CN1348458A - Oligomerisation catalyst - Google Patents
Oligomerisation catalyst Download PDFInfo
- Publication number
- CN1348458A CN1348458A CN00806736A CN00806736A CN1348458A CN 1348458 A CN1348458 A CN 1348458A CN 00806736 A CN00806736 A CN 00806736A CN 00806736 A CN00806736 A CN 00806736A CN 1348458 A CN1348458 A CN 1348458A
- Authority
- CN
- China
- Prior art keywords
- trianacyclohexane
- catalyst
- oligomerization
- alkyl
- independently
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000011651 chromium Substances 0.000 claims abstract description 71
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 62
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000004435 Oxo alcohol Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 150000001639 boron compounds Chemical class 0.000 claims description 7
- 238000007037 hydroformylation reaction Methods 0.000 claims description 7
- 150000001844 chromium Chemical class 0.000 claims description 5
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000001845 chromium compounds Chemical class 0.000 abstract 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- -1 aluminum compound Chemical class 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 11
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000005829 trimerization reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 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 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- 150000003233 pyrroles Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 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 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
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- 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
- 238000001035 drying Methods 0.000 description 2
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 238000002203 pretreatment Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
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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 2
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
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- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
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- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 206010013786 Dry skin Diseases 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- HTFFABIIOAKIBH-UHFFFAOYSA-N diazinane Chemical compound C1CCNNC1 HTFFABIIOAKIBH-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
An oligomerization catalyst for olefins is obtainable from: a) a chromium compound CrX3 and the at least equimolar amount, based on the chromium compound CrX3, of a ligand L or from an existing chromium complex CrX3L, in which the groups X are, independently of one another, abstractable counterions and L is a 1,3,5-triazacyclohexane of the formula Iwhere the groups R<1 >to R<9 >are, independently of one another: hydrogen or organosilicon or substituted or unsubstituted carboorganic groups having from 1 to 30 carbon atoms, where two geminal or vicinal radicals R<1 >to R<9 >may also be joined to form a five-or six-membered ring, andb) at least one activating additiveand also a process for preparing oligomers of olefins using these catalysts, the oligomers thus obtainable, and the oxo alcohols obtainable from these oligomers.
Description
The present invention relates to a kind of olefin oligomerization catalyst, can be from a) a kind of chromium cpd CrX of following acquisition
3, and based on this chromium cpd CrX
3The joining of equimolar amount at least
Body L, perhaps a kind of already present chromium complex CrX
3L, wherein radicals X is independently of one another, for
Removable anti-electron ion, L is 1,3 of formula I, the 5-Trianacyclohexane,
Radicals R wherein
1To R
9Be independently of one another: hydrogen or to have the silicon of 1 to 30 carbon atom organic
Or carbon organic group that replace or non-replacement, wherein two geminals or the adjacent radicals R
1
To R
9Also can connect into five-unit or six-unit's ring, and b) at least a activating additive.
The invention further relates to a kind of technology that adopts new catalyst to prepare alkene oligomer, and oligopolymer that obtains by this way and the oxo alcohol that obtains by these oligopolymers.
Alkene oligomer with 30 carbon atoms nearly has very big importance economically as plastics with multipolymer (as the 1-hexene) or as the precursor (as 1-hexene and decene and four decene) of oxo alcohol, and wherein the latter constitutes tensio-active agent and a plasticiser component of plastics again.In the combination producing of chemical industry, flow to daily living article from for example industrial alkene from the steam cracker, oligomerization process is the step at a center.
Use in the oligomerisation of alpha-olefin by chromium cpd, the catalyzer that amine and aluminum compound are formed is for known usually:
According to EP-A780353, alkene contains under the existence of azole compounds and metal alkylide oligomerisation, particularly trimerization can take place in the chromium source.Yet the pre-treatment meeting of catalyzer causes the loss of active ingredient.
DE-A19607888 has disclosed the catalyst for oligomerization that is used for alpha-olefin, wherein comprises chromium cpd and aluminum compound and also has at least a nitrogenous compound simultaneously, and it can be the pyrroles.Here described in EP-A780353, the pre-treatment of catalyzer also can cause considerable damage.
EP-A537609 has described a kind of technology, and in this technology, ethene reacts in the presence of chromium complex and obtains having the alpha-olefin mixture of 1-hexene relatively at high proportion, and this chromium complex has a kind of coordinate polydentate ligand and a kind of aikyiaiurnirsoxan beta.Yet because low catalyst activity and low simultaneously trimerization selectivity, the economy of described technology is unsatisfactory.
About adopting N, N, N-trioctylphosphine Trianacyclohexane-chromium complex and methylaluminoxane make experiment that the ethylene selectivity trimerization obtains the 1-hexene 29 days-April 2 March in 1998 in Dallas, report to some extent in the 215th ACS international conference that Texas holds.Yet catalyzer only has medium activity and also can cause the polymerisate of quite big quantity, and this is this technology defective economically.
The purpose of this invention is to provide stable catalyst, it can obtain more at an easy rate, and has the active of raising and at the selectivity of the low-molecular-weight oligomer of alkene.
We have found that this purpose can realize by the catalyst for oligomerization that begins to mention.
We also find to adopt new catalyst to prepare the technology of alkene oligomer.Invention further provides oligopolymer that obtains in this way and the oxo alcohol that is obtained by these oligopolymers.
Catalyst for oligomerization of the present invention makes the acquisition high yield, and contains small portion molar mass MW and become possibility greater than the alkene oligomer of 500 by product.Particularly, this catalyzer has high selectivity, especially ethene to the trimerization of alpha-olefin.
Trianacyclohexane and derivative thereof, it is different according to the difference of annular atoms substitute mode, because they usually can be from the raw material that is easy to get by simple, cheap mode prepares, and therefore is known and is applied in the different field in the industry at long time.Like this, trianacyclohexane derivatives can be used for for example desulfurization of kerosene.Yet it is not very extensive that Trianacyclohexane and derivative thereof are used to prepare organometallic complex as part.Have only the existing in the literature report of some complex compounds that contain these parts, for example at J.Chem.Soc., DaltonTrans. (1997), 1363-1368; Z.Naturforsch., B50 part (1995), 1038-1043; Angew.Chem.Int.Ed.Engl.33 (1994), 1877-1878; J.Organomet.Chem.501 (1995), 303-307; Chem.Ber.129 (1996), 25-27; J.Organomet.Chem.520 (1996), 121-129; Inorg.Chem.36 (1997), 6064-6049; Chem.Ber.129 (1996) is among the 1327-1333.
Change 1,3, the substituting group on the 5-Trianacyclohexane ring can make the performance of catalyzer of the present invention be affected.Therefore, catalyst activity can improve by substituting group usually, particularly on nitrogen-atoms.Substituent number and geometry can control center's atom pairs approaching with the a-alkene of reaction, and just can be controlled for the selectivity of various starting olefins reactions thus.Therefore, for specifically being reacted special catalyzer, substituent R
1To R
9Chemical structure can in very wide scope, change.
1,3, on the 5-Trianacyclohexane ring, carbon organic group possible replacement or unsubstituted is, for example:
-C
1-C
18-alkyl is preferably C
1-C
12-alkyl, for example, methyl, ethyl, N, N-two
The methylamino ethyl, n-propyl, sec.-propyl, butyl, amyl group, hexyl, the 2-ethyl is own
Base, heptyl, octyl group, nonyl, decyl, dodecyl, 1,1-dimethyl dodecyl ,-5-is to 7-unit cycloalkyl, and it can then have C
1-C
10-aryl is as substituting group, for example,
Cyclopentyl and cyclohexyl ,-C
6-C
15-aryl, phenyl for example, o-tolyl, p-methylphenyl, a tolyl, 1-naphthalene
Base and 2-naphthyl or-C
6-C
15-aralkyl is preferably C
6-C
8-aralkyl, for example benzyl and 1-phenylethyl.
Possible organosilicon radical is, for example: have the trialkylsilkl of 1 to 10 carbon atom in identical or different alkyl, be preferably trimethyl silyl.
1,3, the substituting group on the 5-Trianacyclohexane ring in C-organic group or the Si-organic group can be in particular the alkyl that has to the body group.Can be neutrality or negatively charged ion for the body group and may contain the heteroatoms of 15-16 family in the periodictable (proposing 1985 according to IUPAC) or can be carbanion.If be neutral, it can form coordinate bond with chromium.Preferably with the chromium complexing.If to body is anionic form, itself and metal center form covalent linkage so.Key can be intramolecularly or intermolecular; Be preferably intramolecularly.Be preferably the neutrality that contains oxygen and/or nitrogen-atoms and give body, it is right wherein to have a unbound electron, wherein also may insert oxygen and/or nitrogen-atoms in alkyl chain.
Preferred 1,3,5-Trianacyclohexane part, wherein radicals R
1, R
2And R
3Independently of one another, be that replace or unsubstituted C
1-C
12-alkyl, C
6-C
15-aryl or C
6-C
8-aralkyl is in particular replacement or unsubstituted C
1-C
12-alkyl or C
6-C
8-aralkyl, as methyl, ethyl, N, N-dimethyl aminoethyl, n-propyl, normal-butyl, the tertiary butyl, hexyl, octyl group, dodecyl, 1,1-dimethyl dodecyl, 1-phenylethyl.
In technology of the present invention, especially preferably adopt 1,3,5-Trianacyclohexane part, wherein radicals R
4, R
5, R
6, R
7, R
8And R
9Independently of one another, be hydrogen or C
1-C
4-alkyl is in particular hydrogen or methyl.
Preferred 1,3, the 5-Trianacyclohexane is
1,3,5-tri-tert-1,3, the 5-Trianacyclohexane,
1,3,5-triethyl-1,3, the 5-Trianacyclohexane,
1,3,5-three (1-phenylethyl)-1,3, the 5-Trianacyclohexane,
1,3,5-three (1,1-dimethyl dodecyl)-1,3, the 5-Trianacyclohexane reaches
1,3-two-dodecyl-5-[2-(N, N-dimethylamino) ethyl]-1,3,5-three azepines
Hexanaphthene and preferred especially 1,3,5-three-n-octylcyclam, 3, the 5-Trianacyclohexane,
1,3,5-three-dodecyl-1,3,5-Trianacyclohexane, 1,3,5-tribenzyl-1,3,5-
Trianacyclohexane, 1,3,5-three (2-ethylhexyl)-1,3,5-Trianacyclohexane, 1,3,5-
Three (2-n-propyl heptyl)-1,3, the 5-Trianacyclohexane.
1,3 of formula I, 5-Trianacyclohexane, wherein radicals R
4To R
9Be hydrogen and R
1To R
3Identical, can prepare by known mode itself, for example pass through R
1NH
2Type primary amine and formaldehyde or PARA FORMALDEHYDE PRILLS(91,95) reaction.Correspondingly, 1,3, the 5-Trianacyclohexane can obtain by acetaldehyde, wherein all has a methyl and a hydrogen atom on the carbon atom on the ring.
1,3 of formula I, 5-Trianacyclohexane, wherein R
1, R
2, R
3At least one is different with other group of this group in the group, also can prepare (for example reference, Beilstein, " organic chemistry handbook ", 4 by known mode itself
ThEd, Vth Suppl. Series, Springer-Verlag, Berlin, Vol26 (1986) 3ff. and the reference of being quoted; R=octyl group: J. Polym. Sci., Polym. Chem. Ed. 329 (1993), 1941-1958; J. Prakt.Chem. 327 (1985), 739-748; EP-A 620 266; DE-A 24 31 862; DE-A 41 00856; Pharmazie 30 (1975), and 699-706) for example some known preparation methods are here set forth tout court.1) mixture (R of two kinds of primary amine
1NH
2And R
2NH
2) anti-with formaldehyde (with the aqueous solution or PARA FORMALDEHYDE PRILLS(91,95))
Should generate various mixture of products, it can separate by the following method:
A) work as R
1With R
2Distilled in enough hour.
B), then adopt big excess amine R if symmetric reaction product can be distilled out
1NH
2Carry out
Reaction.After the distillation, remaining asymmetric product.
C) a kind of product selectivity crystallization.
D) 1,3, the mixture of 5-Trianacyclohexane and chromium cpd, for example CrCl
3Complexing,
The chromium complex of gained is separated, for example pass through chromatographic column.2) amine R
1NH
2With excess formaldehyde reaction obtain that symmetry replaces 1,3, the 5-Trianacyclohexane with mutually
The 1-oxa--3 of answering, the mixture of 5-diaza-cyclohexane, second step, 1-oxa--3,5-
Diaza-cyclohexane and amine R
2NH
2Reaction (if desired in the presence of acid catalyst), the result
Sauerstoffatom is by R on the ring
2N replaces.
Product mixture can be by 1) separating of describing.3) has a little R
1The symmetry 1,3 of (methyl or ethyl), the 5-Trianacyclohexane is about 130
℃ with amine R
2NH
2Reaction.Under this temperature, discharge R
1NH
2, the formation asymmetry
1,3, the mixture of 5-Trianacyclohexane.
Can be by 1) separating of describing.4) two kinds of different symmetries 1,3, the 5-Trianacyclohexane reacts to each other, and causes the substituting group exchange.
Product can be by 1) separating of describing.
At chromium cpd CrX
3Or chromium complex CrX
3The X group that is fit among the L is any removable anti-electron ion that is fit to this purpose in the organometallic chemistry, particularly
-halogen such as fluorine, bromine, iodine, particularly chlorine,
-tosylate, fluoroform sulphonate (triflate), a tetrafluoro borate, hexafluorophosphate, hexafluoro antimonate, tetraphenyl borate salts,
-C
1To C
10-carboxyl is in particular 2-ethylhexoate,
-alkyl, methyl for example, ethyl, sec.-propyl, phenyl, benzyl,
-big non-coordination anion such as B (C
6F
5)
4 -
The radicals X of selecting particularly makes those chromium cpds CrX that contains it
3Or chromium complex CrX
3L shows in used concrete solvent has good solubility.
As preparation chromium cpd CrX
3Or chromium complex CrX
3The raw material of L for example can adopt, and hafnium halide is as CrCl
3, CrBr
3, Cr (fluoroform sulphonate)
3, Cr (III) alkoxide closes the complex compound of neutral complexing ligand as these chromium cpds of 2-ethylhexoate postscript and weak bond, and it can be by 1,3, and the 5-Trianacyclohexane replaces, also may be by the N-of 5-membered aromatic family heterocyclic substituted, ether complexes for example is as CrCl
3(tetrahydrofuran (THF))
3, CrCl
3The (diox)
3, ester complex compound such as CrCl
3(ro-butyl acetate), CrCl
3(ethyl acetate), alcohol complex is as CrCl
3(Virahol)
3, CrCl
3(2-Ethylhexyl Alcohol)
3, amine complex is as CrCl
3(pyridine)
3, CrCl
3(Isopropylamine)
2, or cyano complex, as CrCl
3(acetonitrile)
3Acetonitrile.
In an embodiment preferred of technology of the present invention, adopt catalyst for oligomerization, it has been prepared and isolating chromium complex CrX by inside in advance
3L prepares.
In addition, chromium complex CrX
3L can be by preparing for the known method of those of ordinary skills, or by preparing (for example reference with these similar methods, W.A.Herrmann, A.Salzer: " organo-metallic and inorganic chemical synthetic method " Vo1 1.1-document, experimental technique and common raw material, Thieme Verlag, Stuttgart, 1996).
Chromium complex CrX
3The L in-situ preparing is passed through usually with chromium cpd CrX
3Be dissolved or suspended in the reaction medium, and add 1,3, the 5-Trianacyclohexane, or former state adds or add with the dissolved form and to realize.
In oligomerization process of the present invention, preferably adopt chromium complex CrX
3L, wherein X and L have following implication:
X is independently of one another: halogen, and tosylate, fluoroform sulphonate, alkyl,
L is 1,3 of formula I, 5-Trianacyclohexane, wherein radicals R
4, R
5, R
6, R
7, R
8And R
9Independently of one another, be hydrogen or C
1-C
4-alkyl is in particular hydrogen or methyl, and R wherein
1, R
2And R
3Independently of one another, be methyl, ethyl, N, N-dimethyl aminoethyl, propyl group, normal-butyl, the tertiary butyl, hexyl, octyl group, dodecyl, 1,1-dimethyl dodecyl or (1-phenyl) ethyl.
Especially preferably adopt chromium complex CrX
3L, wherein X and L have following implication:
X is independently of one another: halogen, and tosylate,
L is 1,3 of formula I, 5-Trianacyclohexane, wherein radicals R
4, R
5, R
6, R
7, R
8And R
9Independently of one another, be hydrogen or methyl, and R wherein
1, R
2And R
3Independently of one another, be methyl, ethyl, N, N-dimethyl aminoethyl, propyl group, normal-butyl, the tertiary butyl, hexyl, octyl group, dodecyl, 1,1-dimethyl dodecyl or 1-phenylethyl.
In an embodiment preferred of technology of the present invention, activating additive is made up of the 5-membered aromatic N-heterocycle and at least a aluminum alkyls that do not replace or replace, and some alkyl of aluminum alkyls can be replaced by halogen and/or alkoxyl group.
The 5-membered aromatic N-heterocycle that is fit to has 1,2,3 or 4, the 5-membered aromatic N-heterocycle of preferred 1 or 2 nitrogen-atoms for those on the 5-membered aromatic ring.5-membered aromatic N-heterocycle can replaced by inert group under reaction conditions on the ring carbon atom, as alkyl, preferable methyl and ethyl, perhaps two adjacent carbon atoms of 5-membered aromatic N-heterocyclic can together become the part of the aromatic carbocyclic system that combines, and this system can then have inertia group.The pyrroles of this class N-heterocyclic example for not replacing and replacing, pyrazoles, imidazoles, triazole and tetrazolium, as the pyrroles, 2,5-dimethyl pyrrole, indoles, carbazole, pyrazoles, indazole, imidazoles, benzoglyoxaline.Preferred employing pyrroles, and be in particular the pyrroles that alkyl replaces, especially be 2, the 5-dimethyl pyrrole.
As aluminum alkyls, the some of them alkyl can be replaced by halogen and alkoxyl group, and the aluminum alkyls that may adopt following molecular formula is AlR
3, AlR
2Hal, AlRHal
2, AlR
2OR ', AlRHalOR ' and Al
2R
3Hal
3And composition thereof, wherein R and R ' are independently of one another, are methyl, ethyl or straight chain or branching C
3-C
8-alkyl group, Hal are fluorine, bromine, and iodine, or especially be chlorine, trimethyl aluminium for example, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethylaluminum ethoxide, diethyl phenoxy group aluminium, ethyl oxyethyl group aluminum chloride.The preferred AlR that adopts
3With AlRHal
2The type aluminum alkyls especially preferably adopts the mixture of triethyl aluminum or triethyl aluminum and ethylaluminum dichloride.
As the surrogate of aluminum alkyls, the some of them alkyl can be replaced by halogen and alkoxyl group, may adopt the mixture of corresponding aluminum alkyls and the co-catalyst that is fit to, thereby original position forms required blended aluminum compound in reactor.
The co-catalyst that is fit to is an alkyl halide, alkyl halide silicon and Lewis acid metal halides, preferred normal-butyl chlorination thing, normal-butyl iodate thing, trimethylsilyl chloride, trimethyl silyl bromide, tin tetrachloride, germanium chloride and be in particular normal-butyl bromination thing.
By aluminum alkyls, the some of them alkyl can be replaced by halogen and alkoxyl group, and in the system of forming with co-catalyst, the mol ratio of two components is 1: 3 to 30: 1, preferred 1: 1 to 15: 1.
In technology of the present invention, chromium cpd CrX
3Or chromium complex CrX
3The amount of L is usually at every kilogram of reaction mixture 1 * 10
-7In 1 mole scope, preferred 1 * 10
-6To 0.1 mole, and be in particular 1 * 10
-5To 0.01 mole.
5-membered aromatic N-heterocyclic amount is usually at every kilogram of reaction mixture 1 * 10
-8In 100 moles scope, preferred 1 * 10
-7To 1 mole, and be in particular 1 * 10
-5To 0.05 mole.
The amount of aluminum alkyls, the some of them alkyl can be replaced by halogen and alkoxyl group, usually at every kilogram of reaction mixture 1 * 10
-8In 500 moles scope, preferred 1 * 10
-7To 10 moles, and be in particular 5 * 10
-5To 0.5 mole.
In technology of the present invention, component (a), be 1 with (c) mol ratio (b): 0.1-100: 0.1-500 is preferably 1: 0.1-10: 1-100, and be in particular 1: 1-5: 5-50.
Very particularly preferably be to adopt by (a) (1,3,5-three-n-octylcyclam, 3,5-Trianacyclohexane) CrCl
3Or (1,3,5-tribenzyl-1,3,5-Trianacyclohexane) CrCl
3, (b) 2,5-dimethyl pyrrole and (c) catalyzer formed of triethyl aluminum and ethylaluminum dichloride, wherein the mol ratio of these components is 1: 0.1-10: 0.1-100 is preferably 1: 1-5: 5-50.In component (c), the mol ratio of triethyl aluminum and ethylaluminum dichloride is 1-50: 1, be preferably 3-20: 1.
Oligomerisation is preferably carried out in solvent.The solvent that can be used for oligomerisation is the straight chain with 1-20 carbon atom, branching or alicyclic saturated hydrocarbon, as butane, pentane, the 3-methylpentane, hexane, heptane, 2-methyl hexane, octane, hexanaphthene, methylcyclohexane, 2,2,4-trimethylpentane or naphthalane, straight chain or branching halon are as ethylene dichloride, aromatic hydrocarbon, as benzene, toluene, dimethylbenzene, ethylbenzene, mesitylene or tetraline and be the oligomerisation reaction product of liquid under reaction conditions are as 1-hexene self.Solvent can use or mix use separately.
According to the preferred catalyst for oligomerization of the present invention also can be to comprise as those of the alkylaluminoxane of activating additive.
About this point, those ligand L very particularly preferably are, wherein radicals R
1, R
2And R
3, partly or entirely independently of one another, in the β position or from 1,3, the nitrogen-atoms on the 5-Trianacyclohexane ring has the substituting group that connects by carbon atom on the farther position, is in particular alkyl, the group of aryl or silyl.Preferred especially, this substituting group is in the β position.Preferred more especially, this substituting group is the alkyl that β-alkyl replaces, and especially is 2-ethylhexyl or 2-n-propyl heptyl.In these ligand L, very particularly preferably be those R once more
4, R
5, R
6, R
7, R
8And R
9Group for hydrogen.
The alkylaluminoxane that is fit to is known, and for example in DE-A3007725, its structure is not described in detail.They are products (with reference to DE-A3007725) of the careful partial hydrolysis of aluminum alkyls.These products obviously are not to occur with its pure form, but the mixture of the open chain of Type II a and IIb and ring texture, and it may be in each other the running balance.
In formula IIa and IIb, radicals R
10For identical or different and independently of one another, be C
1-C
12-alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, different heptyl, n-octyl, n-nonyl, positive decyl and dodecyl; Preferred C
1-C
6-alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1, the 2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl is preferably methyl especially.M is 0 to 40 integer, preferred 0 to 25, preferred especially 0 to 22.
Also discussed in the document aikyiaiurnirsoxan beta cagelike structure (with reference to Organometallics1996,15, the 2213-26 page or leaf; Macromol. Symp. 1995,97, the 15-25 page or leaf).
In the context of the invention, alkylaluminoxane has satisfied as activating additive effectively active, forms irrelevant with its structure.
The consumption of activation alkylaluminoxane depends on its characteristic.Chromium cpd CrX
3With/or chromium complex CrX
3The ratio of L and activation alkylaluminoxane is preferably 1: 1 to 1: 1000 usually at 1: 0.1 to 1: 10 000.
When adopting by CrX
3, ligand L and alkylaluminoxane, or by CrX
3During catalyst for oligomerization that L and alkylaluminoxane form, suitable solvent is an aprotic solvent, aliphatics or the aromatic hydrocarbon solvent, particularly toluene enumerated previously above for example.
In another embodiment preferred of technology of the present invention, adopt catalyst for oligomerization, comprising at least a boron compound and at least a aluminum alkyls as activating additive, the some of them alkyl can be replaced by halogen and alkoxyl group.
The example of the boron compound that is fit to for those boron compounds that contain electron-withdrawing group (as three-pentafluorophenyl group borine, N, accelerine four-pentafluorophenyl group borate, three-positive fourth ammonium four-pentafluorophenyl group borate, N, accelerine four (3, the 5-methyl fluoride of enjoying a double blessing)-phenylboronate, three-positive fourth ammoniums four (3,5-enjoy a double blessing methyl fluoride)-phenylboronate, and trityl four-pentafluorophenyl group borate).These activating additives are known in EP-A468537 postscript EP-A426638.Preferred trityl four-pentafluorophenyl group borate, three-pentafluorophenyl group borine is in particular xylidine four (pentafluorophenyl group) borate.
The consumption of activation boron compound depends on its characteristic.Chromium cpd CrX
3With/or chromium complex CrX
3The ratio of L and activation boron compound is preferably 1: 1 to 1: 1000 usually at 1: 0.1 to 1: 10000.
The aluminum alkyls that is fit to, the some of them alkyl can be replaced by halogen and alkoxyl group, is the representative of top this class material of enumerating previously, and it is measured with respect to chromium cpd CrX
3With/or chromium complex CrX
3L is with wherein given amount.
The solvent that is fit in the context is an aprotic solvent, as top aliphatics or the arene of enumerating previously as solvent, is preferably toluene.
In the technology of the present invention, the preferred alkene that is used for oligomerisation is in particular 2-6 for preferably having 2-10, especially is the straight chain of 2-4 carbon atom and branching alpha-olefin and composition thereof, very particularly preferably with himself form: the 1-propylene, 1-butylene, 1-hexene, 1-decene, especially be ethene, 1-butylene especially is 1-butylene and its mixture of isomers, for example exists in oil residual solution II.
Because particularly aluminum compound and possibility co-catalyst be easy to hydrolysis, oligomerisation is fully being carried out under the eliminating moisture usually.Techniques known in themselves can be used for this purpose.Oligomerisation preferably adopts the device of oven dry to carry out under protection gas.Operable protection gas is all chemically inert gas, preferred nitrogen or argon gas under reaction conditions.In addition, the alpha-olefin self of participating in reaction can have the function of protection gas, as long as have sufficiently high vapour pressure under reaction conditions.
Oligomerisation reaction particularly carries out under 70 to 110 ℃ preferably at 1 to 120 ℃, and preferred pressure is in the scope of 3 to 120 crust.Select favourable pressure so that reaction mixture is a liquid under design temperature.
Technology of the present invention can be carried out in batches or continuously, preferably adopts continuous mode in industrially scalable.
Be applicable to the reactor that carries out technology of the present invention continuously, know, Ullmann ' s Enzylop die der technischen Chemie for example, Volume1,3 for those of ordinary skills
RdEdition, 1951,743 pages are described, and voltage-resistant reactor is also described to some extent at 769 pages.
The remaining final condition of this oligomerisation reaction is set on the basis of its common technical knowledge by those of ordinary skills, for example, can obtain from DE-A19607888.
At reaction end, the inactivation of catalyzer on the principle, can be undertaken by using the material that can make the alkylaluminium cpd hydrolysis in a large number, for example water and have the monohydroxy-alcohol of 1 to 10 carbon atom.Also can in these materials, add mineral acid.
