko active IP Right Grant
- 2014-11-10 EP EP14863778.8A patent/EP2987797B1/en active Active
- 2014-11-10 JP JP2016515297A patent/JP6126741B2/ja active Active
- 2014-11-10 CN CN201480032582.XA patent/CN105263942B/zh active Active
- 2014-11-10 US US14/896,608 patent/US9637509B2/en active Active
- 2014-11-10 WO PCT/KR2014/010744 patent/WO2015076520A1/ko active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102307662A (zh) * | 2009-02-16 | 2012-01-04 | Sasol技术股份有限公司 | 在活化的低聚催化剂存在下烯属化合物的低聚 |
CN103270006A (zh) * | 2010-12-29 | 2013-08-28 | 切弗朗菲利浦化学公司 | 烯烃低聚反应催化剂以及制备和使用其的方法 |
Non-Patent Citations (4)
Title |
---|
"Chromium-based ethylene tetramerization with diphosphinoamines bearing pendent amine donors";Seokpil Sa等;《Journal of Molecular Catalysis A: Chemical》;20130525;第378卷;第18页右栏倒数第1段,第19页图1,第20页表1-3 * |
"The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri- and tetramerisation";Esna Killian等;《Journal of Molecular Catalysis A: Chemical》;20070206;第270卷;摘要,第217页图2-3,第215页表2-3,第2.3节 * |
Nicoline Cloete等."Ethylene Tri- and Tetramerization: a Steric Parameter Selectivity Switch from X‑ * |
ray Crystallography and Computational Analysis".《Inorganic Chemistry》.2013,第52卷 * |
Also Published As
Publication number | Publication date |
---|---|
US9637509B2 (en) | 2017-05-02 |
JP6126741B2 (ja) | 2017-05-10 |
KR20150057988A (ko) | 2015-05-28 |
EP2987797A1 (en) | 2016-02-24 |
WO2015076520A1 (ko) | 2015-05-28 |
CN105263942A (zh) | 2016-01-20 |
JP2016520597A (ja) | 2016-07-14 |
EP2987797A4 (en) | 2017-01-04 |
US20160207946A1 (en) | 2016-07-21 |
KR101657259B1 (ko) | 2016-09-13 |
EP2987797B1 (en) | 2018-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105263942B (zh) | 配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 | |
CN105324359B (zh) | 配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 | |
CN104955829B (zh) | 配体化合物、用于烯烃低聚反应的催化剂体系及使用其的烯烃低聚方法 | |
CN107075009A (zh) | 减活剂以及使用该减活剂减少烯烃低聚中的副产物的方法 | |
CN105722846B (zh) | 配体化合物、用于烯烃低聚反应的催化剂体系及使用该催化剂体系的烯烃低聚方法 | |
CN107207545B (zh) | 配体化合物,低聚催化剂体系及使用其的烯烃低聚方法 | |
EP2918340B1 (en) | Ligand compound, catalyst system for oligomerizing olefin, and method for oligomerizing olefin using same | |
US10099971B2 (en) | 1-octene composition | |
CN105308057B (zh) | 配体化合物、用于烯烃低聚反应的催化剂体系以及使用其的用于烯烃低聚反应的方法 | |
EP3118227A1 (en) | 1-octene composition | |
CN107580600B (zh) | 配体化合物、用于烯烃低聚的催化剂体系以及使用该催化剂体系的使烯烃低聚的方法 | |
KR20160110079A (ko) | 올리고머화 촉매계 및 이를 이용한 올레핀 올리고머화 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |