CN1561317A - 链增长反应方法 - Google Patents
链增长反应方法 Download PDFInfo
- Publication number
- CN1561317A CN1561317A CNA028194128A CN02819412A CN1561317A CN 1561317 A CN1561317 A CN 1561317A CN A028194128 A CNA028194128 A CN A028194128A CN 02819412 A CN02819412 A CN 02819412A CN 1561317 A CN1561317 A CN 1561317A
- Authority
- CN
- China
- Prior art keywords
- iii
- group
- zinc
- hydrocarbyl
- substituted
- 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.)
- Granted
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 239000011701 zinc Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 54
- -1 alkoxide compounds Chemical class 0.000 claims abstract description 51
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 150000003624 transition metals Chemical class 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 229910052768 actinide Inorganic materials 0.000 claims abstract description 15
- 150000001255 actinides Chemical class 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 14
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000004711 α-olefin Substances 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 6
- 238000006073 displacement reaction Methods 0.000 claims abstract description 5
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 55
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 38
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical group 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- MIILMDFFARLWKZ-UHFFFAOYSA-L dichlorozirconium;1,2,3,4,5-pentamethylcyclopentane Chemical compound [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1(C)[Zr+2]C1(C)C(C)=C(C)C(C)=C1C MIILMDFFARLWKZ-UHFFFAOYSA-L 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- JUOCTSZRGAFSKS-UHFFFAOYSA-N CCCCCC[Zn]CCCCCC Chemical compound CCCCCC[Zn]CCCCCC JUOCTSZRGAFSKS-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 claims description 3
- FOKGVHRHBBEPPI-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorozirconium Chemical compound Cl[Zr](Cl)Cl.C[C]1[C](C)[C](C)[C](C)[C]1C FOKGVHRHBBEPPI-UHFFFAOYSA-K 0.000 claims description 2
- WCGXJPFHTHQNJL-UHFFFAOYSA-N 1-[5-ethyl-2-hydroxy-4-[6-methyl-6-(2H-tetrazol-5-yl)heptoxy]phenyl]ethanone Chemical compound CCC1=CC(C(C)=O)=C(O)C=C1OCCCCCC(C)(C)C1=NNN=N1 WCGXJPFHTHQNJL-UHFFFAOYSA-N 0.000 claims description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 2
- VVNYDCGZZSTUBC-UHFFFAOYSA-N 5-amino-2-[(2-methylpropan-2-yl)oxycarbonylamino]-5-oxopentanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CCC(N)=O VVNYDCGZZSTUBC-UHFFFAOYSA-N 0.000 claims description 2
- MQNPENQYQXUCOX-UHFFFAOYSA-N C=1C=CC=CC=1C[Zn]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zn]CC1=CC=CC=C1 MQNPENQYQXUCOX-UHFFFAOYSA-N 0.000 claims description 2
- LHHAUUVITWQDQI-UHFFFAOYSA-L CC1=C(C)C(C)(C(C)=C1C)[Zr](Cl)(Cl)C1C=CC=C1 Chemical compound CC1=C(C)C(C)(C(C)=C1C)[Zr](Cl)(Cl)C1C=CC=C1 LHHAUUVITWQDQI-UHFFFAOYSA-L 0.000 claims description 2
- AYEXPZYTCYCMPE-UHFFFAOYSA-N CCCCCCCCCCCC[Zn]CCCCCCCCCCCC Chemical compound CCCCCCCCCCCC[Zn]CCCCCCCCCCCC AYEXPZYTCYCMPE-UHFFFAOYSA-N 0.000 claims description 2
- QGAXJIMCDCDTDX-UHFFFAOYSA-N CCCCCCCCCC[Zn]CCCCCCCCCC Chemical compound CCCCCCCCCC[Zn]CCCCCCCCCC QGAXJIMCDCDTDX-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 239000011574 phosphorus Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 10
- 241000282465 Canis Species 0.000 claims 1
- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 105
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 41
- 239000005977 Ethylene Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- UPDVZRRBDGBFQF-UHFFFAOYSA-N 1-(6-acetylpyridin-2-yl)ethanone;2,4,6-trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1.CC1=CC(C)=C(N)C(C)=C1.CC(=O)C1=CC=CC(C(C)=O)=N1 UPDVZRRBDGBFQF-UHFFFAOYSA-N 0.000 description 2
- UBSOVNJEIALBNU-UHFFFAOYSA-N 3-N-[2,6-di(propan-2-yl)phenyl]butane-2,3-diimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C(C)C(C)=N UBSOVNJEIALBNU-UHFFFAOYSA-N 0.000 description 2
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- WTQSPDBNCMUOKF-UHFFFAOYSA-L naphthalene-1-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 WTQSPDBNCMUOKF-UHFFFAOYSA-L 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- LSUPXLRKMCJALP-UHFFFAOYSA-L 1-[2-(2,3,3a,4,5,6,7,7a-octahydro-1H-inden-1-yl)ethyl]-2,3,3a,4,5,6,7,7a-octahydro-1H-indene zirconium(2+) dichloride Chemical compound [Cl-].[Cl-].[Zr++].C(CC1CCC2CCCCC12)C1CCC2CCCCC12 LSUPXLRKMCJALP-UHFFFAOYSA-L 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 1
- VCLJODPNBNEBKW-UHFFFAOYSA-N 2,2,4,4,6,8,8-heptamethylnonane Chemical compound CC(C)(C)CC(C)CC(C)(C)CC(C)(C)C VCLJODPNBNEBKW-UHFFFAOYSA-N 0.000 description 1
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical group CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
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- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 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
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Abstract
本文公开了一种经由α－烯烃在烷基锌上的催化链增长反应制备烷基锌链增长产物的方法，其中所述催化剂体系使用3－10族过渡金属或3主族金属或者镧系或锕系元素和任选的一种适合的活化剂。可进一步通过用烯烃置换所述烷基锌产物中的增长烷基得到α－烯烃，而将所述产物转变成α－烯烃，或者通过将所得烷基锌链增长产物氧化形成醇盐化合物并接着将该醇盐化合物水解而转变成伯醇。
Description
本发明涉及通过低级烯烃(特别是乙烯)与低分子量烷基锌的链增长反应进行的烷基锌的制备，更具体地说本发明涉及通过包括3-10族过渡金属、3主族金属、镧系或锕系络合物和任选的一种适合的活化剂的催化剂体系催化的对锌的链增长方法。
烷基锌(和烯基锌)与低级烯烃的反应性已有报道，参见Journal ofOrganometallic chemistry 1973，60，1-10页；Liebigs Ann.Chem.1975，1162-75页；Journal of Organometallic Chemistry 1981，221，123-130页。二叔丁基锌与2当量乙烯在-20℃到75℃间反应形成双(3，3-二甲基丁基)锌，各个烷基锌基只有效插入一个乙烯分子。二-2-烯基锌化合物加入到2当量乙烯中形成二-4-烯基锌化合物，每个烯基锌基只与一个乙烯分子反应。烷基锌类物质和烯烃间反应的第二种类型也已知。它涉及一种(α-卤代烷基)锌中间体与烯烃反应形成一种环丙烷产物并且通常称为Simmons-Smith方法[参见J.Am.Chem Soc.81.4256(1959)；Ibid，86，1337，(1964)；Org React.，20，1-131(1973)]。
但是迄今没有通过低级烯烃与低分子量烷基锌反应进行的烷基锌的制备，其中多于1个烯烃插入到烷基锌键中或者所述链增长方法通过催化剂体系催化。这些类型的反应将是按化学剂量的链增长的例子，催化的方法在本领域被称为催化链增长(参见反应式1，M＝Zn)
催化剂
乙烯的催化链增长已经在烷基铝(在反应式1中M＝Al)上证实，其中活性茂金属化合物用作催化剂体系。这描述于美国专利5210338和5276220中。根据US5210338中所述的方法，包括锆和铪的茂金属卤素络合物和相关络合物连同甲基铝氧烷(MAO)的催化剂体系产生烷基铝，其中乙烯增链产物由Schulz-Flory分布最佳地描述；聚乙烯是一种持久存在的副产物。所述Schulz-Flory统计学分布由式xp＝β/(1+β)p表示，其中xp是含p加入乙烯的摩尔分数，β是Schulz-Flory分布系数。根据US5276220中所述的方法，烷基铝链增长在中等温度和压力下用包含活性锕系元素茂金属化合物的催化剂体系催化。此外，来自US5276220中所述方法的乙烯增链产物提供了泊松状烷基链长分布并避免了聚合副产物的形成。泊松链长统计学分布由式xp＝(xpe-x)/p！表示，其中xp是具p加入乙烯的摩尔分数，x是泊松分布系数，其等于每个Al-C键加入的乙烯的平均数。正如在这些专利中所述，用烷基铝的催化乙烯增链方法在比在烷基铝上的非催化化学计量乙烯链增长(100-200℃，2000-4000psi乙烯)低得多的压力和温度下操作。
发现众多在烷基铝上的乙烯增链方法特别可用于制备线性α-烯烃和线性醇。α-烯烃可通过在铝上的烷基链增长来产生，其通过用乙烯置换烯烃产物并同时进行增链反应形成Schulz-Flory型分布的产物或在第二个单独步骤中来进行。发现所述催化的增链方法提供了比进行非催化增链反应所需的更严厉条件下产生的产物更高线性的烷基。
然而，在某些情况下，存在于上述方法中的烷基铝物质的物理和化学特征限制了已知的催化增链方法的有用性。烷基铝化合物形成了组成上复杂的单体和二聚物，其难于相互分离或难以与产物烯烃分离。它们可与产物烯烃反应形成不希望存在的副产物，并且它们高度活性，即使与较低活性的化学物如二氧化碳也是如此，并且其可随时间钝化茂金属增链催化剂体系，由此极大地增加了其费用。
由此需要开发不具有使用烷基铝的已知方法的限制或者实际减少了这些限制的催化链增长方法。
我们发现一些上述问题可成功地通过使用烷基锌化合物代替烷基铝来解决。由此，根据本发明，提供了一种经在烷基锌上的α-烯烃的催化增链反应来制备烷基锌链增长产物的方法，其包括让烷基锌与链增长催化剂体系接触，所述催化剂体系使用3-10族过渡金属、或3主族金属、或者镧系或锕系络合物以及任选的适合的活化剂。这种烷基锌链增长产物可以是单种物质，也可以是化合物的混合物，并且可用于制备α-烯烃、醇、润滑剂、专用化学品、和药剂、催化剂体系、聚合物中间体或聚合物。
提供的还有一种制备α-烯烃的方法，其通过在烷基锌上进行α-烯烃的催化增链反应并接着用烯烃将作为α-烯烃的已增长烷基从烷基锌链增长产物中置换出来，其中所述链增长催化剂体系使用3-10族过渡金属、3主族金属、镧系或锕系络合物以及任选的适合的活化剂。
还提供了一种制备伯醇的方法，其通过在烷基锌上进行α-烯烃的增链反应，将得到的烷基锌增链产物氧化形成醇盐化合物，接着将醇盐化合物水解而产生伯醇，其中所述链增长催化剂体系使用3-10族过渡金属、3主族金属、镧系或锕系络合物以及任选的适合的活化剂。本发明也在另一方面提供其中所述烷基遵循最多约200个碳原子链长的基本上泊松状统计学分布的烷基锌络合物的组合物，和其中烷基遵循最多约50,000个碳原子链长的基本上Schulz-Flory状统计学分布的烷基锌络合物的组合物。
适合于链增长的烯烃的例子包括但不限于C2-C26α-烯烃和其混合物，其中优选C2-C16线性α-烯烃。对于高度线性的烷基锌链增长产物和源于这种产物的物质如线性α-烯烃和线性伯醇的制备来说，乙烯是最优选的烯烃。根据目标用途，可能需要通过本发明产生Schulz-Flory状分布的已增长烷基物质，而在其它情况中泊松状分布的已增长烷基锌物质则可能是有利的。本领域技术人员可通过控制催化剂和/或工艺条件获得在以Schulz-Flory和泊松统计为特征的分布之间的其它产物分布和分布中间体。链增长的烷基和其衍生物的骨架结构同样可通过熟练控制催化剂、烯烃原料、初始烷基化物质、和反应条件而改变。例如，为生产含低温、乙烯基高弹体或塑性体结构的聚合中间体，人们可以使用适合的双(亚胺)镍或Pd催化剂如[1，4-双(2，6-二异丙基苯基)-1，4-二氮杂-2，3-二甲基丁二烯]溴化镍(II)连同具有或不具有另一共聚单体的乙烯以及一种烷基锌物质，得到的Zn-封端的物质可用于制备AB-型嵌段共聚物。
所述催化的链增长反应可在本领域技术人员易了解的工艺条件下进行：作为存在或不存在惰性烃稀释剂如甲苯或庚烷的均相液相反应；作为两相液/液反应；作为淤浆方法，其中催化剂和/或反应产物具有极少或没有溶解性或附载于载体上；作为本体方法，其中基本上纯的烷基锌或烯烃用作主介质；作为气相方法，其中挥发性烷基锌物质和烯烃接触来自气态的催化剂。在某些情况下，链增长反应可在随后的链增长的烷基锌的反应产物存在下进行，一个非限定性例子是十四碳烯和其它链增长线性α-烯烃，其构成乙烯向二丁基锌的液相(催化)加成中所用的部分或所有稀释剂。所述催化的链增长反应可在已知类型的气相反应器(诸如垂直或水平搅拌床、固定床、或流化床反应器)、液相反应器(诸如活塞流、连续搅拌釜或环管反应器)或其组合中进行。
催化链增长反应的反应温度可不同，可在低于环境温度(20℃以下)到约200℃之间变化。乙烯的压力可从约1psig到约5000psig，但是在低于1500psig以下的压力下操作通常是有利的。
适合于链增长的烷基锌原料化合物可以是包含R′R″CH-Zn-或R′R″C-Zn-部分的任何物质或这些物质的混合物，其中R′和R″相互独立，可以是氢、烃基、甲硅烷基或取代烃基；R′和R″可连接并由此形成环状物质；在R′R″C-Zn-的情况下，键合到Zn的C不饱和[R′R″C-Zn-化合物的非限定性例子是二苯基锌和(C5H5)ZnFt]。含R′R″CH-Zn-部分的化合物包括二烷基锌类和烷基锌氢化物类，其可由式RmZnHn表示，其中m为1或2，n为0或1，m+n＝2，并且各个R独立地为C1-C30烷基。可使用这些化合物的混合物。适合的原料化合物的非限定性例子包括二甲基锌、二乙基锌、二正丁基锌、二正己基锌、二苄基锌、二正癸基锌、二正十二烷基锌等。链增长方法的优选烷基锌原料是具有偶数碳原子数的烷基的低分子量烷基锌，特别是二乙基锌和二正丁基锌。二乙基锌可从商业渠道购置，而制备其他二烷基锌的途径可从文献获悉，包括烷基锌卤化物的热歧化、锌盐被烷基铝化合物烷基化、以及Zn与二烷基汞化合物的金属交换。
所述链增长催化剂体系使用3-10族过渡金属、3主族金属、镧系或锕系络合物以及任选的适合的活化剂。适合的络合物是金属茂，其可包含至少一个基于环戊二烯基的环配体。对于本专利申请书来说，术语“金属茂或茂金属”被定义为包含一个或多个未取代或取代的环戊二烯基或环戊二烯基部分连同3-6族过渡金属、3、主族金属、镧系或锕系元素。在一个实施方案中，所述金属茂催化剂组分由通式(Cp)mMRnR′p表示，其中至少一个Cp是未取代或者优选取代的环戊二烯基环，取代或未取代的环体系诸如茚基部分、苯并茚基部分、芴基部分等，或者任何其他能η-5键合的配体诸如borolle和phosphole；M为4、5或6族过渡金属、镧系或锕系元素；R和R′独立地选自卤素、烃基、或具有1-20个碳原子的氢羧基或它们的组合；m＝1-3，n＝0-3，p＝0-3，并且m+n+p的和等于M的氧化态，优选m＝2，n＝1和p＝1。Cp可以被相同或不同的取代基的组合取代。取代基的非限定性例子包括氢或具1到20个碳原子的直链、支链或环状烷基、烯基或芳基。
在另一实施方案中，金属茂催化剂组分由下式表示：
(C5R′m)pR″s(C5R′m)MeQ3-p-x，或
R″s(C5R′m)2MeQ′
其中Me为4、5或6族过渡金属、镧系或锕系元素；至少一个C5R′m是取代的环戊二烯基，可相同或不同的各个R′为氢、具有1-20个碳原子的烷基、烯基、芳基、烷芳基或芳烷基，或者两个碳原子结合一起形成具有4-20个碳原子的取代或未取代环或环系的一部分，R″为含碳、锗、硅、磷或氮原子中的一个或多个或其组合的桥连两个(C5R′m)环或桥连一个(C5R′m)环到M的基团，当p＝0时x＝1，否则″x″总是等于0，可相同或不同的各个Q为具有1-20个碳原子的芳基、烷基、烯基、烷芳基或芳烷基、卤素或醇盐，Q′为具有1-20个碳原子的亚烷基，s为0或1，并且当s为0时，m为5并且p为0、1或2，当s为1时，m为4并且p为1。
优选的茂金属是双(五甲基环戊二烯基)二氯化锆、双(五甲基环戊二烯基)二氯化铪、双(四甲基环戊二烯基)二氯化锆、(五甲基环戊二烯基)三氯化锆、(四甲基环戊二烯基)(叔丁酰胺基)(二甲基硅烷)二甲基钛、和(五甲基环戊二烯基)(环戊二烯基)二氯化锆。
其他适合的络合物是含中性、单阴离子、双阴离子配体的3-10族过渡金属、3主族金属、镧系或锕系络合物，其中所述配体可以是单齿配体、双齿配体、三齿配体或四齿配体，并且其包括至少一个N、P、O或S原子。这种络合物的非限定性例子描述于WO 96/23010、WO 97/02298、WO 98/30609、WO 99/50313、WO 98/40374、WO00/50470、WO 98/42664、WO 99/12981、WO 98/27124、WO 00/47592、WO 01/58966和我们自己同时待审的申请PCT02/02247和PCT02/02144中。
一类优选的过渡金属络合物通常可由下面式(I)表示：
其中M为Y[II]、Y[III]、Sc[II]、Sc[III]、Ti[II]、Ti[III]、Ti[IV]、Zr[II]、Zr[III]、Zr[IV]、Hf[II]、Hf[III]、Hf[IV]、V[II]、V[III]、V[IV]、Nb[II]、Nb[III]、Nb[IV]、Nb[V]、Ta[II]、Ta[III]、Ta[IV]、Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]，X代表一个共价或离子键合到所述过渡金属M上的原子或基团；Y1为C或P(Rc)；Y2为-O(R7)，-O(在这种情况下从O到M的键是共价键)，-C(Rb)＝O，-C(Rb)＝N(R7)，-P(Rb)(Rd)＝N(R7)或-P(Rb)(Rd)＝O；Ra、Rb、Rc、Rd、R5和R7各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代的杂烃基，并且任何相邻的基团可结合一起形成环；G可为Y1和Y2间的一直键，或者是一桥连基团，当q为1时其任选包含连接到M的第三原子；L为配价键合到M的基团；n为0到5；m为1到3并且q为1或2。
一种优选的络合物由通式(II)表示：
式中Rx选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代的杂烃基，并且所有其他取代基如上所述。在式(II)的络合物中，M优选为IV族金属，特别是Ti、Zr，VI族金属，特别是Cr，或VIII族金属，特别是Ni、Co或Pd。优选Ra和Rb结合一起形成苯基，优选被取代的苯基。优选的取代基是C1-C6烷基或C6-C24芳基或芳烷基。具体地说，所述苯基可以在与氧键相邻的位置上被叔丁基或蒽基(其本身可被取代)取代。
再一种优选的络合物是式(III)的络合物：
其中M为Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]、Cu[I]、Cu[II]；X代表一个共价或离子键合到所述过渡金属M上的原子或基团；Ra和Rb各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代杂烃基，并且Ra和Rb可结合一起形成环；R5和R7各如上定义；并且L为配价结合到M的基团；n为0-5；m为1-3并且q为1或2；优选M为Fe、Ni或Pd。
一种特别优选的络合物具有下式(IV)：
其中M[T]为Ti[II]、Ti[III]、Ti[IV]、Zr[II]、Zr[III]、Zr[IV]、Hf[II]、Nf[III]、Hf[IV]、V[II]、V[III]、V[IV]、Nb[II]、Nb[III]、Nb[IV]、Nb[V]、Ta[II]、Ta[III]、Ta[IV]、Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]；X代表共价或离子键合到过渡金属M的原子或基团；T为过渡金属M的氧化态并且b为原子或基团X的价态；Y1为C或P(Rc)，A1到A3各独立地为N或P或CR，条件是至少一个是CR；R、Rc、R4和R6各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代杂烃基；并且R5和R7如上定义。
优选Y1为C。优选A1到A3各独立地为CR，其中各个R如上定义。在另一可替用的实施方案中，A1和A3均为N并且A2为CR，或者A1到A3中的一个为N，其它独立地为CR。这种实施方案的例子包括：
式(IVa) 式(IVb)
式(IVc)
式中R1、R2和R3各独立地为H或C1-C10烷基、芳基或芳烷基。
通常在上式中，R5和R7优选独立地选自取代或未取代的脂环、杂环或芳族基团，例如苯基、1-萘基、2-萘基、2-甲基苯基、2-乙基苯基、2，6-二异丙基苯基、2，3-二异丙基苯基、2，4-二异丙基苯基、2，6-二正丁基苯基、2，6-二甲基苯基、2，3-二甲基苯基、2，4-二甲基苯基、2-叔丁基苯基、2，6-二苯基苯基、2，4，6-三甲基苯基、2，6-三氟甲基苯基、4-溴-2，6-二甲基苯基、3，5-二氯-2，6-二乙基苯基和2，6-双(2，6-二甲基苯基)苯基、环己基、吡咯基、2，5-二甲基吡咯基和吡啶基。
在一优选的实施方案中，R5由基团“P”表示，并且R7由基团“Q”表示，基团P和Q如下：
基团P 基团Q
其中R19到R28独立地选自氢、卤素、烃基、取代烃基、杂烃基或取代杂烃基；当R1到R4、R6和R19到R28中任何两个或多个为烃基、取代烃基、杂烃基或取代杂烃基时，所述两个或多个基团可连接形成一个或多个环状取代基。
优选R19、R20、R21和R22中至少一个为烃基、取代烃基、杂烃基或取代杂烃基。更优选R19和R20的至少一个以及R21和R22的至少一个为烃基、取代烃基、杂烃基或取代杂烃基。最优选R19、R20、R21和R22均独立地选自烃基、取代烃基、杂烃基或取代杂烃基。R19、R20、R21和R22优选独立地选自甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、新戊基、正己基、4-甲基戊基、正辛基、苯基和苄基。
R1、R2、R3、R4、R6、R19、R20、R21、R22、R23、R25、R26和R28优选独立地选自氢和C1-C8烃基，例如甲基、乙基、正丙基、正丁基、叔丁基、正己基、正辛基、苯基和苄基。
一种特别优选的络合物具有式Z
式Z
其中所有取代基均如上所述。优选的络合物是2，6-二乙酰基吡啶双(2，4，6-三甲基缩苯胺)FeCl2和2，6-二乙酰基吡啶双(2，6-二异丙基缩苯胺)FeCl2。
在一可替用实施方案中(可应用于所有上述结构中)，R5为具有式-NR29R30的基团，R7为具有式-NR31R32的基团，其中R29到R32独立地选自氢、卤素、烃基、取代烃基、杂烃基或取代杂烃基，并且可连接形成一个或多个环状取代基。这种化合物的例子公开于WO00/50470。
R5和R7两者的另一优选取代基是如我们自己同时待审的申请PCT02/02247中所述的吡唑基。
特别优选的是具有式(II)的取代基：
式(II)
在上面公开的络合物中X表示的原子或基团可以例如选自卤化物、硫酸根、硝酸根、硫羟酸根、硫代羧酸根、BF4 -、PF6 -、氢化物、烃氧化物、羧酸根、烃基、取代烃基和杂烃基或β-二酮酸根。这种原子或基团的例子有氯化物、溴化物、甲基、乙基、丙基、丁基、辛基、癸基、苯基、苄基、甲氧根、乙氧根、异丙氧根、甲苯磺酸根、三氟甲磺酸根、甲酸根、乙酸根、苯氧基和苯甲酸根。在式(I)化合物中原子或基团X的优选例子是卤化物，例如氯化物、溴化物；氢化物；烃氧化物，如甲醇化物、乙醇化物、异丙醇化物、苯酚化物；羧酸根，例如甲酸根、乙酸根、苯甲酸根；烃基，例如甲基、乙基、丙基、丁基、辛基、癸基、苯基、苄基；取代烃基；杂烃基；甲苯磺酸根；和三氟甲磺酸根。优选的X选自卤化物、氢化物和烃基。特别优选氯化物。
L可以是例如醚诸如四氢呋喃或乙醚，醇诸如乙醇或丁醇，伯、仲或叔胺或膦。
所述链增长催化剂体系任选使用一种适合的活性剂。用于本发明的催化剂的活性剂化合物适当地选自有机铝化合物和烃基硼化合物，并且可包含超过一种的这些化合物。适合的有机铝化合物包括三烷基铝化合物，例如三甲基铝、三乙基铝、三丁基铝、三正辛基铝、乙基二氯化铝、二乙基氯化铝和铝氧烷。铝氧烷通常作为低聚化合物为本领域人们所熟悉，其可通过向烷基铝化合物如三甲基铝中控制加入水进行制备。这种化合物可以线性、环状或其混合物。通常相信商品铝氧烷是线性和环状化合物的混合物。环状铝氧烷可由式[R16AlO]s表示，并且线性铝氧烷由式R17(R18AlO)s表示，其中s为约2到50的一个数，并且其中R16、R17和R18代表烃基，优选C1-C6烷基例如甲基、乙基或丁基。另一适合类型的有机铝化合物为三(五氟苯基)铝。
适合的烃基硼化合物的例子是四苯基硼酸二甲苯基铵、三苯甲基四苯基硼酸盐、三苯基硼、四(五氟苯基)硼酸二甲苯基铵、四[(双-3，5-三氟甲基)苯基]硼酸钠、H+(OEt2)[(双-3，5-三氟甲基)苯基]硼酸盐、三苯甲基四(五氟苯基)硼酸盐和三(五氟苯基)硼。
通常发现其用量足以提供相对于每个过渡金属络合物的过渡金属原子为0.1-20,000个、优选1-2000个的铝原子或硼原子。
本发明中所用的络合物需要时可包括超过一个的上述3-10族过渡金属、3主族金属、镧系或锕系络合物。所述催化剂可包括例如2，6-二乙酰基吡啶二(2，6-二异丙基缩苯胺)FeCl2络合物和2，6-二乙酰基吡啶二(2，4，6-三甲基缩苯胺)FeCl2络合物的混合物，或2，6-二乙酰基吡啶二(2，6-二异丙基缩苯胺)CoCl2络合物和2，6-二乙酰基吡啶二(2，4，6-三甲基缩苯胺)FeCl2络合物的混合物。除了所述一种或多种定义的过渡金属化合物外，本发明的催化剂也可包括一种或多种其它类型的过渡金属或催化剂。
本发明的络合物可没有载体或附载于载体材料如硅石、硅石/矾土、氯化镁、沸石、氧化铝或氧化锆上，或者附载于聚合物或预聚物如聚乙烯、聚苯乙烯或聚(氨基苯乙烯)上，或附载于另一种多相催化剂上。在另一种实施方案中，络合物和活化剂两者共同附载于载体材料、聚合物或预聚物上。
在反应式3中说明的链增长反应可利用纯的烷基锌介质或可利用烃溶剂稀释剂诸如甲苯或庚烷。当所述链通过乙烯增长时，可将较高级(C3-C20+α-烯烃诸如1-辛烯用作溶剂或助溶剂。反应温度可从约室温20℃到150℃。乙烯的压力可从约15psig到约1500psig。
过渡金属与烷基锌的摩尔比率可从约1×10-7到1×10-1，优选从约1×10-6到1×10-2，更优选在2×10-6到5×10-3范围。
当用一些催化剂进行链增长反应时，使催化剂活化以避免诱导期是有帮助的。一种适合的方法是在单独的容器中，将催化剂在铝氧烷溶液中、20℃保温约5分钟。随后加入到烷基锌中而容许立即吸收乙烯。
正如下面实施例中所显示的那样，可通过用乙烯和/或其它α-烯烃作为置换烯烃，用例如Ni催化剂进行催化置换，从烷基锌化合物中回收C2-C20+α-烯烃。或者，链增长产物可氧化成烷基锌过氧化物中间体，使用已知方法氧化和水解成线性伯醇，或使用已知方法制备其它特定物质。
本发明将进一步通过下面通用的方法和实施例来说明，但本发明并不受这些通用方法和实施例的限定。
实施例
在氮气气氛下进行络合物、烷基锌和任选的活化剂的处理以及反应器的组装和拆卸。乙烯为聚合物级，使用时没有纯化。按照WO99/12981中所述的既定方法制备2，6-双[1-(2，6-二异丙基苯基)亚胺基)乙基]吡啶氯化铁(II)和2，6-双[1-(2，6-二异丙基苯基)亚胺基)乙基]吡啶氯化钴(II)。按照GB0100249中所述的方法制备2，4-双[(2，6-二异丙基苯基亚胺基)苄基]-6-甲基嘧啶氯化铁(II)。按照WO 00/50470中的方法制备实施例14中所用的络合物。按照GB 0112023的方法制备实施例15中所用的络合物。
按照既定的文献方法制备双(正丁基环戊二烯基)二氯化锆和[1，4-双(2，6-二异丙基苯基)-1，4-二氮杂-2，3-二甲基丁二烯]溴化镍(II)。MAO(10％(重量)，在甲苯中)购自Witco。双(环戊二烯基)二氯化锆、双(五甲基环戊二烯基)二氯化锆、乙酰基丙酮酸镍(II)、三甲基铝(2M甲苯溶液)、十二烷(无水)、环己烷(无水)、和壬烷(无水)购自Aldrich。十一烷购自Aldrich并在使用前经CaH2蒸馏。二乙基锌溶液购自Acros(0.87M甲苯溶液)或Aldrich(1.1M甲苯或庚烷溶液)。外消旋亚乙基二(茚基)二氯化锆(IV)和萘甲酸镍购自Strem Chemical。1-己烯(98.07％纯度)购自BP。
实施例A
二己基锌的合成
用30分钟向在40ml乙醚中的3.2gMg中加入1-氯己烷(13g，108mmol，通过中性活性氧化铝过滤)在50ml乙醚中的溶液，由此制备正己基氯化镁。让混合物再回流2小时。用30分钟将所述溶液转移到53ml 1.0M ZnCl2(53mmol)的乙醚溶液中并将反应混合物搅拌过夜。将混合物过滤并将剩余的盐用100ml乙醚洗涤两次。合并的滤液通过真空去除溶剂浓缩。真空蒸馏(0.08毫巴，68℃)，以63％的收率(7.83g，33.2mmol)得到无色液体形式的二己基锌。
1H NMR(250MHz，C6D6，298K)：δ1.57(br quintet，2H，Zn-CH2-CH2-，3J＝7Hz)，1.36-1.28(m，6H，-CH2-CH2-CH2-CH3)，0.93(brt，3H，-CH3，3J＝7Hz)，0.29(t，2H，Zn-CH2-，3J＝7Hz)13C NMR(62.9MHz，C6D6，298K)：δ36.6，32.3，26.7，23.1，16.3，14.4.
实施例1-使用吡啶基双亚胺铁催化剂催化的链增长
A)催化剂溶液的制备
在Schlenk烧瓶中装入2，6-双[1-((2，6-二异丙基苯基)亚胺基)乙基]吡啶氯化铁(II)(31mg；0.050mmol)和24ml甲苯。向无色溶液加入MAO(3.0ml)，形成透明橙色溶液，在室温下搅拌5分钟。
B)链增长反应
在500ml Schlenk烧瓶中装入甲苯(50ml)和二乙基锌(2.5ml0.87M己烷溶液)。抽空具suba密封的Schlenk烧瓶并用乙烯回填(0.75巴过压)。向该混合物注入在A)制备的2.5ml催化剂溶液(含5.0微摩尔Fe)，得到淡黄色溶液。在室温下反应30分钟，由此在1分钟内发生放热反应。15分钟后反应混合物变粘稠和浑浊并且温度下降。30分钟后通过用50ml稀HCl溶液(2M)水解停止反应。将沉淀的聚合物过滤，用丙酮洗涤，在真空箱(60℃)中干燥过夜并通过GPC和1H-NMR分析。分离滤液中的有机部分，用硫酸镁干燥并过滤。使用2，2，4，4，6，8，8-七甲基壬烷作为内标测定该有机部分的链烷烃含量。图1显示了甲苯不溶部分(Mn＝600，Mw＝700，PDI＝1.1，活性＝1000g/mmol·h·bar)的GPC图连同在无二乙基锌的相同条件下产生的聚乙烯(Mn＝10000，Mw＝192000，PDI＝19.2，活性＝1200g/mmol·h·bar)的GPC图。在二乙基锌存在下形成的产物的1H-NMR分析表明所述产物完全饱和(每1000个C有43.6甲基和0.2乙烯基端基)。甲苯可溶部分的GC分析证实偶数链烷烃的存在。
实施例2-二乙基锌浓度的增加对使用吡啶双亚胺铁催化剂催化的链增长的影响
在与实施例1类似的实验中，研究二乙基锌浓度对催化的链增长的影响(1微摩尔实施例1中所用的Fe络合物，100当量MAO，1巴乙烯，50ml甲苯，30min，室温)。
图2显示了用2200当量二乙基锌(活性＝2800g/mmol·h·bar)、4400当量二乙基锌(活性＝3000g/mmol·h·bar)和8700当量二乙基锌(活性＝2000g/mmol·h·bar)制备的甲苯溶液中的偶数链烷烃的分布(通过GC测定)。
实施例3-使用吡啶基双亚胺铁催化剂的取决于时间的催化链增长
A)催化剂溶液的制备
在Schlenk烧瓶中装入实施例1中所用的Fe络合物(12mg；0.020mmol)和24ml甲苯。向该无色溶液加入MAO(1.2ml)，得到一种透明橙色溶液，将其在室温下搅拌5分钟。
B)增链反应
在250ml夹套双颈圆底烧瓶中置入甲苯(50ml)、0.40ml经蒸馏的十一烷和二乙基锌(4.0ml 0.87M己烷溶液)。
将烧瓶配上suba封、温度计和水冷却装置并抽空和回填乙烯(0.75巴过压)。向溶液注入2.5ml在A中制备的催化剂溶液(含2.0微摩尔Fe)，得到一种淡黄色溶液。在催化剂注入后30秒钟内温度从19℃上升到32℃并随后下降。通过套管从反应混合物取样(约2ml)监视反应。样品用2ml稀盐酸溶液(2M)水解并使用十一烷作为内标通过GC测定甲苯部分的链烷烃含量。8分钟后反应混合物变得粘稠和浑浊。20分钟后通过用50ml稀盐酸溶液(2M)水解停止反应。样品1-7的GC分析显示了具泊松分布的偶数链烷烃(下面的表1和图3)。
表1.样品1-7的不同链烷烃(C8-C34)的产量(mg)
| 样品 | C8 | C10 | C12 | C14 | C16 | C18 | C20 |
| 1(2min) | 120.2 | 186.4 | 226.1 | 219.5 | 186.6 | 130.5 | 85.5 |
| 2(4min) | 58.7 | 108.0 | 170.0 | 215.2 | 232.1 | 220.1 | 188.7 |
| 3(6min) | 32.9 | 57.4 | 104.3 | 154.0 | 193.9 | 214.8 | 215.5 |
| 4(9min) | 17.4 | 28.9 | 58.6 | 99.6 | 145.6 | 187.4 | 218.1 |
| 5(12min) | 16.6 | 18.5 | 38.5 | 69.7 | 110.1 | 154.7 | 198.1 |
| 6(15min) | 9.8 | 15.3 | 31.8 | 58.8 | 95.5 | 137.4 | 179.3 |
| 7(18min) | 14.8 | 13.4 | 27.5 | 51.1 | 84.2 | 123.8 | 166.0 |
| 样品 | C22 | C24 | C26 | C28 | C30 | C32 | C34 |
| 1(2min) | 50.9 | 28.4 | 15.3 | 7.8 | 4.0 | ||
| 2(4min) | 148.8 | 108.3 | 74.4 | 48.7 | 30.7 | 19.1 | 11.6 |
| 3(6min) | 199.8 | 170.4 | 136.3 | 103.8 | 75.8 | 54.1 | 37.7 |
| 4(9min) | 234.4 | 232.6 | 215.7 | 189.5 | 159.3 | 129.6 | 99.7 |
| 5(12min) | 233.7 | 253.8 | 255.2 | 242.4 | 220.2 | 189.4 | 141.3 |
| 6(15min) | 213.7 | 232.9 | 233.2 | 220.1 | 199.0 | 172.6 | 132.6 |
| 7(18min) | 203.3 | 225.9 | 229.7 | 219.4 | 200.0 | 173.7 | 133.8 |
实施例4-使用二茂锆催化的链增长
在与实施例1类似的实验中，研究双(五甲基环戊二烯基)二氯化锆(ZrCp* 2Cl2)对二乙基锌的链增长的影响(5微摩尔ZrCp* 2Cl2，100当量MAO，1巴乙烯，50ml甲苯，30min，室温)。
图4显示了用440当量二乙基锌(Mn＝1600，Mw＝12000，PDI＝7.7，活性＝3500g/mmol·h·bar)、1750当量二乙基锌(Mn＝700，Mw＝1500，PDI＝2.2，活性＝2600g/mmol·h·bar)和无二乙基锌(Mn＝9300，Mw＝72000，PDI＝7.7，活性＝1200g/mmol·h·bar)制备的甲苯不溶部分的GPC图。1H-NMR分析表明在二乙基锌存在下形成的产物完全饱和(对于用440当量ZnEt2的反应来说每1000个碳有14.9个甲基和0.2个乙烯端基，对于用1750当量ZnEt2的反应来说每1000个碳有37.5个甲基和0.1个乙烯端基)。
实施例5-使用茂金属催化剂催化的链增长
在与实施例1类似的实验中，研究外消旋-亚乙基二(茚基)二氯化锆(IV)(rac-(EBI)ZrCl2)对二乙基锌的链增长反应的影响(5微摩尔rac-(EBI)ZrCl2，100当量MAO，1巴乙烯，50ml甲苯，30min，室温)。
图5显示了用440当量二乙基锌(Mn＝800，Mw＝1600，PDI＝1.9，活性＝2400g/mmol·h·bar)和无二乙基锌(Mn＝66000，Mw＝261000，PDI＝3.9，活性＝1300g/mmol·h·bar)制备的甲苯不溶部分的GPC图。1H-NMR分析表明在二乙基锌存在下形成的产物完全饱和(相对于每1000个碳为31.9个甲基和0.2乙烯端基)。
实施例6-使用茂金属催化剂催化的链增长
在类似于实施例3的实验中，从含(rac-(EBI)ZrCl2)和二乙基锌的反应混合物(2微摩尔rac-(EBI)ZrCl2，100当量MAO，2200当量ZnEt2，1巴乙烯，50ml甲苯，室温)取样。只有在2.5分钟后取的第一个样品得到具图6所示分布和用Fel进行的对比实验的GC图(参见实施例3)的甲苯溶解的链烷烃。
实施例7-使用Ni(α-二亚胺)催化剂催化的链增长
在类似于实施例1的实验中，研究[1，4-双(2，6-二异丙基苯基)-1，4-二氮杂-2，3-二甲基丁二烯]溴化镍(II)((dab)NiBr2)对二乙基锌的链增长反应的影响(5微摩尔(dab)NiBr2，100当量MAO，1巴乙烯，50ml甲苯，1小时，室温)。
图7显示了用440当量二乙基锌(Mn＝23000，Mw＝67000，PDI＝2.9，活性＝250g/mmol·h·bar)、1750当量二乙基锌(Mn＝4300，Mw＝8400，PDI＝1.9，活性＝300g/mmol·h·bar)和无二乙基锌情况下(Mn＝19300，Mw＝435000，PDI＝2.3，活性＝300g/mmol·h·bar)制备的聚合物的GPC图。图8显示了二乙基锌并不影响这些反应中的支化水平。
实施例8-使用嘧啶双亚胺铁催化剂催化的链增长
在类似于实施例1的实验中，研究2，4-二[(2，6-二异丙基苯基亚胺基)苄基]-6-甲基嘧啶氯化铁(II)(N4Fel)对二乙基锌的链增长反应的影响(5微摩尔N4Fe1，100当量MAO，1巴乙烯，50ml甲苯，30分钟，室温)。产物包括甲苯可溶的具如图9所示分布的偶数链烷烃(＞95％)。
实施例9-使用吡啶基双亚胺钴催化剂催化的链增长
在类似于实施例1的实验中，研究2，6-二[1-((2，6-二异丙基苯基)亚胺基)乙基]吡啶氯化钴(II)对二乙基锌的链增长反应的影响(5微摩尔Co，100当量MAO，1巴乙烯，50ml甲苯，30分钟，室温)。图10显示了用500当量二乙基锌(Mn＝1 800，Mw＝3500，PDI＝2.0，活性＝600g/mmol·h·bar)和无二乙基锌情况下(Mn＝3300，Mw＝11000，PDI＝3.2)制备的甲苯不溶部分的GPC图。1H-NMR和GC分析表明用500当量二乙基锌进行反应所形成的产物中85％完全饱和(相对于每1000个C为11.3个甲基和1.3个乙烯基端基)。
实施例10-从二己基锌置换1-己烯
将装有645mg二己基锌(2.74mmol)和40ml甲苯的具suba seal的250ml Schlenk烧瓶抽空并且用乙烯回填(0.75巴过压)。将35.4mgNi(acac)2(0.138mmol)的3ml甲苯溶液注入到溶液中。通过取样监测反应随时间的变化，用2M HCl水解样品并比较甲苯部分的己烷对1-己烯含量(通过GC测定)，如图11所示。
实施例11-催化的链增长后从二烷基锌链置换α-烯烃
在类似于实施例1的反应中制备二烷基锌的混合物(2微摩尔Fel，1750当量ZnEt2，100当量MAO，1巴乙烯，50ml甲苯，8分钟，室温)。8分钟反应后，将Schlenk烧瓶的内容物转移到另一个装有干燥硅石的Schlenk烧瓶中。搅拌15分钟后，在1巴乙烯压力下，将甲苯溶液过滤到装有Ni(acac)2(0.35mmol)的10ml甲苯溶液的Schlenk烧瓶中。30分钟后通过加入50ml 2M HCl水解反应混合物。甲苯溶液的GC分析(图12)表明包括75％偶数1-链烯烃和25％偶数链烷烃的分布。
实施例12-通过1-己烯从二乙基锌置换乙烯
用乙烯(1巴)清洗装有8.0ml二乙基锌、1.0ml壬烷和15.5ml 1-己烯的厚壁Fischer-Porter管三次，采样(t0)、在100psi乙烯下在60℃加热1.0小时，冷却到室温并采样(t＝60分钟)。将萘甲酸镍(0.66ml1.26×10-2M在十二烷中的溶液)溶液加入到在所述F-P管中的溶液中，并在室温下搅拌1.0小时，取样(t＝120min)，用氮气(1巴)冲洗溶液上方的气体空间三次、达到100psi氮气，然后在60℃加热1小时，并采样(t＝180分钟)。将样品水解并用GC分析己烯和己烷。己烷的量相应于用乙烯置换二乙基锌所形成的己基锌部分的量。置换的程度显示于表2。
| 总时间(分钟) | 以己基计的R-Zn基团(％) |
| 0 | 0.00 |
| 60 | 0.41 |
| 120 | 15.14 |
| 180 | 31.49 |
实施例13-使用金属茂催化剂催化的链增长
在类似于实施例1的实验中，研究双(正丁基环戊二烯基)二氯化锆(Zr(CpBu)2Cl2)对二乙基锌的链增长反应的影响(5微摩尔rac-(EBI)ZrCl2，2000当量ZnEt2，100当量MAO，1巴乙烯，50ml甲苯，30分钟，室温)。产物包括甲苯可溶的具如图13中所示分布的偶数链烷烃(＞95％)。
实施例14-使用吡啶基双亚胺铁催化剂催化的链增长
在与实施例1类似的实验中，研究下示吡啶基双亚胺铁络合物对二乙基锌的链增长反应的影响(5微摩尔Fe，2000当量ZnEt2，100当量MAO，1巴乙烯，50ml甲苯，30分钟，室温)。甲苯可溶部分的GC分析显示了一系列低聚物，其75％为偶数链烷烃，25％为偶数链烯烃。
实施例15-使用吡啶基双亚胺铁催化剂催化的链增长
在与实施例1类似的实验中，研究下面的吡啶基双亚胺铁络合物对二乙基锌的链增长反应的影响(5微摩尔Fe，2000当量ZnEt2，100当量MAO，1巴乙烯，50ml甲苯，30分钟，室温)。甲苯可溶部分的GC分析显示了一系列低聚物，其70％为偶数链烷烃，30％为偶数链烯烃。
Claims (23)
1.经由α-烯烃在烷基锌上的催化链增长反应制备烷基锌链增长产物的方法，该方法包括使烷基锌与链增长催化剂体系接触，所述催化剂体系使用3-10族过渡金属或3主族金属或者镧系或锕系络合物和任选的一种适合的活化剂。
2.制备α-烯烃的方法，该方法包括实施权利要求1的方法，接着用烯烃置换所述烷基锌产物中的增长烷基，得到α-烯烃。
3.制备伯醇的方法，包括实施权利要求2的方法，接着将得到的烷基锌链增长产物氧化形成醇盐化合物，接着将该醇盐化合物水解成伯醇。
4.前述权利要求中任一项的方法，其中所述烷基锌化合物包括一种含R′R″CH-Zn或R′R″C-Zn部分的物质或这种物质的混合物，其中R′和R″独立地选自氢、烃基、甲硅烷基和取代烃基，并且可连接形成环状物质，条件是在R′R″C-Zn情况下，键合到Zn的C不饱和。
5.前述权利要求中任一项的方法，其中所述烷基锌化合物具有式RmZnHn，其中m为1或2，n为0或1，m+n＝2，并且各个R独立地为C1-C30烷基。
6.前述权利要求中任一项的方法，其中所述烷基锌化合物选自二甲基锌、二乙基锌、二正丁基锌、二正己基锌、二苄基锌、二正癸基锌、二正十二烷基锌、二苯基锌和(C5H5)ZnEt。
7.前述权利要求中任一项的方法，其中所述α-烯烃选自C2-C16线性α-烯烃。
8.前述权利要求中任一项的方法，其中所述链增长催化剂体系包含茂金属，其可含有至少一种基于环戊二烯基的环配体。
9.权利要求8的方法，其中所述链茂金属催化剂组分由通式(Cp)mMRnR′p表示，其中至少一个Cp选自未取代或者取代的环戊二烯基环，取代或未取代的环体系诸如茚基部分、苯并茚基部分、芴基部分，以及能η-5键合的任何其他配体；M选自4、5或6族过渡金属、镧系或锕系元素；R和R′独立地选自卤素、烃基、和具有1-20个碳原子的氢羧基或它们的组合；m＝1-3，n＝0-3，p＝0-3，并且m+n+p的和等于M的氧化态。
10.权利要求8的方法，其中所述链茂金属催化剂组分选自：
(C5R′m)pR″s(C5R′m)M*Q3-p-x，和
R″s(C5R′m)2M*Q′
其中M*为4、5或6族过渡金属，镧系或锕系元素；至少一个C5R′m是取代的环戊二烯基；可相同或不同的各个R′为氢或具有1-20个碳原子的烷基、烯基、芳基、烷芳基或芳烷基，或者两个碳原子结合一起形成具有4-20个碳原子的取代或未取代环或环系的一部分，R″为含至少一个碳、锗、硅、磷或氮原子的桥连两个(C5R′m)环或桥连一个(C5R′m)环到M*的基团；可相同或不同的各个Q选自具有1-20个碳原子的芳基、烷基、烯基、烷芳基或芳烷基、卤素或醇盐；Q′为具有1-20个碳原子的亚烷基；s为0或1，并且当s为0时，m为5并且p为0、1或2，当s为1时，m为4并且p为1；当p＝0时x＝1，否则″x″ 总是等于0。
11.权利要求8的方法，其中所述链茂金属催化剂组分选自双(五甲基环戊二烯基)二氯化锆、双(五甲基环戊二烯基)二氯化铪、双(四甲基环戊二烯基)二氯化锆、(五甲基环戊二烯基)三氯化锆、(四甲基环戊二烯基)(叔丁酰胺基)(二甲基硅烷)二甲基钛和(五甲基环戊二烯基)(环戊二烯基)二氯化锆。
12.权利要求1-7中任一项的方法，其中所述链增长催化剂体系包括式(I)的络合物：
其中M为Y[II]、Y[III]、Sc[II]、Sc[III]、Ti[II]、Ti[III]、Ti[IV]、Zr[II]、Zr[III]、Zr[IV]、Hf[II]、Hf[III]、Hf[IV]、V[II]、V[III]、V[IV]、Nb[II]、Nb[III]、Nb[IV]、Nb[V]、Ta[II]、Ta[III]、Ta[IV]、Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]，X代表一个共价或离子键合到所述过渡金属M上的原子或基团；Y1为C或P(Rc)；Y2为-O(R7)-O(在这种情况下从O到M的键是共价键)，-C(Rb)＝O，-C(Rb)＝N(R7)，-P(Rb)(Rd)＝N(R7)或-P(Rb)(Rd)＝O；Ra、Rb、Rc、Rd、R5和R7各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代的杂烃基，并且任何相邻的基团可结合一起形成环；G可为Y1和Y2间的一直键，或者是一桥连基团，当q为1时，其任选包含连接到M的第三原子；L为配价键合到M的基团；n为0-5；m为1-3，q为1或2。