Purifying is favourable to the product of oligomerisation reaction of the present invention by distilling in addition.For example, not only can from the reaction product of ethylene oligomerization, fractionate out main distillate fraction (hexene), mainly comprise the 1-hexene, and can obtain decene cut and four decene cuts by this mode.The two kinds of cuts in back mainly are made up of the internal olefin of branching.
In order to realize the high conversion of technology of the present invention, unreacted raw material can be recovered and turn back in the reaction.
The product of optimal process of the present invention is the tripolymer of alpha-olefin, particularly has the alpha-olefin of 2 to 6 carbon atoms, and the 1-hexene that is especially preferably obtained by ethene.
The oligopolymer that adopts technology of the present invention to obtain is particularly suitable for preparing the monohydroxy-alcohol that is used for softening agent and tensio-active agent.For reaching this purpose, oligopolymer suitably carries out hydroformylation, in this process, forms the aldehyde of a carbon atom on the chain extension and the mixture of alcohol, and the hydrogenation subsequently of these mixtures obtains required alcohol.It is known that hydroformylation and hydrogenant are implemented for technician itself, does not therefore need to further specify (reference example as, people such as Beller, Journal of MolecularCatalysis A104 (1995), 17-85 page or leaf).
The following examples have illustrated the present invention.
Embodiment A) catalyzer
2,5-dimethyl pyrrole, CrCl
3(THF)
3, 1,3,5-tribenzyl-1,3,5-Trianacyclohexane and triethyl aluminum are buied from Aldrich Chemical Ltd., and Kieselgur obtains from Riedel deHaen AG.1,3, the preparation 1,3 of 5-Trianacyclohexane, 5-three n-octylcyclams, 3, the preparation of 5-Trianacyclohexane
100 gram (0.774 mole) n-octyl amine are divided in the suspension join 20.2 gram (0.637 mole) PARA FORMALDEHYDE PRILLS(91,95) that are cooled to 0 ℃ and 500 milliliters of toluene in small batches.Subsequently, to boiling point, PARA FORMALDEHYDE PRILLS(91,95) enters into solution with mixture heating up.Then water and toluene are steamed.Resistates discharges volatile matter under 1 millibar, be collected in 100 ml methanol, filters by the layer of silica gel of 1 cm thick.Under 1 millibar, the volatile matter in the filtrate is removed subsequently, obtain 82.3 the gram (83% productive rate) title in compound, it is the limpid liquid of thickness.
Below 1,3, the 5-Trianacyclohexane prepares by similar mode:
-1,3,5-three-dodecyl-1,3,5-Trianacyclohexane
-1,3,5-tri-tert-1,3,5-Trianacyclohexane
-1,3,5-triethyl-1,3,5-Trianacyclohexane
-1,3,5-three (1-phenylethyl)-1,3,5-Trianacyclohexane
-1,3,5-three (1,1-dimethyl dodecyl)-1,3,5-Trianacyclohexane
-1,3-two-dodecyl-5-[2-(N, N-dimethylamino) ethyl]-1,3, the 5-Trianacyclohexane
-1,3,5-three (2-ethylhexyl)-1,3,5-Trianacyclohexane
-1,3,5-three (2-n-propyl heptyl)-1,3, the preparation of 5-Trianacyclohexane Preparation of catalysts " chromium complex 1 ": [(1,3,5-three-n-octylcyclam, 3,5-Trianacyclohexane) CrCl
3]
662 milligrams of (1.768 mmole) tetrahydrofuran complex CrCl
3(THF)
3With 728 milligrams of (1.855 mmoles) 1,3,5-three-n-octylcyclam, 3,5-Trianacyclohexane (on seeing) places reaction flask under 25 ℃.At-78 ℃, 100 milliliters have been concentrated in this mixture with sodium exsiccant Anaesthetie Ether.The suspension that obtains by this mode was 25 ℃ of following stir abouts 30 minutes.Filter by frit then, filtered residue is washed with Anaesthetie Ether, no longer is green up to elutant.Then with resistates at 25 ℃, 1 millibar is down dry, obtains 885 milligrams of compounds (98% productive rate) in the title.The preparation of " chromium complex 2 ": [(1,3,5-tribenzyl-1,3,5-Trianacyclohexane) CrCl
3]
10 milliliters of exsiccant Anaesthetie Ethers join in the Glass Containers that toasted in 25 ℃ under argon gas.Add 749 milligrams of (20 mmole) tetrahydrofuran complex CrCl there
3(THF)
3Form suspension, and (1,3,5-tribenzyl-1,3 is added drop-wise in the mixture under the solution stirring of 5-Trianacyclohexane in 2 milliliters of Anaesthetie Ethers with 715 milligrams (20 mmoles).Subsequently with reaction mixture 20 ℃ of following restir 30 minutes, under argon gas, filter then by frit, filtered residue is with Anaesthetie Ether washing three times, each 10 milliliters, then at 25 ℃, 1 millibar is dry down.Obtain the compound in the 0.64 gram title, be the purple solid.The preparation of " chromium complex 3-10 "
Adopt and preparation complex compound 1 and 2 similar methods the complex compound of the chromium trichloride that preparation is following: " chromium complex 3 ": [(1,3,5-three dodecyls-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 4 ": [(1,3,5-tri-tert-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 5 ": [(1,3,5-triethyl-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 6 ": [(1,3,5-three (1-phenylethyl)-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 7 ": [(1,3,5-three (1,1-dimethyl dodecyl)-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 8 ": [(1,3-two-dodecyl-5-[2-(N, N-dimethylamino) ethyl]-1,3, the 5-Trianacyclohexane) CrCl
3] " chromium complex 9 ": [(1,3,5-three (2-ethylhexyl)-1,3,5-Trianacyclohexane) CrCl
3] " chromium complex 10 ": [(1,3,5-three (2-n-propyl heptyl)-1,3,5-Trianacyclohexane) CrCl
3] B) oligomerisation embodiment 1: at " complex compound 1 " and 2, there is the oligomerisation of ethene down in the 5-dimethyl pyrrole
Capacity is 100 milliliters a stainless steel autoclave, under argon gas stream in 105 ℃ of bakings 60 minutes.Subsequently, under 25 ℃, add 14.5 milligrams " chromium complexes 1 ", then add and used 25 milliliters of normal heptanes of sodium exsiccant and 0.5 milliliter 143 milligrams 2, the mixing solutions of 5-dimethyl pyrrole and 10 milliliters of normal heptanes is equivalent to 0.075 mmole 2, the 5-dimethyl pyrrole.Subsequently autoclave is washed three times with ethene under normal pressure.The n-heptane solution that adds the triethyl aluminum of 0.75 milliliter of 1 volumetric molar concentration then, the ethene with 25 crust pressurizes subsequently.Temperature is raised to 80 ℃ subsequently, and ethylene pressure is increased to 40 crust.Reaction mixture in the autoclave stirred 2 hours under these conditions, the pressure release of autoclave cooling afterwards.Catalyzer comes inactivation by add 1 ml water in reaction mixture.Isolate insoluble component in the reaction mixture, drying is weighed.Productivity is calculated as 18.6 kilograms of products by each gram chromium in the catalyzer.Measure the relative amount of products therefrom by using heptane as interior target gas chromatographic analysis: hexene 44.4% weight decene 33.1% weight four decene, 10.9% weight " polymkeric substance " 1.5% weight