13.权利要求1-7中任一项的方法，其中所述链增长催化剂体系包含式(II)的络合物：
其中M为Y[II]、Y[III]、Sc[II]、Sc[III]、Ti[II]、Ti[III]、Ti[IV]、Zr[II]、Zr[III]、Zr[IV]、Hf[II]、Hf[III]、Hf[IV]、V[II]、V[III]、V[IV]、Nb[II]、Nb[III]、Nb[IV]、Nb[V]、Ta[II]、Ta[III]、Ta[IV]、Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]，X代表一个共价或离子键合到所述过渡金属M上的原子或基团；Ra、Rb、Rx和R5各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代的杂烃基，并且任何相邻的基团可结合一起形成环；L为配价键合到M的基团；n为0-5；m为1-3，q为1或2。
14.权利要求1-7中任一项的方法，其中所述链增长催化剂体系包含式(III)的络合物：
其中M为Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]、Cu[I]、Cu[II]；X代表一个共价或离子键合到所述过渡金属M上的原子或基团；Ra和Rb各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代杂烃基，并且Ra和Rb可结合一起形成环；R5和R7各如上定义；并且L为配价结合到M的基团；n为0-5；m为1-3，q为1或2。
15.权利要求1-7中任一项的方法，其中所述链增长催化剂体系包含式(IV)的络合物：
其中M[T]为Ti[II]、Ti[III]、Ti[IV]、Zr[II]、Zr[III]、Zr[IV]、Hf[II]、Hf[III]、Hf[IV]、V[II]、V[III]、V[IV]、Nb[II]、Nb[III]、Nb[IV]、Nb[V]、Ta[II]、Ta[III]、Ta[IV]、Cr[II]、Cr[III]、Mn[II]、Mn[III]、Mn[IV]、Fe[II]、Fe[III]、Ru[II]、Ru[III]、Ru[IV]、Co[II]、Co[III]、Rh[II]、Rh[III]、Ni[II]、Pd[II]；X代表共价或离子键合到过渡金属M的原子或基团；T为过渡金属M的氧化态并且b为原子或基团X的价态；Y1为C或P(Rc)，A1到A3各独立地为N或P或CR，条件是至少一个为CR；R、Rc、R4、R5、R6和R7各独立地选自氢、卤素、烃基、取代烃基、杂烃基、取代杂烃基或SiR′3，其中各个R′独立地选自氢、卤素、烃基、取代烃基、杂烃基和取代杂烃基。
16.权利要求15的方法，其中Y1为C，并且A1到A3各独立地为CR，或A1和A3均为N并且A2为CR，或者A1到A3的一个为N而其余独立地为CR。
17.权利要求15的方法，其中Y1为C，A1到A3各独立地为CR，R5由基团“P”表示，并且R7由基团“Q”表示，基团P和Q如下：
基团P 基团Q
其中R19到R28独立地选自氢、卤素、烃基、取代烃基、杂烃基或取代杂烃基；当R1到R4、R6和R19到R28的任何两个或多个为烃基、取代烃基、杂烃基或取代杂烃基时，所述两个或多个基团可连接形成一个或多个环状取代基。
18.权利要求1-7中任一项的方法，其中所述链增长催化剂体系选自2，6-二乙酰基吡啶二(2，4，6-三甲基缩苯胺)FeCl2和2，6-二乙酰基吡啶二(2，6-二异丙基缩苯胺)FeCl2。
19.前述权利要求中任一项的方法，其中所述链增长催化剂体系的活化剂选自有机铝化合物和烃基硼化合物。
20.前述权利要求中任一项的方法，其中所述链增长反应使用纯的烷基锌介质或烃溶剂稀释剂。
21.前述权利要求中任一项的方法，其中过渡金属与烷基锌的摩尔比率在1×10-7到1×10-1之间。
22.前述权利要求中任一项的方法，其中所述催化剂在加入到烷基锌前通过在20℃于铝氧烷溶液中保温约5分钟而使其活化。
23.包含烷基锌络合物的组合物，其中所述烷基遵循最多约200个碳原子链长的基本上泊松状的统计学分布，或者最多约50,000碳原子链长的基本上Schulz-Flory状的统计学分布。
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- 2002-07-05 CN CN2007101264295A patent/CN101070261B/zh not_active Expired - Lifetime
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107709383A (zh) * | 2015-05-29 | 2018-02-16 | 陶氏环球技术有限责任公司 | 一种用于制造聚烯烃的方法 |
| CN109422828A (zh) * | 2017-09-05 | 2019-03-05 | 中国石油化工股份有限公司 | 用于烯烃聚合的催化剂体系和制备低分子量聚乙烯的催化体系及方法和低分子量聚乙烯 |
| CN116490268A (zh) * | 2020-09-14 | 2023-07-25 | 切弗朗菲利浦化学公司 | 由烃通过过渡金属催化生产醇和羰基化合物 |
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| KR100895599B1 (ko) | 2009-05-06 |
| US20070142656A1 (en) | 2007-06-21 |
| EA007922B1 (ru) | 2007-02-27 |
| ES2711251T3 (es) | 2019-04-30 |
| EP2308815B1 (en) | 2018-11-14 |
| US20030078458A1 (en) | 2003-04-24 |
| EA011711B1 (ru) | 2009-04-28 |
| US7964681B2 (en) | 2011-06-21 |
| ES2623164T3 (es) | 2017-07-10 |
| CN101070261A (zh) | 2007-11-14 |
| MY143732A (en) | 2011-07-15 |
| CA2456711A1 (en) | 2003-02-20 |
| CN100457695C (zh) | 2009-02-04 |
| EP2308815A1 (en) | 2011-04-13 |
| EA200400255A1 (ru) | 2004-10-28 |
| US20080200709A1 (en) | 2008-08-21 |
| CN101070261B (zh) | 2012-11-14 |
| WO2003014046A1 (en) | 2003-02-20 |
| EP1414772A1 (en) | 2004-05-06 |
| US7087686B2 (en) | 2006-08-08 |
| EP1414772B1 (en) | 2017-02-01 |
| US7767771B2 (en) | 2010-08-03 |
| EA200601455A1 (ru) | 2006-12-29 |
| KR20040032897A (ko) | 2004-04-17 |
| CA2456711C (en) | 2013-01-08 |
| JP2004537584A (ja) | 2004-12-16 |
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