Embodiment 2 to 11 embodiment 2 to 11 are undertaken by adopting method similar to Example 1.Adopt n-butyl bromide (n-BuBr) and the 0.1M solution of ethylaluminum dichloride (EADC) in heptane.Raw material, relevant amount and experimental result provide in the following Table 1.The data of table 1: embodiment 2 to 11
Abbreviation: Cat chromium complex CrX
3The amount C of L
6The ratio DMP 2 of alkene in the product, the amount C of 5-dimethyl pyrrole
10The amount C of the ratio TEA triethyl aluminum of decene in the product
14The trimerization of amount embodiment 12:1-butylene in the presence of " chromium complex 9 " and methylaluminoxane of the ratio normal heptane normal heptane of polymkeric substance in the ratio Cocat co-catalyst of four decene and the amount polym product in the product, and the trimerical hydroformylation of gained obtains corresponding oxo alcohol.A) trimerization
| Embodiment | Chromium complex CrX 3L | Cat [micromole] | DMP [micromole] | TEA [micromole] | Cocat [micromole] | Normal heptane [milliliter] | C6 [% weight] | C10 [% weight] | C14 [% weight] | Polymkeric substance [% weight] | Productivity [kilogram/gram Cr] |
| ???2 | ????2 | ????25 | ????75 | ????750 | ????- | ????25 | ???56.1 | ???27.5 | ????6.5 | ????7.3 | ?????27.4 |
| ???3 | ????2 | ????10 | ????30 | ????300 | ????- | ????10 | ???62.1 | ???21.7 | ????4.7 | ????7.6 | ?????44.8 |
| ???4 | ????3 | ????10 | ????30 | ????300 | ????- | ????10 | ???53.5 | ???25.0 | ????6.3 | ????9.1 | ?????33.5 |
| ???5 | ????4 | ????10 | ????30 | ????300 | ????- | ????10 | ???59.4 | ???24.4 | ????7.3 | ????2.6 | ?????21.1 |
| ???6 | ????5 | ????10 | ????30 | ????300 | ????- | ????10 | ???63.3 | ???21.1 | ????5.3 | ????8.8 | ?????16.4 |
| ???7 | ????6 | ????10 | ????30 | ????300 | ????- | ????10 | ???55.6 | ???23.9 | ????7.0 | ????4.4 | ?????19.3 |
| ???8 | ????7 | ????10 | ????30 | ????300 | ????- | ????10 | ???61.7 | ???23.5 | ????6.0 | ????4.9 | ?????28.0 |
| ???9 | ????8 | ????10 | ????30 | ????300 | ????- | ????10 | ???48.3 | ???23.0 | ????7.0 | ????10.5 | ?????24.8 |
| ???10 | ????2 | ????10 | ????30 | ????300 | N-butyl bromide 30 | ????10 | ???68.1 | ???20.7 | ????6.2 | ????2.2 | ?????75.3 |
| ???11 | ????2 | ????10 | ????30 | ????300 | ???EADC ????30 | ????10 | ???82.8 | ???14.3 | ????2.1 | ????0.3 | ????106.1 |
Volume is that 2500 milliliters stainless steel autoclave toasts down in 120 ℃ under argon gas stream.Under 25 ℃, 750 milligrams " chromium complexes 9 " and 500 grams are joined in the autoclave with sodium exsiccant toluene, then it is washed three times with 1-butylene.Subsequently, the 1M solution of 50 gram methylaluminoxane in toluene, and 500 gram 1-butylene join in the autoclave by vent plug.Temperature with autoclave rises to 40 ℃ then, and pressure uses nitrogen to be adjusted to 15 crust.After reacting 2 hours with this understanding, with autoclave cooling and pressure release.Make catalyst deactivation by adding the 2-propyl alcohol.By gas-chromatography the discharge material (800 gram) of reactor being analyzed unique oligopolymer of finding existence is isomerized laurylene.The ISO index of the dodecane mixture that obtains by hydrogenation is 2.3.B1) hydroformylation in the presence of cobalt-carbonyl
1.06 kilograms of laurylene mixtures according to a) part preparation restrain CO 4.0
2(CO)
8Exist down, in the autoclave that 2500 milliliters of rotations are stirred, in 185 ℃ and 280 CO/H that cling to
2(1: 1) adds 100 gram water reactions down and carried out hydroformylation in 5 hours.Reaction is discharged product and is carried out oxidation at 90 ℃ of acetate that use 10% concentration down and bubbling air subsequently and take off cobalt.The products of oxo synthesis that obtains thus is in 2500 milliliters of tubular reactors with the formal operations that flow downward, in 175 ℃ and 280 H that cling to
2The following water that adds based on organic phase 10% weight carries out hydrogenation by Co/Mo is catalyst fixed bed.The alcohol mixture that generates in the reaction distills, and isolates the tridecanol mixture, and its OH number is 279 milligrams of KOH/ grams.By
1The H-NMR spectrum finds that its average degree of branching is 2.7.B2) adopt the two rhodium carbonyl/polymines of methyl ethyl diketone to carry out hydroformylation
50 milligrams of two rhodium carbonyls of methyl ethyl diketone, 4.5 gram molar mass M
W=460000 polymine wherein 60% of all nitrogen-atoms has adopted lauric amideization, and 800 grams restrain toluene in 2500 milliliters of lift agitated autoclave, at CO/H according to the laurylene mixture and 196 of a) part preparation
2Be heated to 150 ℃ under (1: 1).Pass through CO/H
2Set 280 bar pressures.After 7 hours, the autoclave cooling, pressure release also empties.Find that by gas-chromatography olefin conversion is 93%.The gained products of oxo synthesis is in 2500 milliliters of tubular reactors with the formal operations that flow downward, in 175 ℃ and 280 crust H
2The following water that adds based on organic phase 10% weight carries out hydrogenation by Co/Mo is catalyst fixed bed.Handle the alcohol mixture that generates in this reaction by distillation, the OH number is 279 milligrams of KOH/ grams in the tridecanol mixture of gained.By
1It is 2.9 that the H-NMR spectrum is measured its average degree of branching.Embodiment 13-22: a) the selectable preparation of " chromium complex 9 " of the trimerization in the presence of " chromium complex 9 " and methylaluminoxane
15 milliliters (+/-)-2 ethyl hexylamine (92 mmole) is dissolved in 200 milliliters of toluene, adds 2.75 gram PARA FORMALDEHYDE PRILLS(91,95) (92 mmole).Mixture stirred after 1 hour, and the toluene azeotrope distills out up to boiling point and reaches 110 ℃.Mixture is cooled to below the boiling point under argon gas stream subsequently, adds the anhydrous CrCl of 4.82 grams
3(31 mmole).After distilling out several milliliters of toluene once more, under argon gas stream, cool off, add 0.5 gram zinc powder.Further toluene is removed in distillation, and suspension becomes deep purple solution.Steamed toluene once more 30 minutes, resistates is cooled to 25 ℃.After removing zinc powder, deep purple solution is decanted in air, boil off solvent with rotatory evaporator.Purple, some buttery solid residue is dissolved in the acetone, and solution is filtered.The gained deep purple solution is mixed the little apparent lilac of solution up to purple precipitation top with water.After the filtration, purple resistates decompression down (approximately 1Pa) in 50 ℃ of dryings 40 hours up to end.Obtain 13.12 gram (74%) purples " chromium complex 9 ".B) trimeric carries out
Trimerization is at one 1 liter the contact thermometer that is equipped with, and agitator carries out in the four-hole boiling flask of heating jacket and gas introduction tube, at 40 ℃, adds 30-50 micromole " chromium complex 9 " under the argon shield in 250 milliliters of toluene.
Methylaluminoxane (" MAO ") is used with the form of 1.6M solution in toluene.
Used boron compound is Dimethyl Ammonium ion four (pentafluorophenyl group) borate (" DMAB ").After adding, reaction mixture is heated to 70 ℃, is cooled to 40 ℃ then, and (" TIBAL ") mixes with triisobutyl aluminium.
20 to 40 liters of/hour ethene or 1-butylene feed in the light green/yellow solution of gained after adding MAO or DMAB/TIBAL, or drip the 1-hexene of respective amount.
In the experimentation of reaction times t, homo(io)thermism is a temperature T.Reaction stops by add 15 milliliters of concentrated hydrochloric acids in 50 ml methanol, and reaction mixture stirred 15 minutes subsequently.Add 250 ml methanol then, continue to stir 15 minutes.After removing by filter any insoluble polymkeric substance, product is washed with water three times, use dried over sodium sulfate.Productive rate and products distribution are measured by the gas chromatographic analysis to the solution that obtains thus.More reactant data and experimental result provide in table 2.
Table 2: the data of embodiment 13-22
| Embodiment | The amount of chromium complex 9 | Atomic ratio Al: Cr | Atomic ratio B 1)∶Cr | ????T ???(℃) | Monomer | ???DMP 3)[micromole] | T [minute] | |
| [milligram] | (micromole) | |||||||
| ????13 | ???16.6 | ????33.6 | ???300∶1 | ??????- | ????40 | ??C 2H 4+ 5 milliliters of 1-hexenes | ????- | ????60 |
| ????14 | ???19.0 | ????32.6 | ???350∶1 | ??????- | ????40 | ??????C 2H 4 4 | ????- | ????60 |
| ????15 | ???30.2 | ????51.9 | ???50∶1 | ????2.2∶1 | ????40 | ??????C 2H 4 4 | ????- | ????60 |
| ????16 | ???25.5 | ????43.8 | ???350∶1 | ??????- | ????40 | ??????C 2H 4 4 | ????- | ????60 |
| ????17 | ???23.8 | ????40.9 | ???50∶1 2) | ????2∶1 | ????40 | 500 milliliters of 1-hexenes | ????123 | ????90 |
| ????18 | ???20.4 | ????35.1 | ???50∶1 | ????2∶1 | ????40 | 500 milliliters of 1-hexenes | ????60 | ?????- |
| ????19 | ???21.2 | ????36.4 | ???300∶1 | ??????- | ????40 | 500 milliliters of 1-hexenes | ????- | ????60 |
| ????20 | ???26.6 | ????45.7 | ???350∶1 | ??????- | ????40 | 1-butylene 4 | ????- | ????60 |
| ????21 | ???22.2 | ????38.1 | ???50∶1 | ????10∶1 | ????40 | 1-butylene 4 | ????- | ????60 |
| ????22 | ???18.4 | ????31.6 | ???300∶1 | ??????- | ????20 | 1-butylene 4 | ????- | ????60 |
Continuous table 2: the data of embodiment 13-22
| Embodiment | Polymkeric substance [gram] | Product [gram] | The activity of catalyst system therefor [kilogram/(mole Cr* hour)] | ||||||||
| ????C 6 | ????C 10 | ????C 14 | ????C 18 | Polymkeric substance | ???C 6 | ???C 10 | ???C 14 | ????C 18 | Add up to | ||
| ????13 | ?????- | ????13.0 | ????16.5 | ????3.08 | ?????- | ?????- | ???387 | ???488 | ???91 | ????- | ????965 |
| ????14 | ????0.52 | ????6.9 | ????10 | ????2.3 | ?????- | ????16 | ???213 | ???307 | ???71 | ????- | ????607 |
| ????15 | ????0.9 | ????4.9 | ????7.78 | ????2.5 | ?????- | ????17 | ???94 | ???149 | ???48 | ????- | ????308 |
| ????16 | ????0.56 | ????5.96 | ????12.5 | ????2.99 | ?????- | ????12.8 | ???136 | ???286 | ???68 | ????- | ????502 |
| ????17 | ?????- | ?????- | ?????- | ????- | ????3.47 | ????- | ????- | ????- | ???- | ????84 | ????84 |
| ????18 | ?????- | ?????- | ?????- | ????- | ????1.02 | ????- | ????- | ????- | ???- | ????29.1 | ????29.1 |
| ????19 | ?????- | ?????- | ?????- | ????- | ????2.7 | ????- | ????- | ????- | ???- | ????75.8 | ????75.8 |
| ????20 | ?????- | ????????????????????2.08 | ????- | ?????????????43.1 | ????43.1 | ||||||
| ????21 | ?????- | ????????????????????2.58 | ????- | ??????????????67 | ????67 | ||||||
| ????22 | ?????- | ????????????????????1.19 | ????- | ?????????????37.65 | ????37.65 | ||||||
1 activates by adding DMAB and TIBAL
2 use triethyl aluminum to replace TIBAL
32, the 5-dimethyl pyrrole
4 feed gas embodiment 23 to 26: a) the selectable preparation of " chromium complex 10 " of the trimerization in the presence of " chromium complex 10 " and methylaluminoxane
The similar method of selectable preparation according to embodiment 13-22 " chromium complex 9 " is prepared.B) trimeric carries out
The trimerization of embodiment 23-25 is similar to embodiment 13-22 to carry out under the solvent.
On the other hand, embodiment 26 is reflected in 1000 milliliters of autoclaves, carries out under 40 bar pressures, also in toluene.
More reactant data and experimental result provide in table 3.
Table 3: the data of embodiment 23-26
| Embodiment | The amount of chromium complex 10 | Atomic ratio Al: Cr | Atomic ratio B 1)∶Cr | ????T ???[℃] | Monomer | ????DMP 3)[micromole] | T [minute] | |
| [milligram] | (micromole) | |||||||
| ????23 | ????19.5 | ????29.3 | ?????300∶1 | ??????- | ????40 | ????C 2H 4 4) | ??????- | ????60 |
| ????24 | ????28.3 | ????42.5 | ?????50∶1 5) | ????5.3∶1 | ????40 | 1-butylene 4) | ????127.5 | ????60 |
| ????25 | ????12.1 | ????18.2 | ?????500∶1 | ??????- | ????50 | Ethene | ??????- | ????30 |
| ????26 | ????55 | ????83 | ?????300∶1 | ??????- | ????40 | 200 milliliters of 1-butylene | ??????- | ????60 |
| Embodiment | Polymkeric substance [gram] | Product [gram] | The activity of catalyst system therefor [kilogram/(mole Cr* hour)] | ||||||||
| ???C6 | ???C10 | ????C14 | ????C18 | Polymkeric substance | ????C6 | ????C10 | ????C14 | ????C18 | Add up to | ||
| ????23 | ???0.43 | ???9.02 | ???10.9 | ????2.06 | ????0.16 | ????14.7 | ????308 | ????372 | ????70 | ????5.5 | ????770 |
| ????24 | ????- | ????????????????????C12∶2.31 | ?????- | ??????????????????C12∶54.3 | ????54.3 | ||||||
| ????25 | ???0.07 | ???6.63 | ???1.96 | ?????- | ?????- | ????3.8 | ????730 | ????215 | ????0 | ????0 | ????945 |
| ????26 | ????- | ??????????????C10∶0.24，C12∶2.09 | ?????- | ?????????????C10∶2.9，C12∶25.2 | ????28.1 | ||||||
1 activates by adding DMAB and TIBAL
2 use triethyl aluminum to replace TIBAL
32, the 5-dimethyl pyrrole
4 feed gas
5 use triethyl aluminum
Claims (12)
1. olefin oligomerization catalyst can be from a) a kind of chromium cpd CrX of following acquisition
3, and based on this chromium cpd CrX
3Equimolar amount at least
Ligand L, perhaps a kind of already present chromium complex CrX
3L, wherein radicals X is independently of one another,
Be removable anti-electron ion, L is 1,3 of formula I, the 5-Trianacyclohexane,
Radicals R wherein
1To R
9Be independently of one another: hydrogen or the silicon with 1 to 30 carbon atom have
Carbon organic group machine or replacement or non-replacement, wherein two geminals or the adjacent base
The R of group
1To R
9Also can connect into five-unit or six-unit's ring, and b) at least a activating additive.
2. catalyst for oligomerization as claimed in claim 1, can obtain by adopting a kind of activating additive, this additive comprises a kind of unsubstituted or the N-of the 5-membered aromatic family heterocycle and at least a aluminum alkyls that replace, and the part alkyl of this aluminum alkyls can be by halogen and alkoxyl group replacement.
3. catalyst for oligomerization as claimed in claim 1 can obtain by adopting at least a activating additive.
4. catalyst for oligomerization as claimed in claim 1 can obtain as activating additive by adopting at least a boron compound and at least a aluminum alkyls, and the part alkyl of this aluminum alkyls can be replaced by halogen and alkoxyl group.
5. as any one described catalyst for oligomerization in the claim 1 to 4, wherein 1,3, the radicals R among the 5-Trianacyclohexane I
1, R
2And R
3Independently of one another, be C unsubstituted or that replace
1-C
12-alkyl, C
6-C
15-aryl or C
6-C
8-aralkyl.
6. catalyst for oligomerization as claimed in claim 5, wherein 1,3, the radicals R among the 5-Trianacyclohexane I
1, R
2And R
3Independently of one another, be that replace or unsubstituted C
1-C
12-alkyl or C
6-C
8-aralkyl.
7. as any one described catalyst for oligomerization in the claim 1 to 6, wherein 1,3, the radicals R among the 5-Trianacyclohexane I
4, R
5, R
6, R
7, R
8And R
9Independently of one another, be hydrogen or methyl.
8. preparation has the nearly technology of the oligopolymer of 30 carbon atoms, this technology by with alkene or alkene mixture in the presence of as any one described catalyst for oligomerization in the claim 1 to 7, in 0 to 150 ℃, react under 1 to 200 bar pressure.
9. an oligopolymer can obtain by technology as claimed in claim 8.
10. an oxo alcohol can obtain by oligopolymer as described in claim 9 being carried out known hydroformylation own.
11.[(1,3,5-three (2-n-propyl heptyl)-1,3,5-Trianacyclohexane) CrCl
3].
12.[(1,3,5-A
3-1,3, the 5-Trianacyclohexane) CrCl
3], wherein A is an alkyl, it 2 is replaced by alkyl in the position.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27782399A | 1999-03-29 | 1999-03-29 | |
| US09/277,823 | 1999-03-29 | ||
| DE19922048.4 | 1999-05-14 | ||
| DE19943544.8 | 1999-09-11 | ||
| DE19943544A DE19943544A1 (en) | 1999-09-11 | 1999-09-11 | New olefin oligomerization catalyst, useful for making oligomers for oxo-alcohol production, comprises chromium compound, triazacyclohexane ligand and activator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1348458A true CN1348458A (en) | 2002-05-08 |
| CN1227257C CN1227257C (en) | 2005-11-16 |
Family
ID=35396001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008067368A Expired - Fee Related CN1227257C (en) | 1999-03-29 | 2000-03-25 | Oligomerisation catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1227257C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340533C (en) * | 2002-03-14 | 2007-10-03 | 巴斯福股份公司 | Oligomerization of olefins comprising at least three carbon atoms |
| CN104941682A (en) * | 2014-03-25 | 2015-09-30 | Ifp新能源公司 | Novel catalytic composition and process for oligomerizing ethylene into 1-hexene |
| CN107580600A (en) * | 2015-09-02 | 2018-01-12 | Lg化学株式会社 | Ligand compound, the catalyst system for olefin oligomerization and the method for making olefin oligomerization using the catalyst system |
| CN111285903A (en) * | 2018-12-06 | 2020-06-16 | 中国石油天然气股份有限公司 | Chromium-based catalyst, preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101735687B1 (en) * | 2015-09-23 | 2017-05-15 | 롯데케미칼 주식회사 | Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
-
2000
- 2000-03-25 CN CNB008067368A patent/CN1227257C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340533C (en) * | 2002-03-14 | 2007-10-03 | 巴斯福股份公司 | Oligomerization of olefins comprising at least three carbon atoms |
| CN104941682A (en) * | 2014-03-25 | 2015-09-30 | Ifp新能源公司 | Novel catalytic composition and process for oligomerizing ethylene into 1-hexene |
| CN104941682B (en) * | 2014-03-25 | 2019-07-30 | Ifp 新能源公司 | Catalyst composition and for making ethylene oligomerization at the method for 1- hexene |
| CN107580600A (en) * | 2015-09-02 | 2018-01-12 | Lg化学株式会社 | Ligand compound, the catalyst system for olefin oligomerization and the method for making olefin oligomerization using the catalyst system |
| CN111285903A (en) * | 2018-12-06 | 2020-06-16 | 中国石油天然气股份有限公司 | Chromium-based catalyst, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1227257C (en) | 2005-11-16 |
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